CN101659617A - Preparation method of alky-substituted aromatic diamine - Google Patents
Preparation method of alky-substituted aromatic diamine Download PDFInfo
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- CN101659617A CN101659617A CN200910195472A CN200910195472A CN101659617A CN 101659617 A CN101659617 A CN 101659617A CN 200910195472 A CN200910195472 A CN 200910195472A CN 200910195472 A CN200910195472 A CN 200910195472A CN 101659617 A CN101659617 A CN 101659617A
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Abstract
The invention aims at providing an efficient preparation method of alky-substituted aromatic diamine, which is especially applicable to preparing the alky-substituted aromatic diamine with large volume such as 4,4-diamino 3,3-di-tert-butyl diphenylmethane. In the process, alkylaniline and formaldehyde are taken as raw materials, and the alky-substituted aromatic diamine is obtained by an intermittent one-step condensation reaction at the temperature of 100-150 DEG C for 1-20h under the action of a solid-acid catalyst. While the mol ratio of the alkylaniline and paraformaldehyde is 10/1-2/1. Inthe invention, the catalyst is SiO2, SiO2-Al2O3 and SiO2-TiO2 or ZrO2 with a mesoporous structure, is soaked in sulfuric acid or phosphoric acid solution for 4-24h, dried at the temperature of 110-150 DEG C for 12h and roasted in an air atmosphere at the temperature of 200-500 DEG C for 4-12h to obtain the solid acid catalyst with the mesoporous structure through acid processing; and the catalystcan be recycled, and has high activity for the alky-substituted aromatic diamine synthesized by the alkylaniline and the formaldehyde, particularly for the 4,4-diamino 3,3-di-tert-butyl diphenylmethane.
Description
Technical field
The present invention relates to a kind of preparation method of alkyl substituent aromatic diamines of environmental protection, particularly relate to a kind of 4,4-diamino 3, the preparation method of 3-di-tert-butyl diphenylmethane.
Background technology
The alkyl substituent aromatic diamines is the important raw and processed materials of preparation fire resistant polyimide resin, high temperature resistant multifunctional glycidyl amine type epoxy resin, liquid crystal aligning arrangement agent, low water absorbable carbon fiber enhancing advanced composite material matrix resin, high impact-resistant epoxy curing agent, polyurethane chain extender, electronic devices and components packaged material, insulating material, super large-scale integration passivating coating and printing electronic circuit base material matrix resin or tackiness agent.
In the benzene ring structure of aromatic diamine, introduce the alkyl substituent of large volume, help improving moisture resistance and optical transparence, reduction specific inductivity and the dielectric loss etc. of its phase emergencing copolymer; As epoxy curing agent the time, can improve the stability in storage of whole system; When arranging agent, help improving the tilt angle of liquid crystal aligning as polyimide liquid crystal direct action.
Tertiary butyl 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 tert-butyl substituents aromatic diamine in the molecular structure and will have comprehensive performance.
At present, the main synthesis technique of alkyl substituent aromatic diamines is in the presence of strong acid especially hydrochloric acid, is undertaken by the condensation of alkyl substituted benzene amine and formaldehyde.This process choice is on the low side, and the complex process of further separating and purifying need underpressure distillation under the high temperature high vacuum, the equipment complexity.In reaction process, the existence of strong acid can bring serious etching problem, and in addition, the adding of strong acid makes and must neutralize with alkaline solution that the disposal of resulting neutral salt solution also is serious problems when reaction finishes.
Other technology is as U.S. Patent No. 3,362,797,4,039,580 and 4,039,581, adopt solid acid catalyst, for example clay, zeolite, diatomite etc. are as catalyzer, can eliminate the use of strong acid catalyst and the disadvantageous effect in the follow-up N-process, but the shortcoming of these technologies is complicated process of preparation, aniline and formaldehyde need be carried out the dehydration earlier of precondensation, product, then could be in the rearrangement of carrying out the precondensation product under the solid acid catalyst effect.CN 101007767A discloses a kind of under the molecular sieve catalyst effect, and aniline and formaldehyde one step condensation reaction obtain 4, the method for 4-diaminodiphenylmethane.But, in these technologies, because the restriction of catalyzer can not be synthesized and be had the bigger substituted alkyl aromatic diamine of volume.
Summary of the invention
The purpose of this invention is to provide that a kind of reaction process is simple, the preparation method of the alkyl substituent aromatic diamines of environmental protection, the present invention is specially adapted to have the bigger substituted alkyl aromatic diamine of volume, as 4,4-diamino 3, the 3-di-tert-butyl diphenylmethane, can remedy the deficiencies in the prior art and defective, meet the demands of production and living.
The preparation method of alkyl substituent aromatic diamines of the present invention is to be raw material with alkyl benzene amine and formaldehyde, adopts acid-treated solid acid catalyst with meso-hole structure, and a step condensation reaction obtains, and preparation process is:
1. the SiO that will have meso-hole structure
2, SiO
2-Al
2O
3, SiO
2-TiO
2Or ZrO
2, in sulfuric acid or phosphoric acid solution, soaked 4～24 hours, in 110～150 ℃ of dryings 12 hours, under air atmosphere,, make finished catalyst in 200～500 ℃ of roasting 4～12h;
2. alkyl benzene amine, formaldehyde and organic solvent being joined one has in the reactor of reflux condensation mode, the consumption mole ratio of alkyl benzene amine and formaldehyde is 10/1～2/1, add catalyzer, the amount ratio of catalyzer and formaldehyde is 1/50～1/2, protect with the high pure nitrogen bubbling, stir, under 100～150 ℃ temperature, reacted 1～20 hour;
3. with reaction product and catalyzer centrifugation, catalyst recovery can be reused;
4. reaction solution carries out rectification under vacuum, and organic solvent and unreacted alkyl benzene amine can reclaim the back and reuse;
5. with the solid product after the dissolve with ethanol rectifying, recrystallization obtains product alkyl substituent aromatic diamines.
Formaldehyde of the present invention is selected Paraformaldehyde 96, trioxymethylene.
The preferred molar number amount ratio of o-tert-butyl aniline of the present invention and formaldehyde is 4/1～2/1.
Catalyzer of the present invention is 10/1～4/1 with the preferable amount ratio of formaldehyde.
Organic solvent of the present invention selects boiling point at the ester class more than 90 ℃, ethers, alcohols, sulfone class, amides organic solvent, preferred oxalic acid diethyl ester, butylacetate, pentyl acetate, dioxane, n-hexyl alcohol, methyl-sulphoxide, DMF.
SiO with meso-hole structure of the present invention
2, SiO
2-Al
2O
3, SiO
2-TiO
2Or ZrO
2, be adopt the preparation of open source literature method have structures such as MCM, SBA, MSU, duct a SiO at 2～50nm
2, SiO
2-Al
2O
3, SiO
2-TiO
2Or ZrO
2Material.
Condensation reaction preferable reaction temperature of the present invention is 110～140 ℃, 2～4 hours reaction times.
The preparation method of the alkyl substituent aromatic diamines that the present invention relates to, particularly 4,4-diamino-3, the catalysis of 3-di-tert-butyl diphenylmethane is synthetic, catalyzer directly synthesizes 4 for o-tert-butyl aniline and formaldehyde, 4-diamino-3,3-di-tert-butyl diphenylmethane have very high reactive behavior, target product selectivity and repeated use activity.This technology is a kind of environmental protection efficiently 4,4-diamino-3,3-di-tert-butyl diphenylmethane catalysis synthesizing technology.
Embodiment
Embodiment 1: reference literature method (Science (1998,279:548-552)), preparation Si-SBA-15 mesoporous material.
10g Si-SBA-15 is placed the phosphoric acid solution of 20mL 5%, leave standstill 24h under 60 ℃,, under air atmosphere,, obtain acid mesoporous Si-SBA-15 catalyzer in 400 ℃ of roasting 6h then in 120 ℃ of dry 12h.
Have in the there-necked flask of reflux exchanger at 100mL, add 29.8g (0.2mol) o-tert-butyl aniline, 1.50g (0.05mol) Paraformaldehyde 96, the acid mesoporous Si-SBA-15 catalyzer of 0.5g, add 30ml DMF, heated and stirred, temperature is controlled at 130 ℃, reaction times 4h.
With reaction product and catalyzer centrifugation, catalyst recovery can be reused.Reaction solution carries out rectification under vacuum, and solvent and unreacted o-tert-butyl aniline can reclaim the back and reuse.With the solid product after the dissolve with ethanol rectifying, recrystallization once obtains white solid product 10.1g.Identify that products obtained therefrom is 4,4-diamino-3,3-di-tert-butyl diphenylmethane through nucleus magnetic resonance, infrared, mass spectrum.
Embodiment 2: according to the same method for preparing catalyst of embodiment 1, prepare acid mesoporous SiO
2-Al
2O
3, SiO
2-TiO
2And ZrO
2Catalyzer.
Same reaction conditions, raw material according to embodiment 1 are formed and separating and purifying method, adopt acid SiO successively
2-Al
2O
3, SiO
2-TiO
2And ZrO
2Catalyzer reacts, and obtains 4,4-diamino-3, and the result of 3-di-tert-butyl diphenylmethane is as shown in table 1:
Table 1, different catalysts effect synthesize 4 down, 4-diamino-3, the reaction result of 3-di-tert-butyl diphenylmethane
Embodiment 3: same reaction conditions, raw material according to embodiment 1 are formed and separating and purifying method, adopting acid mesoporous Si-SBA-15 is catalyzer, adopt oxalic acid diethyl ester, butylacetate, pentyl acetate, dioxane to react successively, obtain 4,4-diamino-3, the result of 3-di-tert-butyl diphenylmethane is as shown in table 2:
Synthesize 4 in table 2, the different solvents, 4-diamino-3, the reaction result of 3-di-tert-butyl diphenylmethane
Embodiment 4: same reaction conditions, raw material according to embodiment 1 are formed and separating and purifying method, employing DMF is a solvent, acid mesoporous Si-SBA-15 is a catalyzer, has investigated 0.1g successively, 0.3g, 0.5g, 0.7g, react under the catalyst action of 0.9g metering and synthesize 4,4-diamino-3, the 3-di-tert-butyl diphenylmethane, the result is as shown in table 3:
Table 3, the acid mesoporous Si-SBA-15 catalyst action of different mass synthesize 4 down, 4-diamino-3, the reaction result of 3-di-tert-butyl diphenylmethane
Embodiment 5: the same raw material according to embodiment 1 is formed and separating and purifying method, and employing DMF is a solvent, and the acid mesoporous Si-SBA-15 of 0.5g is a catalyzer, investigated under the differential responses time 4 successively, 4-diamino-3, the yield of 3-di-tert-butyl diphenylmethane, the result is as shown in table 4:
Table 4, differential responses time synthesize 4,4-diamino-3, the reaction result of 3-di-tert-butyl diphenylmethane
Embodiment 6: according to same reaction conditions and the separating and purifying method of embodiment 1, employing DMF is a solvent, 0.5g acid mesoporous Si-SBA-15 is a catalyzer, investigated 2-isopropyl aniline, 2-ethylaniline, 2-aminotoluene successively and be the result that raw material reacts synthetic corresponding alkyl substituent aromatic diamines, as shown in table 5:
The reaction result of table 5, the down synthetic different alkyl substituent aromatic diamines of mesoporous Si-SBA-15 catalyst action
Embodiment 7: same reaction conditions, raw material according to embodiment 1 are formed and separating and purifying method, employing DMF is a solvent, 0.5g acid mesoporous Si-SBA-15 is a catalyzer, reaction times is 4h, investigate when reusing catalyzer 5 times 4,4-diamino-3, the yield of 3-di-tert-butyl diphenylmethane, the result is as shown in table 5:
Table 6, catalyst recirculation are used synthesizing 4,4-diamino-3, the influence of 3-di-tert-butyl diphenylmethane
Claims (7)
1. the preparation method of an alkyl substituent aromatic diamines is characterized in that, comprises the steps:
(1) alkyl benzene amine, formaldehyde and organic solvent being joined one has in the reactor of reflux condensation mode, the consumption mole ratio of alkyl benzene amine and formaldehyde is 10/1～2/1, add catalyzer, the amount ratio of catalyzer and formaldehyde is 1/50～1/2, protect with the high pure nitrogen bubbling, stir, under 100～150 ℃ temperature, reacted 1～20 hour;
(2) with reaction product and catalyzer centrifugation, catalyst recovery can be reused;
(3) reaction solution carries out rectification under vacuum, and organic solvent and unreacted alkyl benzene amine can reclaim the back and reuse;
(4) with the solid product after the dissolve with ethanol rectifying, recrystallization obtains product alkyl substituent aromatic diamines.
2. according to the described method of claim 1, it is characterized in that said catalyzer is to have the SiO of meso-hole structure
2, SiO
2-Al
2O
3, SiO
2-TiO
2Or ZrO
2, in sulfuric acid or phosphoric acid solution, soaked 4～24 hours, in 110～150 ℃ of dryings 12 hours, under air atmosphere in 200～500 ℃ of roasting 4～12h, the acid-treated solid acid catalyst that makes with meso-hole structure.
3. according to the described method of claim 1, it is characterized in that described formaldehyde is Paraformaldehyde 96, trioxymethylene.
4. according to the described method of claim 1, it is characterized in that the amount ratio of described catalyzer and formaldehyde is 50/1～2/1, the preferable amount ratio is 10/1～4/1.
5. according to the described method of claim 1, it is characterized in that the mole number amount ratio of described alkyl benzene amine and formaldehyde is 10/1～2/1, the preferred molar number amount ratio is 4/1～2/1.
6. according to the described method of claim 1, it is characterized in that, described organic solvent be boiling point at the ester class more than 90 ℃, ethers, alcohols, sulfone class, amides organic solvent, preferred oxalic acid diethyl ester, butylacetate, pentyl acetate, dioxane, n-hexyl alcohol, methyl-sulphoxide, DMF.
7. according to the described method of claim 1, it is characterized in that described condensation reaction preferable reaction temperature is 110～140 ℃, 2～4 hours reaction times.
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| CN200910195472A CN101659617A (en) | 2009-09-10 | 2009-09-10 | Preparation method of alky-substituted aromatic diamine |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483206A (en) * | 2013-09-27 | 2014-01-01 | 桂林理工大学 | Diamine monomer containing asymmetric and non-coplanar structure, and preparation method of diamine monomer |
| CN104892430A (en) * | 2015-06-04 | 2015-09-09 | 沈阳化工研究院有限公司 | Method for clean preparation of alkyl substituted diamine fluorene compound |
| CN111498862A (en) * | 2020-04-03 | 2020-08-07 | 三峡大学 | Preparation method and application of spherical SBA-15 mesoporous molecular sieve |
| CN115121263A (en) * | 2022-06-30 | 2022-09-30 | 华东理工大学 | Solid acid catalyst and preparation method and application thereof |
-
2009
- 2009-09-10 CN CN200910195472A patent/CN101659617A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483206A (en) * | 2013-09-27 | 2014-01-01 | 桂林理工大学 | Diamine monomer containing asymmetric and non-coplanar structure, and preparation method of diamine monomer |
| CN104892430A (en) * | 2015-06-04 | 2015-09-09 | 沈阳化工研究院有限公司 | Method for clean preparation of alkyl substituted diamine fluorene compound |
| CN111498862A (en) * | 2020-04-03 | 2020-08-07 | 三峡大学 | Preparation method and application of spherical SBA-15 mesoporous molecular sieve |
| CN115121263A (en) * | 2022-06-30 | 2022-09-30 | 华东理工大学 | Solid acid catalyst and preparation method and application thereof |
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Application publication date: 20100303 |