CN105218381A - A kind of 4,4-diamino 3,3-di-tert-butyl diphenylmethane synthetic method - Google Patents
A kind of 4,4-diamino 3,3-di-tert-butyl diphenylmethane synthetic method Download PDFInfo
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- CN105218381A CN105218381A CN201510723419.4A CN201510723419A CN105218381A CN 105218381 A CN105218381 A CN 105218381A CN 201510723419 A CN201510723419 A CN 201510723419A CN 105218381 A CN105218381 A CN 105218381A
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Abstract
The object of this invention is to provide a kind of 4,4-diamino 3,3-di-tert-butyl diphenylmethane synthesis technique.Described technique for raw material, under the effect of solid acid catalyst, obtains 4,4-diamino 3,3-di-tert-butyl diphenylmethane with the condensation reaction of formaldehyde one step with o-tert-butyl aniline.Temperature of reaction is 90 ~ 150 DEG C, and the reaction times is 1 ~ 8 hour.O-tert-butyl aniline of the present invention obtains through methyl tertiary butyl ether or trimethyl carbinol alkylated reaction by aniline, greatly reduces the cost of raw material, is that 4,4-diamino 3,3-di-tert-butyl diphenylmethane industrial applications provides huge possibility; Catalyzer of the present invention is commercially available polynite or the kaolin with laminate structure; Catalyzer of the present invention can recycle, and has very high activity for o-tert-butyl aniline and formaldehyde synthesis 4,4-diamino 3,3-di-tert-butyl diphenylmethane.This technique is the synthesis technique of a kind of environmental protection, efficient 4,4-diamino 3,3-di-tert-butyl diphenylmethanes.
Description
Technical field
The present invention relates to a kind of synthesis technique of 4,4-diamino 3,3-di-tert-butyl diphenylmethane.
Background technology
4,4-diamino 3,3-di-tert-butyl diphenylmethane is a kind of broad-spectrum chemical, can be used as epoxy resin tough curing agent, polyurethane chain agent, liquid crystal aligning arrangement agent.The insulating material such as the polyester-imide prepared with it and polyimide insulative paint, bimaleimide resin show good insulation, mechanics, high temperature resistant, a series of performance such as radiation hardness and abrasion performance.Particularly relate in synthesis highly soluble polyimide resin field, owing to introducing flexible alkyl group side chain, add the free volume of polyimide molecule chain, produce space steric effect and effectively prevent the accumulation between polyimide molecule chain and close, reduce intermolecular interaction, thus greatly improve the solvability of polyimide, reduce second-order transition temperature, improve processing characteristics.
At present, the main synthesis technique of 4,4-diamino 3,3-di-tert-butyl diphenylmethane be with o-tert-butyl aniline and formaldehyde for raw material, be catalyzer with liquid acid, produced by homogeneous catalytic reaction.Patent CN1323783A describes under strong acid salt acid catalysis, and o-tert-butyl aniline and formaldehyde solution generate 4,4-diamino 3,3-di-tert-butyl diphenylmethane, and chemical equation is as follows:
Costly, the complex process of further isolation andpurification, need underpressure distillation under high temperature high vacuum, energy consumption is large for this operational path raw materials cost.Meanwhile, there are the serious problems such as strong acid etching apparatus and environmental pollution in this reaction system.
In order to solve the problem of above two aspects, the present invention adopts solid acid catalyst to replace liquid acid catalyst, solves defect impassable in ready-made technology.
Summary of the invention
The object of this invention is to provide that a kind of reaction process is simple, raw materials cost is lower, the synthesis technique of industrial feasible, efficient 4,4-diamino 3,3-di-tert-butyl diphenylmethanes of environmental protection.
Of the present invention 4,4-diamino 3, the catalysis synthesizing technology of 3-di-tert-butyl diphenylmethane is for raw material with o-tert-butyl aniline and formaldehyde, adopt the solid acid with laminate structure as catalyzer, one step catalyzing and condensing reaction, its step is as follows: o-tert-butyl aniline, formaldehyde, organic solvent and solid acid catalyst are joined one with in the reactor of reflux condensation mode, the consumption mol ratio of o-tert-butyl aniline and formaldehyde is 2/1 ~ 10/1, protect with nitrogen bubble, stir, at 90 ~ 150 DEG C of temperature, react 1 ~ 8 hour; After reaction terminates, reactant and catalyzer are carried out centrifugation, and catalyzer is recyclable to be re-used; Reaction solution carries out rectification under vacuum, and organic solvent and the complete o-tert-butyl aniline of unreacted can reclaim and re-use; With the solid product after dissolve with ethanol rectifying, recrystallization obtains high purity product 4,4-diamino 3,3-di-tert-butyl diphenylmethane.
Described o-tert-butyl aniline can be commercially available o-tert-butyl aniline, also can be the o-tert-butyl aniline obtained by the alkylated reaction of aniline.
Described formaldehyde can be paraformaldehyde, trioxymethylene and formaldehyde solution.
The preferred butylacetate of described organic solvent, pentyl acetate, dioxane.
Described catalyzer is solid acid, preferably with polynite and the kaolin of laminate structure.
The present invention relates to low, industrial feasible, the environmental protection efficient 4 of a kind of raw materials cost, 4-diamino 3, the catalysis synthesizing technology of 3-di-tert-butyl diphenylmethane, selected laminate structure solid acid catalyst for the condensation reaction of o-tert-butyl aniline and formaldehyde have very high reactive behavior, target product selective activization and reuse active etc.
Embodiment
Embodiment one
Take 11.18g (0.12mol) aniline, 0.48mol methyl tertiary butyl ether, the commercially available polynite of 3.83g join in 100ml reactor, logical nitrogen to replace in still air 5 times continuously, reacting by heating liquid is to after 165 DEG C, open mechanical stirring, rotating speed is 900rpm, start reaction, control temperature of reaction maintain desired reaction temperature ± 1 DEG C within the scope of.After reaction 4h terminates, close and stir, and cooled by reaction material liquid, centrifugation goes out catalyzer.By distillation and chromatographic separation, obtaining purity is 98% o-tert-butyl aniline.
In the there-necked flask of 250ml with reflux condensate device, add above-mentioned made 44.7g (0.3mol) o-tert-butyl aniline, 2.25g (0.075mol) paraformaldehyde, 9g polynite, add 50ml butylacetate, heated and stirred, temperature controls at 130 DEG C, reaction times 4h.
By reactant, product, catalyzer centrifugation, catalyzer can reclaim and reuse.Reaction solution carries out rectification under vacuum, reuses after solvent and the complete o-tert-butyl aniline of unreacted can reclaim.With the solid product after dissolve with ethanol rectifying, carry out recrystallization at 4 DEG C, obtain white crystals product 8.8g.Through nuclear-magnetism, mass spectrum, infrared analysis, qualification products obtained therefrom is 4,4-diamino 3,3-di-tert-butyl diphenylmethane.
Embodiment two
Take 11.18g (0.12mol) aniline, the 0.48mol trimethyl carbinol, the commercially available AlCl of 5g
3join in 100ml reactor, logical nitrogen, continuously air 5 times in displacement still, reacting by heating liquid is to after 165 DEG C, and open mechanical stirring, rotating speed is 900rpm, starts reaction, control temperature of reaction maintain desired reaction temperature ± 1 DEG C within the scope of.After reaction 4h terminates, close and stir, and cooled by reaction material liquid, centrifugation goes out catalyzer.By distillation and chromatographic separation, obtaining purity is 98% o-tert-butyl aniline.
In the there-necked flask of 250ml with reflux condensate device, add the polynite that above-mentioned homemade 44.7g (0.3mol) o-tert-butyl aniline, 9g are commercially available, add 50ml butylacetate, heated and stirred, temperature controls at 130 DEG C.Adopt ram pump to drip the formalin of 37 ~ 40% commercially available (massfractions) continuously, rate of addition is 0.050mL/min, reaction times 4h.
By reactant, product and catalyzer centrifugation, catalyzer can reclaim and reuse, and reaction solution carries out rectification under vacuum, reuses after solvent and the complete o-tert-butyl aniline of unreacted can reclaim.With the solid product after dissolve with ethanol rectifying, carry out recrystallization at 4 DEG C, obtain white crystals product 18.5g.Through nuclear-magnetism, mass spectrum, infrared analysis, qualification products obtained therefrom is 4,4-diamino 3,3-di-tert-butyl diphenylmethane.
Embodiment three
Take the AlCl that 11.18g (0.12mol) aniline, the 0.48mol trimethyl carbinol, 3.83g are commercially available
3join in 100ml reactor, logical nitrogen, continuously air 5 times in displacement still, reacting by heating liquid is to after 155 DEG C, and open mechanical stirring, rotating speed is 900rpm, starts reaction, control temperature of reaction maintain desired reaction temperature ± 1 DEG C within the scope of.After reaction 4h terminates, close and stir, and cooled by reaction material liquid, centrifugation goes out catalyzer.By distillation and chromatographic separation, obtaining purity is 98% o-tert-butyl aniline.
In the there-necked flask of 250ml with reflux condensate device, add the polynite that the above-mentioned obtained o-tert-butyl aniline of 44.7g (0.3mol), 9g are commercially available, add 50ml butylacetate, heated and stirred, temperature controls at 130 DEG C, adopt ram pump to drip the formalin of 37 ~ 40% commercially available (massfractions) continuously, rate of addition is 0.040mL/min, reaction times 4h.
By reactant, product, catalyzer centrifugation, catalyzer can reclaim and reuse, and reaction solution carries out rectification under vacuum, reuses after solvent and the complete o-tert-butyl aniline of unreacted can reclaim.With the solid product after dissolve with ethanol rectifying, carry out recrystallization at 4 DEG C, obtain white crystals product 19.8g.Through nuclear-magnetism, mass spectrum, infrared analysis, qualification products obtained therefrom is 4,4-diamino 3,3-di-tert-butyl diphenylmethane.
Embodiment four
Take the AlCl that 11.18g (0.12mol) aniline, the 0.48mol trimethyl carbinol, 3.83g are commercially available
3join in 100ml reactor, logical nitrogen to replace in still air 5 times continuously, and reacting by heating liquid is to after 145 DEG C, and open mechanical stirring, rotating speed is 900rpm, starts reaction, control temperature of reaction maintain desired reaction temperature ± 1 DEG C within the scope of.After reaction 4h terminates, close and stir, and cooled by reaction material liquid, centrifugation goes out catalyzer.By distillation and chromatographic separation, obtaining purity is 98% o-tert-butyl aniline.
In the there-necked flask of 250ml with reflux condensate device, add the kaolin that 44.7g (0.3mol) o-tert-butyl aniline, 2.25g (0.075mol) paraformaldehyde, 9g are commercially available, add 50ml butylacetate, heated and stirred, temperature controls at 130 DEG C, reaction times 4h.
By reactant and catalyzer centrifugation, catalyzer can reclaim and reuse, and reaction solution carries out rectification under vacuum, reuses after solvent and the complete o-tert-butyl aniline of unreacted can reclaim.With the solid product after dissolve with ethanol rectifying, carry out recrystallization at 4 DEG C, obtain white crystals product 7.8g.Through nuclear-magnetism, mass spectrum, infrared analysis, qualification products obtained therefrom is 4,4-diamino 3,3-di-tert-butyl diphenylmethane.
Embodiment five
In the there-necked flask of 250ml with reflux condensate device, add the kaolin that the commercially available o-tert-butyl aniline of 44.7g (0.3mol), 9g are commercially available, add 50ml butylacetate, heated and stirred, temperature of reaction controls at 130 DEG C, adopt ram pump to drip the formalin of 37 ~ 40% commercially available (massfractions) continuously, rate of addition is 0.040mL/min, reaction times 4h.
By reactant, product and catalyzer centrifugation, catalyzer can reclaim and reuse, and reaction solution carries out rectification under vacuum, reuses after solvent and the complete o-tert-butyl aniline of unreacted can reclaim.With the solid product after dissolve with ethanol rectifying, carry out recrystallization at 4 DEG C, obtain white crystals product 21.6g.Through nuclear-magnetism, mass spectrum, infrared analysis, qualification products obtained therefrom is 4,4-diamino 3,3-di-tert-butyl diphenylmethane.
Claims (7)
1. the preparation method of a diamino 3,3-di-tert-butyl diphenylmethane, is characterized in that, comprises the steps:
(1) under solid acid effect, adopt methyl tertiary butyl ether or the trimethyl carbinol to carry out alkylated reaction at the ortho position of aniline and obtain o-tert-butyl aniline;
(2) o-tert-butyl aniline, formaldehyde, organic solvent and solid acid catalyst are added in the reactor of reflux condensation mode, the consumption mol ratio of o-tert-butyl aniline and formaldehyde is 2/1 ~ 10/1, and o-tert-butyl aniline is protected with nitrogen bubble, stirs, at 90 ~ 150 DEG C of temperature, react 1 ~ 8 hour;
(3), after reaction terminates, catalyzer is reused after reclaiming by centrifugation; In reaction solution, organic solvent and the complete o-tert-butyl aniline of unreacted re-use after can reclaiming;
(4) products therefrom obtains high purity product 4,4-diamino 3,3-di-tert-butyl diphenylmethane through dissolve with ethanol, recrystallization.
2. processing method according to claim 1, it is characterized in that, described aniline alkylating catalyzer is acid solid, can be commercially available AlCl
3, ZnCl
2, heteropolyacid, mineral acid treatment polynite, kaolin, mesopore molecular sieve etc.
3. processing method according to claim 1, it is characterized in that, described aniline alkylating temperature of reaction is 120 ~ 170 DEG C; The ratio of aniline and alkylating reagent methyl tertiary butyl ether or the trimethyl carbinol is 1/2 ~ 1/6.
4. processing method according to claim 1, it is characterized in that, described raw material is o-tert-butyl aniline, can commercially availablely also can be that aniline obtains through methyl tertiary butyl ether alkylated reaction.
5. processing method according to claim 1, it is characterized in that, described formaldehyde can be paraformaldehyde, trioxymethylene and formaldehyde solution.
6. processing method according to claim 1, it is characterized in that, described catalyzer is solid acid, preferably with polynite and the kaolin of laminate structure.
7. processing method according to claim 1, is characterized in that, the preferred butylacetate of described organic solvent, pentyl acetate, dioxane.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108355706A (en) * | 2018-03-13 | 2018-08-03 | 江苏清泉化学股份有限公司 | Multistage porous molecular sieve, preparation method and its application in synthesizing diamino diphenylmethane derivatives |
| CN112023979A (en) * | 2019-06-03 | 2020-12-04 | 中石化南京化工研究院有限公司 | Catalyst for synthesizing 2-tert-butyl aniline and preparation method and application thereof |
-
2015
- 2015-10-29 CN CN201510723419.4A patent/CN105218381A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108355706A (en) * | 2018-03-13 | 2018-08-03 | 江苏清泉化学股份有限公司 | Multistage porous molecular sieve, preparation method and its application in synthesizing diamino diphenylmethane derivatives |
| CN112023979A (en) * | 2019-06-03 | 2020-12-04 | 中石化南京化工研究院有限公司 | Catalyst for synthesizing 2-tert-butyl aniline and preparation method and application thereof |
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Application publication date: 20160106 |