CN100463898C - Preparation method of 3,3'-dimethyl-4,4'-diamino dibenzyl methane - Google Patents
Preparation method of 3,3'-dimethyl-4,4'-diamino dibenzyl methane Download PDFInfo
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- CN100463898C CN100463898C CNB2005100303912A CN200510030391A CN100463898C CN 100463898 C CN100463898 C CN 100463898C CN B2005100303912 A CNB2005100303912 A CN B2005100303912A CN 200510030391 A CN200510030391 A CN 200510030391A CN 100463898 C CN100463898 C CN 100463898C
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- diaminodiphenylmethane
- ortho toluidine
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Abstract
The present invention discloses a preparation method of 3,3-dimethyl-4,4-diaminodiphenyl methane. Said method includes the following steps: using o-toluidine as raw material, making it be reacted with hydrochloric acid to form salt, making it and condensation agent implement condensation reaction in the presence of catalyst, using alkaline solution to neutralize reaction product, and using mixed solution to make recrystallization so as to obtain the invented object product. Its purity can be up to above 99%, and its yield is 77-82%, and its melting point is 158-159 deg.C.
Description
Technical field
The present invention relates to a kind of 3,3 '-dimethyl-4, the preparation method of 4 '-diaminodiphenylmethane.
Background technology
3,3 '-dimethyl-4,4 '-diaminodiphenylmethane is a kind of important chemical material, especially can be used as the raw material of polyimide monomer or impregnating varnish.Its structural formula is:
Reported method such as Scanlan are to react with Ortho Toluidine, hydrochloric acid and formaldehyde solution, under alkaline condition, steam distillation goes out unreacted raw material Ortho Toluidine, the reactant that obtains obtains 3 through twice recrystallization, 3 '-dimethyl-4,4 '-diaminodiphenylmethane, yield 63% (J.Am.Chem.Soc., 1935, May:887-892).This method temperature of reaction height, by product is many, and aftertreatment is loaded down with trivial details, and yield is low, needs repeatedly recrystallization, the cost height, industrial prospect is little.
Barluenga etc. reported Ortho Toluidine in the presence of sodium methylate with the Paraformaldehyde 96 effect, obtain N-methoxyl methyl Ortho Toluidine, reflux with o-toluidine hydrochloride then and obtain 3,3 '-dimethyl-4, the method of 4 '-diaminodiphenylmethane (J.Chem.Soc.Perkin Trans I, 1988:1631-1636).This preparation method's expensive raw material price, the inconvenience of sodium methylate storage and transport, intermediate product N-methoxyl methyl Ortho Toluidine need be separated and react complex operation, cost height with another molecule o-toluidine hydrochloride.
Summary of the invention
The object of the present invention is to provide a kind of 3,3 '-dimethyl-4, the preparation method of 4 '-diaminodiphenylmethane, many to overcome in the prior art byproduct of reaction, yield is low; Expensive raw material price, cost height, the deficiency of complex operation.
Technical conceive of the present invention is such:
With the Ortho Toluidine is raw material, with the hydrochloric acid reaction salify, carries out condensation with condensing agent in the presence of catalyzer, alkaline solution neutralization, from reaction product, collect 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane crude product carries out recrystallization with mixing solutions, promptly obtains target product of the present invention.
Technical scheme of the present invention:
Ortho Toluidine and hydrochloric acid soln were reacted 15-30 minute down at 20-30 ℃, add catalyzer, keep this temperature, splash into condensing agent, reacted 2-5 hour, 80-100 ℃ was reacted 2-3 hour down, 20-30 ℃ of alkaline solution regulated pH value to 7.0, collects 3 from reaction product, 3 '-dimethyl-4,4 '-diaminodiphenylmethane crude product mixing solutions recrystallization obtains target product.
According to the present invention, said catalyzer is 4,4 '-Dimethylamino pyridine (DMAP), condensing agent is 37% formaldehyde solution or Paraformaldehyde 96, regulates pH value with the 20-40% NaOH or the KOH aqueous solution.
Said hydrochloric acid soln is by hydrochloric acid: the volume ratio of water=1: 2 is prepared, and the consumption of hydrochloric acid soln is an Ortho Toluidine: hydrochloric acid=1: 1-1.05, and mol ratio, wherein said hydrochloric acid is commercially available concentrated hydrochloric acid
Said catalyst consumption is an Ortho Toluidine: catalyzer=1: 0.005-0.01, mass ratio, the consumption of preferred catalyst are Ortho Toluidine: catalyzer=1: 0.006, mass ratio.
The consumption of said condensing agent is an Ortho Toluidine: condensing agent=2: 1-1.05, mol ratio.
According to the present invention, the mixing solutions of forming with ethanol and dimethyl formamide (with ethanol: dimethyl formamide=1-5: 1 volume ratio is prepared) carries out recrystallization, the consumption of mixed solvent is 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane: mixed solvent=1.0: 2.0-10.0, mass ratio.
Reaction formula of the present invention is as follows:
With preparation method of the present invention obtain 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane purity reaches more than 99%, productive rate is 77-82%, and fusing point is 158-159 ℃, with document (J.Am.Chem.Soc., 1935, May:887-892) the fusing point unanimity behind recrystallization repeatedly of report.
The present invention compared with prior art, it is cheap and easy to get to have a raw material, yield improves, cost is low, advantages of simple operation can obtain target product with high purity through a recrystallization, is suitable for suitability for industrialized production.
Embodiment
Below by embodiment the invention will be further described the present invention, but embodiment does not limit protection scope of the present invention.
Embodiment 1
In having the 500ml reactor of heating, stirring, thermometer, reflux condensing tube, add 200ml water, 100ml (1.0mol) concentrated hydrochloric acid, control reaction temperature splash into 106g (1.0mol) Ortho Toluidine at 20-30 ℃ under stirring, continue to stir 20 minutes, add 0.6g 4,4 '-Dimethylamino pyridine (DMAP), keep this temperature, slowly splash into the formaldehyde solution of 40g (0.5mol) 37%, dripped off afterreaction 2 hours, and slowly be warming up to 80-90 ℃, reacted 3 hours.Be cooled to 25 ℃, regulate PH=7, separate out white solid with 25% NaOH solution.Filter washing, drying, obtain 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane crude product 113g adds 800ml ethanol, dimethyl formamide mixing solutions (by ethanol: the volume ratio of dimethyl formamide=5: 1 is prepared) and carries out recrystallization, obtain 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane white crystal 87g, productive rate 77%, purity 99.3% (HPLC), fusing point 158-159 ℃
Embodiment 2
In having the 500ml reactor of heating, stirring, thermometer, reflux condensing tube, add 200ml water, 100ml (1.0mol) concentrated hydrochloric acid, temperature of reaction is controlled at 20-30 ℃, splashes into 106g (1.0mol) Ortho Toluidine under stirring, and continues to stir 20 minutes, add 0.8g 4,4 '-Dimethylamino pyridine (DMAP), keep this temperature and add 15g (0.5mol) Paraformaldehyde 96 in batches, reacted 2 hours, slowly be warming up to 80-90 ℃, reacted 3 hours.Be cooled to 20 ℃, regulate PH=7, separate out white solid with 25% KOH solution.Filter washing, drying, obtain 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane crude product 115g adds 400ml ethanol, dimethyl formamide mixing solutions (by ethanol: the volume ratio of dimethyl formamide=1: 1 is prepared) and carries out recrystallization, obtain 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane white crystal 91g, productive rate 80.5%, purity 99.2% (HPLC), fusing point 158-159 ℃.
Comparative example
In having the 500ml reactor of heating, stirring, thermometer, reflux condensing tube, add 200ml water, 100ml (1.0mol) concentrated hydrochloric acid, temperature of reaction is controlled at 20-30 ℃, splash into 106g (1.0mol) Ortho Toluidine under stirring, heat up, keep 40-50 ℃ of reaction 20 minutes, keep the formaldehyde solution that this temperature slowly splashes into 40g (0.5mol) 37%, dripped off afterreaction 2 hours, and slowly be warming up to 80-90 ℃, reacted 3 hours.Be cooled to room temperature, regulate PH=7 with 25% NaOH solution, the yellow solid of separating out filters, washing, and drying obtains 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane crude product 98g, purity 82% (HPLC).(press ethanol: the volume ratio preparation of dimethyl formamide=5: 1) recrystallization is 3 times to add each 900ml ethanol, dimethyl formamide mixing solutions, obtain 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane white crystal 58g, productive rate: 51.3%, purity 99.2% (HPLC), fusing point 158-159 ℃.
Claims (8)
1. one kind 3,3 '-dimethyl-4, the preparation method of 4 '-diaminodiphenylmethane is characterized in that comprising the steps:
Ortho Toluidine and hydrochloric acid soln were reacted 15-30 minute down at 20-30 ℃, add catalyzer 4,4 '-Dimethylamino pyridine, splash into the formaldehyde solution or the Paraformaldehyde 96 of condensing agent 37% under the equality of temperature, reacted 2-5 hour, 80-100 ℃ was reacted 2-3 hour down, and 20-30 ℃ of alkaline solution regulated pH value to 7.0, collects 3 from reaction product, 3 '-dimethyl-4,4 '-diaminodiphenylmethane crude product is used the mixing solutions recrystallization, obtains target product.
2. method according to claim 1 is characterized in that, said hydrochloric acid soln is by hydrochloric acid: the aqueous hydrochloric acid that the volume ratio of water=1: 2 is prepared.
3. method according to claim 1 is characterized in that, regulates pH value with the 20-40% NaOH or the KOH aqueous solution.
4. method according to claim 1 is characterized in that, the consumption of hydrochloric acid soln is an Ortho Toluidine: hydrochloric acid=1: 1-1.05, mol ratio.
5. method according to claim 1 is characterized in that, catalyst consumption is an Ortho Toluidine: catalyzer=1: 0.005-0.01, mass ratio.
6. method according to claim 5 is characterized in that, catalyst consumption is an Ortho Toluidine: catalyzer=1: 0.006, mass ratio.
7. method according to claim 1 is characterized in that, the consumption of condensing agent is an Ortho Toluidine: condensing agent=2: 1-1.05, mol ratio.
8. method according to claim 1, it is characterized in that, the mixing solutions of forming with ethanol and dimethyl formamide carries out recrystallization, mixed solvent is by ethanol: dimethyl formamide=1-5: 1 volume ratio is prepared, the consumption of mixed solvent is 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane crude product: mixed solvent=1.0: 2.0-10.0, mass ratio.
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| CN102249930B (en) * | 2011-05-17 | 2013-10-23 | 兰州交通大学 | Method for synthesizing 3,3',5,5'-dimethyl-4,4'-diaminodiphenylmethane |
| CN103130654B (en) * | 2013-01-21 | 2015-01-28 | 浙江大学宁波理工学院 | 3,'3-dimethyl-4,4'-diaminodiphenyl methane (MDT) preparation method |
| CN111995725B (en) * | 2020-09-07 | 2022-02-11 | 江苏湘园化工有限公司 | Environment-friendly liquid polyurethane curing agent and application method thereof |
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| JP2001233814A (en) * | 2000-02-28 | 2001-08-28 | Dainippon Ink & Chem Inc | New phenol compound, new polycarbonate resin and material for optical part |
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| JP2001233814A (en) * | 2000-02-28 | 2001-08-28 | Dainippon Ink & Chem Inc | New phenol compound, new polycarbonate resin and material for optical part |
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