CN100457714C - Preparing and separating purifying method for 3,4'-diamino diphenyl ether - Google Patents

Preparing and separating purifying method for 3,4'-diamino diphenyl ether Download PDF

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CN100457714C
CN100457714C CNB2006100508137A CN200610050813A CN100457714C CN 100457714 C CN100457714 C CN 100457714C CN B2006100508137 A CNB2006100508137 A CN B2006100508137A CN 200610050813 A CN200610050813 A CN 200610050813A CN 100457714 C CN100457714 C CN 100457714C
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reaction solvent
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raw material
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diphenyl ether
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伍川
邱化玉
蒋可志
吴连斌
李文清
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Hangzhou Normal University
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Hangzhou Normal College
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Abstract

The present invention relates to 3, 4'-diamino diphenyl ether preparing, separating and purifying process. The present invention features that the material 3-amino-4'-nitro diphenyl ether or 3, 4'-dinitro diphenyl ether produces nitro radical reduction reaction in reaction solvent with hydrazine hydrate as reductant under protection of nitrogen and in the presence of supported catalyst; and that after reaction, the hot catalyst is filtered out and washed with reaction solvent, and the washed liquid, and the filtrate are merged, heated at normal pressure to evaporate, concentrate and separate out 3, 4'-diamino diphenyl ether crystal. Through further filtering and vacuum drying, high purity 3, 4'-diamino diphenyl ether crystal is obtained.

Description

A kind of 3,4 '-preparation and the separating and purifying method of diaminodiphenyl oxide
Technical field
The present invention relates to organic chemistry filed, specifically be a kind of prepare aramid fiber and polyimide monomer 3,4 commonly used '-preparation and the separating and purifying method of diaminodiphenyl oxide.
Background technology
3,4 '-diaminodiphenyl oxide is a kind of important chemical material, can be used to the engineering plastics-aramid fiber and the polyimide of synthesized high-performance, also can be used for preparing high-temperature insulation material, coating, synthetic drugs and agricultural chemicals.Its chemical structural formula is:
Figure C20061005081300041
That Chinese patent CN1485315A discloses is a kind of 3,4 '-preparation method of diaminodiphenyl oxide, it is a raw material with the itrodiphenyl ethers, is solvent with the alcohols, hydrazine hydrate is a reductive agent, at gac and catalyst Fe Cl 3.6H 2O exists down and carries out the normal pressure reduction reaction, and after the reaction product filtration, filter cake washs with alcohols, thereafter filtrate is mixed with washings, adds entry in the mixing liquid that obtains, separate out 3,4 '-the diaminodiphenyl oxide crystal.
Chinese patent CN1583713A has disclosed and has utilized sodium hydroxide to be condensing agent, with Metha Amino Phenon or m-nitrophenol is raw material, reaction generates the phenol sodium salt in toluene solvant, phenol sodium salt and p-Nitrophenyl chloride wait the reaction of mole ratio of components in solvent dimethylformamide, at 110～130 ℃, reacted 3～4 hours, make 3-amino-4 '-itrodiphenyl ethers or 3,4 '-dinitro diphenyl ether; 3-amino-4 '-itrodiphenyl ethers adds hydrogen reduction, 3,4 '-dinitro diphenyl ether adds iron powder reducing and obtains 3,4 '-the thick product of diaminodiphenyl oxide, then under high vacuum through underpressure distillation obtain 3,4 '-diaminodiphenyl oxide.
That Japanese Patent JP61221159 discloses is a kind of 3,4 '-preparation method of diaminodiphenyl oxide, its with thick 3,4 '-diaminodiphenyl oxide joins in 240～350 ℃ the high boiling solvent, through molecular distillation obtain 3,4 '-diaminodiphenyl oxide.
Above-mentioned various preparation 3,4 '-method of diaminodiphenyl oxide in, 3,4 '-sepn process of diaminodiphenyl oxide is by adding entry or being achieved by molecular distillation in the mixed system after reaction is finished.Water is added in the mixed system that reacts after finishing, utilize water as extraction agent, can be with 3,4 '-diaminodiphenyl oxide separates from alcoholic solvent, but after in alcoholic solvent, adding entry, not the itrodiphenyl ethers of complete reaction also with 3,4 '-diaminodiphenyl oxide together separates out, influence 3,4 '-purity of diaminodiphenyl oxide; Moreover in the crystal precipitation process, crystal habit is uncontrollable, causes the parcel of crystal reunion and impurity (as activated carbon, iron ion etc.) easily; Secondly, alcoholic solvent concentration reduces after adding water, can not directly use as reaction solvent, after must removing most water through rectificating method, alcoholic solvent could reclaim use, the dehydration of alcoholic solvent is one and expends time in a large number and the process of energy, some alcohols (as methyl alcohol) even form azeotrope with water, can't purify with rectificating method, also must adopt more complicated azeotropic distillation technology, therefore, add elutriation in the mixed system after reduction reaction is finished and go out 3,4 '-diaminodiphenyl oxide, this method exists crystal habit poor, product purity is not high, alcoholic solvent reclaims difficulty and increases the deficiency of production cost, has limited its industrial applications; And utilize molecular distillation separation and purification 3,4 '-method of diaminodiphenyl oxide, have the shortcoming that facility investment is big, energy waste is big, high temperature is amino easily oxidized down.
Summary of the invention
The object of the present invention is to provide a kind of 3,4 '-preparation and the separating and purifying method of diaminodiphenyl oxide, with solve available technology adopting add water extraction 3,4 '-crystal habit that exists in the diaminodiphenyl oxide method is poor, product purity is not high, alcoholic solvent reclaims difficulty and increase the problem of production cost and molecular distillation in the problem that facility investment is big, energy waste is big, high temperature is amino easily oxidized down that exists.
Of the present invention 3,4 '-preparation and the separating and purifying method of diaminodiphenyl oxide, it is characterized in that: with 3-amino-4 '-itrodiphenyl ethers or 3,4 '-dinitro diphenyl ether is a raw material, is reductive agent with the hydrazine hydrate, under nitrogen protection, in reaction solvent, carry out nitro-reduction reaction in the presence of supported catalyst, after reaction was finished, filtered while hot reclaimed catalyzer, use the reaction solvent washing catalyst, after washing lotion and filtrate merged, often voltage rise temperature evaporation concentration separated out 3 by the crystalline mode, 4 '-the diaminodiphenyl oxide crystal, again through filtering, vacuum-drying, make at last highly purified 3,4 '-the diaminodiphenyl oxide crystal;
Reduction reaction equation general formula is as follows:
Figure C20061005081300061
Wherein R is amino or nitro, as R when being amino, Compound I be 3-amino-4 '-itrodiphenyl ethers; When R is nitro, Compound I is 3,4 '-dinitro diphenyl ether;
Described supported catalyst is FeCl 3.6H 2O/C or Pd/C are preferably FeCl 3.6H 2O/C;
Described reaction solvent is the fatty compounds that C1～C5 contains hydroxyl: a kind of in ethylene glycol monomethyl ether, methyl alcohol, ethanol, propyl alcohol, 2-methyl-2-propyl alcohol, 2-methyl-2-butanols, Virahol, propyl carbinol, 2-butanols, 2-methylpropanol or the 3-methyl isophthalic acid-butanols; Be preferably ethylene glycol monomethyl ether.
According to the present invention, target product 3 after nitro-reduction reaction was finished, 4 '-separation of diaminodiphenyl oxide purifies and may further comprise the steps: at a certain temperature reaction mixture filtered, with a small amount of fresh solvent wash supported catalyst filter cake, washing lotion and filtrate with its normal pressure intensification evaporation concentration recovery part solvent, separate out 3 by the crystalline mode after merging, 4 '-the diaminodiphenyl oxide crystal, more after filtration, vacuum-drying promptly obtains target product of the present invention.Obtained 3,4 '-diaminodiphenyl oxide crystal good crystalline, epigranular, purity 〉=99.2%, 74.2～75.8 ℃ of fusing points, consistent with bibliographical information (document JP 61221159 value: 74～76 ℃) identifies its structure with Fourier's infrared spectra and nucleus magnetic resonance.
Among the present invention, the weight ratio of raw material and reaction solvent is 1: 2.5～25 (be preferably 1: 5～10); Raw material and catalyst Fe Cl 3.6H 2The mol ratio of O/C is 25～700: 1, and (be preferably 150～500: 1), the mol ratio of raw material and catalyst P d/C is (to be preferably 3000～7500: 1) at 400～8000: 1; The mol ratio of nitro is (to be preferably 1.5～3.0: 1) at 1.0～10.0: 1 in reductive agent hydrazine hydrate and the reactant feed; The content of reductive agent hydrazine hydrate is 40～100% (being preferably 70%～85%) weight; The reaction solvent that normal pressure intensification evaporation concentration reclaims and the weight ratio of the reaction solvent of adding and the reaction solvent sum that the wash load catalyzer is used are (to be preferably 0.45～0.75: 1) at 0.05～0.95: 1; The temperature that described filtered while hot reclaims catalyzer is to the temperature between the boiling point that is lower than used reaction solvent 30 ℃ (being preferably 50 ℃).
Crystallization mode of the present invention is meant a kind of or its combination in natural cooling crystallization, constant rate of cooling crystallization or the isothermal crystal, preferred natural cooling crystallization.
Preparation of the present invention and separating and purifying method, it is good to have a crystal habit, the product purity height, alcoholic solvent reclaims simple, and the lower advantage of production cost, is suitable for large-scale commercial production.
Embodiment
The present invention can further specify by following embodiment, but embodiment is not a limiting the scope of the invention.
Embodiment 1
Add the 600g ethylene glycol monomethyl ether in the 1000mL four-hole boiling flask that reflux exchanger, agitator, rare gas element bottom insert canal, constant voltage feed hopper and Pt-100 temperature sensor are housed, the 25g charge capacity is the FeCl of 0.8wt% 3.6H 2The O/C catalyzer feeds nitrogen from the rare gas element bottom insert canal in four-hole boiling flask, start to stir, and is warmed up to 120 ℃, keeps refluxing 1 hour; Cool to 75 ± 5 ℃ then, add 78g (0.339mol) 3-amino-4 '-itrodiphenyl ethers after, under 70 ℃, hydrazine hydrate (0.68mol) with 40g 85wt% in 1 hour is added drop-wise in the four-hole boiling flask by the constant voltage feed hopper lentamente, after hydrazine hydrate dropwises, system temperature is elevated to 80 ℃, under this temperature, kept 4 hours, temperature is elevated to 115 ℃, kept 1 hour, be cooled to 90 ℃ then, filtered while hot, with the fresh ethylene glycol monomethyl ether washing leaching cake of 10g, behind the suction filtration, obtain 37g supported catalyst wet cake; Washings and filtrate merge, and being poured into tower still volume is in the distillation tower of 1000mL, after normal pressure reclaims the 420g solvent, the still raffinate naturally cools to room temperature, separates out white crystal, filters, obtain 103g filtrate, after filter cake was used the 80g washing with alcohol, vacuum-drying obtained 52.1g 3,4 '-diaminodiphenyl oxide, productive rate 76.84%, purity 99.3% (HPLC), 74.6～75.5 ℃ of fusing points (value among the document CN1485315A: 74.0～75.6 ℃).
Embodiment 2
The solvent that the ethylene glycol monomethyl ether that 420g solvent, 103g filtrate and the 77g that reclaims with embodiment 1 is fresh is formed replaces the 600g ethylene glycol monomethyl ether of use among the embodiment 1, is the FeCl of 0.8wt% with embodiment 1 37g catalyzer wet cake that obtains and the 5g charge capacity of adding 3.6H 2O/C is a catalyzer, and other is the same with embodiment 1, can obtain 63.0g 3,4 '-diaminodiphenyl oxide, productive rate 92.92%, purity 99.4% (HPLC), 74.7～75.5 ℃ of fusing points.
Embodiment 3
Adopt the method identical with embodiment 1, as catalyzer, can obtain 55.4g 3,4 '-diaminodiphenyl oxide with the Pd/C of 0.1g 5wt%, productive rate is 81.71%, purity 99.4% (HPLC), 74.7～75.4 ℃ of fusing points.In the preparation process, filtered and recycled 2.1g catalyzer wet cake, atmospheric evaporation concentrate and reclaim the 425g solvent, after the natural cooling crystallization, obtain 85g filtrate.
Embodiment 4
The ethylene glycol monomethyl ether that 425g solvent, 85g filtrate and the 90g that reclaims with embodiment 3 is fresh replaces the 600g ethylene glycol monomethyl ether of use among the embodiment 3, Pd/C with the fresh 5wt% of catalyzer wet cake that reclaims among the embodiment 3 and the 0.02g that adds makes catalyzer, other is the same with embodiment 3, can obtain 66.2g 3,4 '-diaminodiphenyl oxide, productive rate 97.64%, purity 99.4% (HPLC), 74.6～75.5 ℃ of fusing points.
Embodiment 5
Add the 300g ethylene glycol monomethyl ether in the 500mL four-hole boiling flask that reflux exchanger, agitator, rare gas element bottom insert canal, constant voltage feed hopper and Pt-100 temperature sensor are housed, the 15g charge capacity is 1% FeCl 3.6H 2The O/C catalyzer feeds nitrogen from the rare gas element bottom insert canal in four-hole boiling flask, start to stir, and is warmed up to 120 ℃, keeps refluxing 1 hour; Cool to 75 ± 5 ℃ then, add 52g (0.2mol) 3,4 '-dinitro diphenyl ether after, under 70 ℃, the hydrazine hydrate (0.9mol) with 53g 85wt% in 1 hour is added drop-wise in the four-hole boiling flask lentamente by the constant voltage feed hopper, after hydrazine hydrate dropwises, system temperature is elevated to 80 ℃, under this temperature, kept 4 hours, temperature is elevated to 115 ℃ then, kept 1 hour.Be cooled to 90 ℃, filtered while hot with the fresh ethylene glycol monomethyl ether washing leaching cake of 10g, behind the suction filtration, obtains 21g catalyzer wet cake; Washings and filtrate merge, and being poured into tower still volume is in the distillation tower of 500mL, after atmospheric evaporation concentrates and reclaims the 160g solvent, the still raffinate naturally cools to room temperature, separates out white crystal, filters, obtain 87g filtrate, after filter cake was used the 50g washing with alcohol, vacuum-drying obtained 32.1g 3,4 '-diaminodiphenyl oxide, productive rate 80.25%, purity 99.2% (HPLC), 74.4～75.7 ℃ of fusing points.
Embodiment 6
The solvent that the ethylene glycol monomethyl ether that 160g solvent, 87g filtrate and the 53g that reclaims with embodiment 5 is fresh is formed replaces the 300g ethylene glycol monomethyl ether of use among the embodiment 5, is 1% FeCl with embodiment 5 21g catalyzer wet cake that obtains and the 5g charge capacity of adding 3.6H 2O/C is a catalyzer, and other is the same with embodiment 5, can obtain 37.4g 3,4 '-diaminodiphenyl oxide, productive rate 93.5%, purity 99.3% (HPLC), 74.7～75.6 ℃ of fusing points.

Claims (2)

1, a kind of 3,4 '-preparation and the separating and purifying method of diaminodiphenyl oxide, it is characterized in that: with 3-amino-4 '-itrodiphenyl ethers or 3,4 '-dinitro diphenyl ether is a raw material, is reductive agent with the hydrazine hydrate, under nitrogen protection, in reaction solvent, carry out nitro-reduction reaction in the presence of supported catalyst, after reaction was finished, filtered while hot reclaimed catalyzer, use the reaction solvent washing catalyst, after washing lotion and filtrate merged, often voltage rise temperature evaporation concentration separated out 3 by the mode of natural cooling crystallization, 4 '-the diaminodiphenyl oxide crystal, again through filtering, vacuum-drying, make 3,4 at last '-the diaminodiphenyl oxide crystal;
Reduction reaction equation general formula is as follows:
Figure C2006100508130002C1
Wherein R is amino or nitro, as R when being amino, Compound I be 3-amino-4 '-itrodiphenyl ethers; When R is nitro, Compound I is 3,4 '-dinitro diphenyl ether;
Described supported catalyst is FeCl 3.6H 2O/C or Pd/C;
Described reaction solvent is an ethylene glycol monomethyl ether;
Wherein,
The weight ratio of raw material and reaction solvent is 1: 2.5～25, and reaction solvent is an ethylene glycol monomethyl ether;
Raw material and catalyst Fe Cl 3.6H 2The mol ratio of O/C is 25～700: 1; The mol ratio of raw material and catalyst P d/C is 400～8000: 1;
The mol ratio of nitro is 1.0～10.0: 1 in reductive agent hydrazine hydrate and the reactant feed;
The content of reductive agent hydrazine hydrate is 40～100% weight;
The reaction solvent that normal pressure intensification evaporation concentration reclaims and the reaction solvent of adding and the weight ratio of the reaction solvent sum that the wash load catalyzer is used are 0.05～0.95: 1;
The temperature that described filtered while hot reclaims catalyzer is to the temperature between the boiling point that is lower than used reaction solvent at 30 ℃.
2, preparation according to claim 1 and separating and purifying method is characterized in that:
The weight ratio of raw material and reaction solvent is 1: 5～10;
Raw material and catalyst Fe Cl 3.6H 2The mol ratio of O/C is 150～500: 1; The mol ratio of raw material and catalyst P d/C is 3000～7500: 1;
The mol ratio of nitro is 1.5～3.0: 1 in reductive agent hydrazine hydrate and the reactant feed;
The content of reductive agent hydrazine hydrate is 70～85% weight;
The reaction solvent that normal pressure intensification evaporation concentration reclaims and the reaction solvent of adding and the weight ratio of the reaction solvent sum that the wash load catalyzer is used are 0.45～0.75: 1;
The temperature that described filtered while hot reclaims catalyzer is to the temperature between the boiling point that is lower than used reaction solvent at 50 ℃.
CNB2006100508137A 2006-05-18 2006-05-18 Preparing and separating purifying method for 3,4'-diamino diphenyl ether Expired - Fee Related CN100457714C (en)

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CN111072503A (en) * 2019-12-28 2020-04-28 南通汇顺化工有限公司 Method for preparing 3, 4' -diaminodiphenyl ether
CN116462596A (en) * 2023-04-12 2023-07-21 山东欧亚新材料科技有限公司 Method for preparing 4,4' -diaminodiphenyl ether by hydrogenation one-step crystallization method

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CN1485315A (en) * 2002-09-26 2004-03-31 上海化学试剂研究所 Process for preparing 3,4-diaminodiphenyl ether

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Publication number Priority date Publication date Assignee Title
CN1485315A (en) * 2002-09-26 2004-03-31 上海化学试剂研究所 Process for preparing 3,4-diaminodiphenyl ether

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4，4'－二氨基二苯醚的合成. 赵继全等.化学试剂，第17卷第6期. 1995
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