CN1807399A - Method for preparing 4,4'-diaminodiphenyl ether - Google Patents
Method for preparing 4,4'-diaminodiphenyl ether Download PDFInfo
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- CN1807399A CN1807399A CN 200610023814 CN200610023814A CN1807399A CN 1807399 A CN1807399 A CN 1807399A CN 200610023814 CN200610023814 CN 200610023814 CN 200610023814 A CN200610023814 A CN 200610023814A CN 1807399 A CN1807399 A CN 1807399A
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- diaminodiphenyl oxide
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- dimethyl formamide
- methyl alcohol
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Abstract
The invention relates to a preparation method for 4, 4'-diamino diphenyl ether, which comprises: taking catalytic hydrogenation reduction reaction to the 4, 4'-dinitro diphenyl ether in alcohol solvent; crystallizing to obtain the coarse product; reducing pressure to sublimate and refine the coarse product for final product. This invention has well product quality and no pollution with low cost, and more fit to spread than the traditional ferrous powder-chlorhydric acid reduction method.
Description
Affiliated technical field
The present invention relates to a kind of preparation 4, the method for 4 '-diaminodiphenyl oxide belongs to the fine chemical technology field.
Background technology
4,4 '-diaminodiphenyl oxide is a kind of meticulous organic products of high added value.It is one of important source material of fire resistant resins such as new special engineering plastics polyimide, polyetherimide, polyester-imide, polyamide-imide, poly maleimide, polyaramide.It is still synthetic 3,3 ', 4, the raw material of 4 '-tetramino phenyl ether, and the latter is the principal monomer of a series of heat resistance aromatic heterocycle polymer materials of preparation such as polybenzimidazole, polyphenylene quinoline, polyimidazole pyrrole throat.It also can be used as the raw material and the linking agent of synthesized polymer materials such as high performance heat resistant epoxy resin, urethane.Also be used for substituting p-diaminodiphenyl simultaneously and produce fields such as azoic dyestuff, reactive dyestuffs and spices with carcinogenesis.Make raw material with diamines at present, developed the substantive dyestuff of bright red, bright red, Sha Hong, yellowish-brown, green, grey, blue, gorgeous orange, different color ranges such as black, can be used for the dyeing of silk, hair, cloth, aspects such as its color and luster fastness and degree of exhaustion all are better than benzidine dye.Along with the increasingly mature of China's polyimide product development technology popularized, the specification kind is complete day by day, and 4,4 '-diaminodiphenyl oxide will more and more come into one's own as emphasis novel material monomer.The expansion of Application Areas, to 4, the demand of 4 '-diaminodiphenyl oxide and output are also increasing year by year.So 4,4 '-dinitro diphenyl ether hydrogenation preparing 4,4 '-diaminodiphenyl oxide process has economic worth and social effect.
Industry 4 at present, 4 '-dinitro diphenyl ether reduction preparation 4,4 '-diaminodiphenyl oxide mainly adopts iron powder-hydrochloric acid reduction method, hydrazine hydrate reduction method and catalytic hydrogenation reduction method.Iron powder-hydrochloric acid reduction method with iron powder as reductive agent, NH
4Cl is a catalyzer.This method product yield is lower, and molar yield only is about 75%, poor product quality, and technology labour intensity is big, and has a large amount of three wastes, and environmental pollution is serious, belongs to eliminating technology.The hydrazine hydrate reduction method is a solvent with methyl alcohol or ethanol, and hydrazine hydrate is as hydrogen donor and reductive agent, and the reflux reduction prepares.The quality product that this method is produced is better, and yield is also higher, and molar yield can reach about 90%, and reaction conditions is gentle.But the hydrazine hydrate price is more expensive, and cost is higher, and corrodibility is strong, and toxicity is big.This production technique also progressively is eliminated.
Summary of the invention
In order to overcome existing preparation 4, the deficiency of the method for 4 '-diaminodiphenyl oxide the purpose of this invention is to provide that a kind of production cost is low, environmental pollution is little, good product quality, preparation 4 that yield is high, the method for 4 '-diaminodiphenyl oxide.
The present invention solves technology and the case that its technical problem adopts: a kind of preparation 4, the method of 4 '-diaminodiphenyl oxide, has following technical process: by 4,4 '-dinitro diphenyl ether carries out the catalytic hydrogenation reduction reaction in Pd/C catalyzer (palladium carbon catalyst) and the mixed solvent of alcohols, through crystallization treatment, slightly 4,4 '-diaminodiphenyl oxide; Thick 4,4 '-diaminodiphenyl oxide behind the decompression sublimation purifying 4,4 '-diaminodiphenyl oxide.
As preferably: described preparation 4, the method of 4 '-diaminodiphenyl oxide, has following technical process: in high-pressure reaction pot, add 4,4 '-dinitro diphenyl ether, the mixed solvent of alcohols and Pd/C catalyzer, heat temperature raising carries out the catalytic hydrogenation reduction reaction, after question response finishes, filter while hot, isolate the Pd/C catalyzer, filtrate is put into the ice bath crystallisation by cooling, filtration drying, slightly 4,4 '-diaminodiphenyl oxide, thick 4,4 '-diaminodiphenyl oxide gets 4,4 '-diaminodiphenyl oxide through the decompression sublimation purifying.
As preferably: described catalytic hydrogenation reduction reaction is carried out under 95～100 ℃, 0.4Mpa condition.
As preferably: the content of Pd is 0.5%-10% in the described Pd/C catalyzer.
As preferably: the content of Pd is 3%-5% in the described Pd/C catalyzer.
As preferably: described alcohols mixed solvent is a methyl alcohol and dimethyl formamide or N,N-DIMETHYLACETAMIDE blended mixed solvent mutually, or ethanol and dimethyl formamide or N,N-DIMETHYLACETAMIDE blended mixed solvent mutually.Select for use the mixed solvent of methyl alcohol or ethanol and dimethyl formamide or N,N-DIMETHYLACETAMIDE to replace original pure alcoholic solvent that uses, make raw material 4,4 '-dinitro diphenyl ether and reduzate 4,4 '-diaminodiphenyl oxide all can be dissolved in mixed solvent well, precious metals pd/C convenient catalyst is separated, recycle after cleaning activation, mixed solvent also can be recycled, and greatly reduces production cost.
As preferably: described alcohols mixed solvent is a methyl alcohol and dimethyl formamide blended mixed solvent mutually.
As preferably: described methyl alcohol and dimethyl formamide be the blended mixed solvent mutually, the mixed of methyl alcohol and dimethyl formamide 1: 0.1 by volume～1.
As preferably: described methyl alcohol and dimethyl formamide be the blended mixed solvent mutually, the mixed of methyl alcohol and dimethyl formamide 1: 0.2 by volume～0.5.
Reactional equation of the present invention is:
The invention has the beneficial effects as follows, preparation 4 of the present invention, the method for 4 '-diaminodiphenyl oxide has following advantage:
1, production cost is low: the precious metals pd of use/C catalyzer and methyl alcohol, dimethyl formamide mixed solvent be the energy recycled all, greatly reduces production cost.
2, environmental pollution is little: traditional iron powder-hydrochloric acid reducing process produces the iron mud that macro-mixing has nitro thing, amino substance, serious environment pollution.This reaction only generates product and water, environmental protection.
3, good product quality, the yield height: owing to adopted the Pd/C catalyzer, the resultant metal ion content is low, and especially iron ion content is extremely low, less than 2 μ g/g.The product purity height, quality is good, can satisfy the microelectronics industry service requirements.Compare the product yield height with traditional iron powder-hydrochloric acid technology.
Production cost of the present invention is low, and environmental pollution is little, good product quality, and the yield height, the market competitiveness is strong, easily carries out industry and applies.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Embodiment 1:
In the autoclave of 50L band whipping appts, drop into 4Kg 4,4 '-dinitro diphenyl ether, 20g Pd content are the mixed solvent that 3% Pd/c catalyzer, 25L methyl alcohol and 5L dimethyl formamide are formed, feeding steam heating to the autoclave interlayer heats up, autoclave is used nitrogen replacement three times earlier, replace respectively three times with hydrogen again, under 95～100 ℃, 0.4Mpa condition, carry out the catalytic hydrogenation reduction reaction.After hydrogenation finishes, filtered while hot, isolate the Pd/C catalyzer, recycle behind the isolated Pd/C catalyst wash purifying activator, isolate filtrate behind the Pd/C catalyzer with 0 ℃ frozen water mixed solution cooling, separate out thick 4,4 '-diaminodiphenyl oxide 2.78Kg, molten point is 190.0～190.4 ℃, molar yield is 90.4%, mixed solvent also can be recycled, thick 4,4 '-diaminodiphenyl oxide gets polymerization-grade 4 through vacuum-sublimation, 4 '-diaminodiphenyl oxide white crystals 2.77Kg, molten point is 190.9～191.4 ℃, molar yield 90.1%.
Embodiment 2:
Other conditions are identical with embodiment 1, and just Pd/c catalyzer employing Pd content is 5% Pd/c catalyzer.Obtain thick 4,4 '-diaminodiphenyl oxide 2.83Kg, molten point is 190.1～190.5 ℃, molar yield is 91.8%.Thick 4,4 '-diaminodiphenyl oxide distils to such an extent that polymerization-grade is thick 4 through decompression, 4 '-diaminodiphenyl oxide white crystals 2.80Kg, and molten point is 191.0～191.5 ℃, molar yield 91.0%.
Claims (9)
1. one kind prepares 4, and the method for 4 '-diaminodiphenyl oxide is characterized in that having following technical process: by 4,4 '-dinitro diphenyl ether carries out the catalytic hydrogenation reduction reaction in Pd/C catalyzer and the mixed solvent of alcohols, through crystallization treatment, slightly 4,4 '-diaminodiphenyl oxide; Thick 4,4 '-diaminodiphenyl oxide behind the decompression sublimation purifying 4,4 '-diaminodiphenyl oxide.
2. preparation 4 according to claim 1, the method of 4 '-diaminodiphenyl oxide, it is characterized in that having following technical process: in high-pressure reaction pot, add 4,4 '-dinitro diphenyl ether, the mixed solvent of alcohols and Pd/C catalyzer, heat temperature raising carries out the catalytic hydrogenation reduction reaction, after question response finishes, filter while hot, isolate the Pd/C catalyzer, filtrate is put into the ice bath crystallisation by cooling, filtration drying, slightly 4,4 '-diaminodiphenyl oxide, thick 4,4 '-diaminodiphenyl oxide gets 4,4 '-diaminodiphenyl oxide through the decompression sublimation purifying.
3. preparation 4 according to claim 2, the method for 4 '-diaminodiphenyl oxide is characterized in that: described catalytic hydrogenation reduction reaction is carried out under 95～100 ℃, 0.4Mpa condition.
4. preparation 4 according to claim 2, the method for 4 '-diaminodiphenyl oxide is characterized in that: the content of Pd is 0.5%～10% in the described Pd/C catalyzer.
5. preparation 4 according to claim 4, the method for 4 '-diaminodiphenyl oxide is characterized in that: the content of Pd is 3%～5% in the described Pd/C catalyzer.
6. preparation 4 according to claim 2, the method of 4 '-diaminodiphenyl oxide, it is characterized in that: described alcohols mixed solvent is a methyl alcohol and dimethyl formamide or N,N-DIMETHYLACETAMIDE blended mixed solvent mutually, or ethanol and dimethyl formamide or N,N-DIMETHYLACETAMIDE blended mixed solvent mutually.
7. preparation 4 according to claim 6, the method for 4 '-diaminodiphenyl oxide is characterized in that: described alcohols mixed solvent is a methyl alcohol and dimethyl formamide blended mixed solvent mutually.
8. preparation 4 according to claim 7, the method for 4 '-diaminodiphenyl oxide is characterized in that: described methyl alcohol and dimethyl formamide be the blended mixed solvent mutually, the mixed of methyl alcohol and dimethyl formamide 1: 0.1 by volume～1.
9. preparation 4 according to claim 8, the method for 4 '-diaminodiphenyl oxide is characterized in that: described methyl alcohol and dimethyl formamide be the blended mixed solvent mutually, the mixed of methyl alcohol and dimethyl formamide 1: 0.2 by volume～0.5.
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| CN 200610023814 CN1807399A (en) | 2006-02-10 | 2006-02-10 | Method for preparing 4,4'-diaminodiphenyl ether |
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| CN 200610023814 CN1807399A (en) | 2006-02-10 | 2006-02-10 | Method for preparing 4,4'-diaminodiphenyl ether |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391136A (en) * | 2011-10-27 | 2012-03-28 | 东营市冠森绝缘制品有限公司 | Method and device for producing 4,4-diaminodiphenyl ethers by using catalytic hydrogenation process |
| CN102898375A (en) * | 2012-11-13 | 2013-01-30 | 齐鲁动物保健品有限公司 | Preparation method of 2-(3-aminophenyl) imidazoline hydrochloride |
| CN108276297A (en) * | 2017-12-29 | 2018-07-13 | 上海固创化工新材料有限公司 | A kind of preparation method of 4,4 '-diaminodiphenyl ethers |
| CN109180504A (en) * | 2018-08-20 | 2019-01-11 | 万达集团股份有限公司 | A kind of recovery and treatment method of 4,4`- diaminodiphenyl ether distillation residue |
| CN109180501A (en) * | 2018-08-01 | 2019-01-11 | 青岛泰玛新材料科技有限公司 | A kind of synthetic method of 4,4 '-diaminodiphenyl ethers |
| CN110164821A (en) * | 2019-06-12 | 2019-08-23 | 京东方科技集团股份有限公司 | The manufacturing method of flexible display panels |
| CN113788760A (en) * | 2021-09-16 | 2021-12-14 | 山东能源集团有限公司 | Preparation method of 4, 4' -diaminodiphenyl ether |
-
2006
- 2006-02-10 CN CN 200610023814 patent/CN1807399A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391136A (en) * | 2011-10-27 | 2012-03-28 | 东营市冠森绝缘制品有限公司 | Method and device for producing 4,4-diaminodiphenyl ethers by using catalytic hydrogenation process |
| CN102898375A (en) * | 2012-11-13 | 2013-01-30 | 齐鲁动物保健品有限公司 | Preparation method of 2-(3-aminophenyl) imidazoline hydrochloride |
| CN108276297A (en) * | 2017-12-29 | 2018-07-13 | 上海固创化工新材料有限公司 | A kind of preparation method of 4,4 '-diaminodiphenyl ethers |
| CN109180501A (en) * | 2018-08-01 | 2019-01-11 | 青岛泰玛新材料科技有限公司 | A kind of synthetic method of 4,4 '-diaminodiphenyl ethers |
| CN109180501B (en) * | 2018-08-01 | 2021-03-16 | 青岛泰玛新材料科技有限公司 | Synthetic method of 4, 4' -diaminodiphenyl ether |
| CN109180504A (en) * | 2018-08-20 | 2019-01-11 | 万达集团股份有限公司 | A kind of recovery and treatment method of 4,4`- diaminodiphenyl ether distillation residue |
| CN109180504B (en) * | 2018-08-20 | 2021-04-09 | 万达集团股份有限公司 | Recovery treatment method of 4,4' -diaminodiphenyl ether sublimation residue |
| CN110164821A (en) * | 2019-06-12 | 2019-08-23 | 京东方科技集团股份有限公司 | The manufacturing method of flexible display panels |
| CN113788760A (en) * | 2021-09-16 | 2021-12-14 | 山东能源集团有限公司 | Preparation method of 4, 4' -diaminodiphenyl ether |
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