CN102924298B - Separation method of 1,5-diaminonaphthalene and 1,8-diaminonaphthalene - Google Patents
Separation method of 1,5-diaminonaphthalene and 1,8-diaminonaphthalene Download PDFInfo
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Abstract
The invention provides a separation method of 1,5-diaminonaphthalene and 1,8-diaminonaphthalene. At present, both the separation quality and the purity of mixtures of 1,5-diaminonaphthalene and 1,8-diaminonaphthalene cannot meet the requirements. The method comprises the following steps: (1) adding the mixtures of 1,5-diaminonaphthalene and 1,8-diaminonaphthalene, which are obtained by nitrifying naphthalene, into a reaction kettle with an agitator, adding an organic solvent and adding Pd/C catalyst in the mass percentage concentration of 5%, closing the reaction kettle and then filling hydrogen for catalytic hydrogenation to prepare diaminonaphthalene mixtures; (2) extracting the catalyst after finishing the reaction, performing first refrigeration to crystallize one part of 1,5-diaminonaphthalene, and distilling out one part of the organic solvent at normal pressure; and (3) performing the refrigeration again to crystallize 1,5-diaminonaphthalene, adding an antioxidant and distilling out the organic solvent at the normal pressure, and then depressurizing and distilling to obtain 1,8-diaminonaphthalene. The method is used for separating 1,5-diaminonaphthalene and 1,8-diaminonaphthalene, the product recycling rate is high, and the product purity is high at the same time.
Description
Technical field
The present invention relates to the separation method of a kind of 1,5-diaminonaphthalene and 1,8-diaminonaphthalene.
Background technology
1,5-diaminonaphthalene and 1,8-diaminonaphthalene are two important compounds in diaminonaphthalene isomer, and 1,5-diaminonaphthalene is mainly prepared 1,5-naphthalene diisocyanate, and then prepares polyurethane elastomer; 1,8-diaminonaphthalene is mainly for the production of solvent dye, as C.I. solvent of red 135 and C.I. solvent orange 60 etc.
Traditional prepare diaminonaphthalene method be naphthalene after nitrated to 1,5-dinitronaphthalene and 1, the mixture of 8-dinitronaphthalene, carries out separation to mixture and obtains 1,5-dinitronaphthalene and 1,8-dinitronaphthalene, then respectively 1,5-dinitronaphthalene and 1,8-dinitronaphthalene are reduced and obtain 1,5-diaminonaphthalene and 1,8-diaminonaphthalene.But because 1,5-dinitronaphthalene is close with 1,8-dinitronaphthalene character, separation is difficulty comparatively.Also there is report with the mixture direct-reduction of 1,5-dinitronaphthalene and 1,8-dinitronaphthalene, to obtain the mixture of 1,5-diaminonaphthalene and 1,8-diaminonaphthalene.As Chinese patent CN:200910142890.9, but for 1, the separation of the mixture of 5-diaminonaphthalene and 1,8-diaminonaphthalene, patent CN:200910142890.9 adopts and first isolates 1,8-diaminonaphthalene isolates 1 again, 5-diaminonaphthalene, produces a large amount of tar and impurity owing to first distilling out 1,8-diaminonaphthalene, isolated 1,5-diaminonaphthalene quality and purity all do not reach requirement.
Summary of the invention
The object of the invention is to provide for the problem of above-mentioned existence the separation method of a kind of 1,5-diaminonaphthalene and 1,8-diaminonaphthalene, the product recovery rate obtaining is high, and product purity is high simultaneously.
Above-mentioned object is achieved through the following technical solutions:
The separation method of 1,5-diaminonaphthalene and 1,8-diaminonaphthalene, the method comprises the steps:
(1) in the reactor stirring at band, obtain after adding naphthalene nitrated 1,5-dinitronaphthalene and 1, the mixture of 8-dinitronaphthalene, adds organic solvent, and adding mass percentage concentration is 5% Pd/C catalyzer, off-response still, is then filled with hydrogen and carries out preparing diaminonaphthalene by catalytic hydrogenation mixture;
(2) reaction is isolated catalyzer after finishing, and carries out freezing and crystallizing for the first time and goes out a part of 1,5-diaminonaphthalene, and air distillation goes out part organic solvent;
(3) freezing and crystallizing goes out 1,5-diaminonaphthalene for the second time, adds antioxidant air distillation to go out organic solvent, and rear underpressure distillation obtains 1,8-diaminonaphthalene.
The separation method of described 1,5-diaminonaphthalene and 1,8-diaminonaphthalene, described organic solvent is a kind of in aniline, ethanol, Virahol, tetrahydrofuran (THF), its consumption be 1,5-dinitronaphthalene and 1,8-dinitronaphthalene mixture quality sum 3-4 doubly.
The separation method of described 1,5-diaminonaphthalene and 1,8-diaminonaphthalene, the temperature of described freezing and crystallizing is for the first time 0-5 degree.
The separation method of described 1,5-diaminonaphthalene and 1,8-diaminonaphthalene, the temperature of described freezing and crystallizing is for the second time 15-20 degree.
The separation method of described 1,5-diaminonaphthalene and 1,8-diaminonaphthalene, described antioxidant is V-Brite B, its add-on be 1,5-dinitronaphthalene and 1,8-dinitronaphthalene mixture quality sum 0.5%.
The separation method of described 1,5-diaminonaphthalene and 1,8-diaminonaphthalene, the amount that the air distillation described in step (2) goes out organic solvent is 1/2nd of total organic solvent amount.
The separation method of described 1,5-diaminonaphthalene and 1,8-diaminonaphthalene, the vacuum tightness that the underpressure distillation described in step (3) goes out 1,8-diaminonaphthalene is-0.097MPa that temperature is 220-260 degree.
Beneficial effect:
The separation method of diaminonaphthalene of the present invention, the technology of underpressure distillation after employing secondary freezing and crystallizing, effectively raise 1, 5-diaminonaphthalene and 1, the separation efficiency of 8-diaminonaphthalene, and keep product 1, 5-diaminonaphthalene and 1, the high purity of 8-diaminonaphthalene, avoided mixing that first underpressure distillation obtains after dinitronaphthalene hydrogenation reaction 1, the feature that 8-diaminonaphthalene purity is low, avoided because first underpressure distillation obtains 1 simultaneously, during 8-diaminonaphthalene due to a large amount of tar of the higher generation of temperature, after obtain 1, 5-diaminonaphthalene need to be repeatedly refining shortcoming, simplified production technique, reduced production cost.Through experiment, show, compared with prior art, when product recovery rate is high, product purity is high for the inventive method.
Embodiment
The separation method of 1,5-diaminonaphthalene and 1,8-diaminonaphthalene, the method comprises the steps:
(1) in the reactor stirring at band, obtain after adding naphthalene nitrated 1, the mixture of 5-dinitronaphthalene and 1,8-dinitronaphthalene, wherein 1, the mass ratio of 5-dinitronaphthalene and 1,8-dinitronaphthalene is between 4:6-3:7.Add organic solvent, adding mass percentage concentration is 5% Pd/C catalyzer, and off-response still, is then filled with hydrogen and carries out preparing diaminonaphthalene by catalytic hydrogenation mixture;
(2) reaction is isolated catalyzer after finishing, and carries out freezing and crystallizing for the first time and goes out a part of 1,5-diaminonaphthalene, and air distillation goes out part organic solvent;
(3) freezing and crystallizing goes out 1,5-diaminonaphthalene for the second time, adds antioxidant air distillation to go out organic solvent, and rear underpressure distillation obtains 1,8-diaminonaphthalene.
The separation method of described 1,5-diaminonaphthalene and 1,8-diaminonaphthalene, described organic solvent is a kind of in aniline, ethanol, Virahol, tetrahydrofuran (THF), its consumption be 1,5-dinitronaphthalene and 1,8-dinitronaphthalene mixture quality sum 3-4 doubly.
The separation method of described 1,5-diaminonaphthalene and 1,8-diaminonaphthalene, the temperature of described freezing and crystallizing is for the first time 0-5 degree.
The separation method of described 1,5-diaminonaphthalene and 1,8-diaminonaphthalene, the temperature of described freezing and crystallizing is for the second time 15-20 degree.
The separation method of described 1,5-diaminonaphthalene and 1,8-diaminonaphthalene, described antioxidant is V-Brite B, its add-on be 1,5-dinitronaphthalene and 1,8-dinitronaphthalene mixture quality sum 0.5%.
The separation method of described 1,5-diaminonaphthalene and 1,8-diaminonaphthalene, the amount that the air distillation described in step (2) goes out organic solvent is 1/2nd of total organic solvent amount.
The separation method of described 1,5-diaminonaphthalene and 1,8-diaminonaphthalene, the vacuum tightness that the underpressure distillation described in step (3) goes out 1,8-diaminonaphthalene is-0.097MPa that temperature is 220-260 degree.
Embodiment 1:
In the autoclave high-pressure reactor that is 1000mL at volume, put into the mixed dinitronaphthalene of 120g (wherein 1, 45.6 grams of 5-dinitronaphthalene, 1, 74.4 grams of 8-dinitronaphthalene), 480 grams of ethanol, the Pd/C catalyzer of 0.15g (catalyzer of giving money as a gift) 5%, airtight rear nitrogen replacement air 3～5 times of using, with hydrogen exchange nitrogen 3～5 times, then be filled with hydrogen and carry out catalytic hydrogenation reaction, after finishing, reaction removes catalyzer, in filtrate shift-in 1000mL there-necked flask, icy salt solution is cooled to 5 degree, filtration obtains 1, 5-diaminonaphthalene, filtrate is again in shift-in there-necked flask, air distillation goes out 240 grams of ethanol, icy salt solution is cooled to 15 degree, filtration obtains 1, 5-diaminonaphthalene.In filtrate shift-in there-necked flask, add 0.6g V-Brite B, air distillation goes out after ethanol, in vacuum tightness, is-0.097MPa, and temperature is that under 220-260 degree condition, underpressure distillation obtains 1,8-diaminonaphthalene.After drying, 1,5-diaminonaphthalene is 32 grams, and the purity of survey is 52.3 grams of 99.0%, 1,8-diaminonaphthalenes, and the purity of survey is 99.2%.
Embodiment 2:
In the autoclave high-pressure reactor that is 1000mL at volume, put into the mixed dinitronaphthalene of 120g (wherein 1, 36 grams of 5-dinitronaphthalene, 1, 84 grams of 8-dinitronaphthalene, 360 grams of tetrahydrofuran (THF)s, the Pd/C catalyzer of 0.15g (catalyzer of giving money as a gift) 5%, airtight rear nitrogen replacement air 3～5 times of using, with hydrogen exchange nitrogen 3～5 times, then be filled with hydrogen and carry out catalytic hydrogenation reaction, after finishing, reaction removes catalyzer, in filtrate shift-in 1000mL there-necked flask, icy salt solution is cooled to 0 degree, filtration obtains 1, 5-diaminonaphthalene, filtrate is again in shift-in there-necked flask, air distillation goes out 150 grams of tetrahydrofuran (THF)s, icy salt solution is cooled to 0 degree, filtration obtains 1, 5-diaminonaphthalene.In filtrate shift-in there-necked flask, add 0.6g V-Brite B, air distillation goes out after tetrahydrofuran (THF), in vacuum tightness, is-0.097MPa, and temperature is that under 220-260 degree condition, underpressure distillation obtains 1,8-diaminonaphthalene.After drying, 1,5-diaminonaphthalene is 25.05 grams, and the purity of survey is 59.7 grams of 99.4%, 1,8-diaminonaphthalenes, and the purity of survey is 99.4%.
Embodiment 3:
In the autoclave high-pressure reactor that is 1000mL at volume, put into the mixed dinitronaphthalene of 120g (wherein 1, 48 grams of 5-dinitronaphthalene, 1, 72 grams of 8-dinitronaphthalene, 360 grams of aniline, the Pd/C catalyzer of 0.15g (catalyzer of giving money as a gift) 5%, airtight rear nitrogen replacement air 3～5 times of using, with hydrogen exchange nitrogen 3～5 times, then be filled with hydrogen and carry out catalytic hydrogenation reaction, after finishing, reaction removes catalyzer, in filtrate shift-in 1000mL there-necked flask, icy salt solution is cooled to 5 degree, filtration obtains 1, 5-diaminonaphthalene, filtrate is again in shift-in there-necked flask, air distillation goes out 150 grams of aniline, icy salt solution is cooled to 5 degree, filtration obtains 1, 5-diaminonaphthalene.In filtrate shift-in there-necked flask, often adding 0.6g V-Brite B, press and distill out after aniline, is-0.097MPa that temperature is that under 220-260 degree condition, underpressure distillation obtains 1,8-diaminonaphthalene in vacuum tightness.After drying, 1,5-diaminonaphthalene is 34.1 grams, the purity 99.2%, 1 of survey, and 50.1 grams of 8-diaminonaphthalenes, the purity of survey is 99.0%.
Embodiment 4:
In the autoclave high-pressure reactor that is 1000mL at volume, put into the mixed dinitronaphthalene of 120g (wherein 1, 45.6 grams of 5-dinitronaphthalene, 1, 74.4 grams of 8-dinitronaphthalene, 480 grams of Virahols, the Pd/C catalyzer of 0.15g (catalyzer of giving money as a gift) 5%, airtight rear nitrogen replacement air 3～5 times of using, with hydrogen exchange nitrogen 3～5 times, then be filled with hydrogen and carry out catalytic hydrogenation reaction, after finishing, reaction removes catalyzer, in filtrate shift-in 1000mL there-necked flask, icy salt solution is cooled to 5 degree, filtration obtains 1, 5-diaminonaphthalene, filtrate is again in shift-in there-necked flask, air distillation goes out 150 grams of aniline, icy salt solution is cooled to 5 degree, filtration obtains 1, 5-diaminonaphthalene.In filtrate shift-in there-necked flask, add 0.6g V-Brite B, air distillation goes out after Virahol, in vacuum tightness, is-0.097MPa, and temperature is that under 220-260 degree condition, underpressure distillation obtains 1,8-diaminonaphthalene.After drying, 1,5-diaminonaphthalene is 32 grams, the purity 99.1%, 1 of survey, 52.3 grams of 8-diaminonaphthalenes, the purity 99.2% of survey.
Claims (1)
1. the separation method of a 1,5-diaminonaphthalene and 1,8-diaminonaphthalene, is characterized in that: the method comprises the steps:
(1) in the reactor stirring at band, obtain after adding naphthalene nitrated 1,5-dinitronaphthalene and 1, the mixture of 8-dinitronaphthalene, adds organic solvent, and adding mass percentage concentration is 5% Pd/C catalyzer, off-response still, is then filled with hydrogen and carries out preparing diaminonaphthalene by catalytic hydrogenation mixture;
(2) reaction is isolated catalyzer after finishing, and carries out freezing and crystallizing for the first time and goes out a part of 1,5-diaminonaphthalene, and air distillation goes out part organic solvent;
(3) freezing and crystallizing goes out 1,5-diaminonaphthalene for the second time, adds antioxidant air distillation to go out organic solvent, and rear underpressure distillation obtains 1,8-diaminonaphthalene.
2. the separation method of 1,5-diaminonaphthalene according to claim 1 and 1,8-diaminonaphthalene, described organic solvent is a kind of in aniline, ethanol, Virahol, tetrahydrofuran (THF), its consumption is 1,5-dinitronaphthalene and 1,8-dinitronaphthalene mixture quality sum 3-4 times.
3. the separation method of 1,5-diaminonaphthalene according to claim 1 and 2 and 1,8-diaminonaphthalene, the temperature of described freezing and crystallizing is for the first time 0-5 degree.
4. the separation method of 1,5-diaminonaphthalene according to claim 1 and 2 and 1,8-diaminonaphthalene, the temperature of described freezing and crystallizing is for the second time 15-20 degree.
5. the separation method of 1,5-diaminonaphthalene according to claim 1 and 2 and 1,8-diaminonaphthalene, described antioxidant is V-Brite B, its add-on be 1,5-dinitronaphthalene and 1,8-dinitronaphthalene mixture quality sum 0.5%.
6. the separation method of 1,5-diaminonaphthalene according to claim 1 and 2 and 1,8-diaminonaphthalene, the amount that the air distillation described in step (2) goes out organic solvent is 1/2nd of total organic solvent amount.
7. the separation method of 1,5-diaminonaphthalene according to claim 1 and 2 and 1,8-diaminonaphthalene, the vacuum tightness that the underpressure distillation described in step (3) goes out 1,8-diaminonaphthalene is-0.097MPa that temperature is 220-260 degree.
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| CN106631821B (en) * | 2016-10-25 | 2018-07-31 | 西安彩晶光电科技股份有限公司 | A kind of preparation method of diaminonaphthalene |
| CN111116378A (en) * | 2019-12-20 | 2020-05-08 | 南京金浩医药科技有限公司 | Method for synthesizing 1, 8-diaminonaphthalene by selective reduction of 1, 8-dinitronaphthalene |
| CN115057783A (en) * | 2022-07-15 | 2022-09-16 | 宁夏瑞泰科技股份有限公司 | Method for separating 1, 5-diaminonaphthalene and 1, 8-diaminonaphthalene |
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