CN106977408A - The preparation method of p-Leuconiline - Google Patents
The preparation method of p-Leuconiline Download PDFInfo
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- CN106977408A CN106977408A CN201710256856.9A CN201710256856A CN106977408A CN 106977408 A CN106977408 A CN 106977408A CN 201710256856 A CN201710256856 A CN 201710256856A CN 106977408 A CN106977408 A CN 106977408A
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- leuconiline
- warming
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- crude product
- suction filtration
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/78—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton from carbonyl compounds, e.g. from formaldehyde, and amines having amino groups bound to carbon atoms of six-membered aromatic rings, with formation of methylene-diarylamines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention provides a kind of preparation method of p-Leuconiline, it is characterised in that comprise the following steps：Step a, prepare p-Leuconiline crude product；It is step b, refined.The preparation method for the p-Leuconiline that the present invention is provided, the technique that leading portion prepares p-Leuconiline crude product can be reduced because technique changes the fluctuation to product quality with constant.Material is not boiled in subtractive process, the usage amount of steam is reduced, energy consumption is reduced；Without steam water and the gas-condensate liquid for boiling material, the generation of waste liquid is reduced.Finished product fusing point is up to 192 DEG C, content 93%, and quality is higher.
Description
Technical field
The present invention relates to adhesive field, more particularly to a kind of preparation method of p-Leuconiline.
Background technology
P-Leuconiline is a kind of chemical substance, is mainly used as manufacture rubber and Metal adhesive i.e. polymeric isocyanate glue
Raw material, 208 DEG C of sterling fusing point.Traditional handicraft is to make reducing agent with sodium polysulfide, and para-nitrotoluene oxygen is made in ethanol medium
Change reduction, then in presence of hydrochloric acid with aniline condensation, neutralized through caustic soda, aniline, suction filtration be evaporated off, washed material and obtain p-Leuconiline
Crude product.Crude product adds diluted acid fully to dissolve, and adds activated carbon decolorizing processing, and suction filtration obtains filtrate and is neutralized to alkalescence with diluted alkaline,
Heating boil 6~8 hours, suction filtration, wash material, drying, crushing obtain p-Leuconiline finished product.
This technique needs to make material boil 6~8 hours in subtractive process, using a large amount of steam, causes technique productions mistake
The substantial increase of energy consumption in journey.And during material is boiled, original process steam and material directly contact, a large amount of steam become useless
Liquid, directly results in waste liquid amount increase；And material boils rear gas, directly discharge will result in the pollution of air and production environment,
Waste liquid will be transformed into using condensation recycling method, the substantial increase of waste liquid amount in art production process is ultimately caused.Original work
184 DEG C of the fusing point of finished product p-Leuconiline prepared by skill, content 87%, quality is low.
The content of the invention
In view of this, the present invention provides a kind of preparation method of p-Leuconiline.
The present invention provides a kind of preparation method of p-Leuconiline, and it comprises the following steps：
Step a, prepare p-Leuconiline crude product；
It is step b, refined, specifically include：
B1, suction filtration p-Leuconiline crude product, improve vacuum to Shui Fen≤30%；
B2, dissolve p-Leuconiline crude product with concentrated hydrochloric acid, stirring is to well mixed；
The material that b3, suction filtration step b2 are obtained, obtains yellow solid；
B4, the obtained yellow solids of step b3 are added water, be warming up to 60 DEG C, insulated and stirred to material dissolved clarification；To reactor
Interior addition activated carbon, stirs 2h；Suction filtration material, removes activated carbon, impurity and accessory substance in filter cake, obtains filtrate；
B5, filtrate neutralized with 10% sodium hydroxide solution, it is uniform be added dropwise sodium hydroxide solution to material PH be 8；Take out
Screening material, it is 7 that material, which is washed with water, to PH in filter cake, dries, crushes, obtain p-Leuconiline.
Further, the step a is specifically included：
A1, prepare sodium polysulfide
28.8~25.2wt% sodium hydroxide solution is configured, 80 DEG C is warming up to, is uniformly added into sulphur, it is warming up to 96~
100 DEG C of insulation reactions 4 hours；
A2, redox reaction
Ethanol is added into reactor, 40 DEG C of para-nitrotoluene for adding melting is warming up to, is warming up to 83~84 DEG C, keep second
Alcohol reflux uniformly drips sodium polysulfide in 40 minutes, 1~1.5 hour, insulation reaction 3 hours is cooled to 45 DEG C, stands 2 small
When, separate inorganic phase raffinate, heating distillation, recovery ethanol, temperature to 96 DEG C of stoppings；
A3, condensation reaction
The obtained reducing solutions of step a2 are cooled to 60 DEG C, aniline is added, 80 DEG C are warming up to, hydrochloric acid is added, heating 106~
108 DEG C are reacted 6 hours, are cooled to 80 DEG C, and it is 8.5~9 that caustic soda, which is added dropwise, and is neutralized to PH, is cooled to 40 DEG C, filtrate is distilled to recover benzene
Amine, filter cake washes material to neutrality with more than 40 DEG C of warm water, obtains p-Leuconiline crude product.
The preparation method for the p-Leuconiline that the present invention is provided, the technique that leading portion prepares p-Leuconiline crude product can
With constant, reduce because technique changes the fluctuation to product quality.Material is not boiled in subtractive process, the usage amount of steam is reduced,
Reduce energy consumption；Without steam water and the gas-condensate liquid for boiling material, the generation of waste liquid is reduced.Finished product fusing point up to 192 DEG C,
Content 93%, improves product quality.
Embodiment
The invention discloses a kind of preparation method of p-Leuconiline, those skilled in the art can be used for reference in herein
Hold, be suitably modified technological parameter realization.In particular, all similar replacements and change are to those skilled in the art
For be it will be apparent that they are considered as being included in the present invention.The method of the present invention and application are by preferably implementing
Example is described, related personnel substantially can not departing from present invention, in spirit and scope to method described herein and
Using being modified or suitably changing with combining, to realize and apply the technology of the present invention.
In order to solve the preparation high energy consumption of p-Leuconiline present in prior art, waste liquid amount is big, and quality of finished is low
Defect, the present invention provides a kind of preparation method of p-Leuconiline, comprises the following steps：
Step a, prepare p-Leuconiline crude product；
It is step b, refined, specifically include：
B1, suction filtration p-Leuconiline crude product, improve vacuum to Shui Fen≤30%；
B2, dissolve p-Leuconiline crude product with concentrated hydrochloric acid, stirring is to well mixed；Principle equation is as follows：
HC(C6H4NH2)3+3HCl→HC(C6H4NH2·HCl)3
The material that b3, suction filtration step b2 are obtained, obtains yellow solid；
B4, the obtained yellow solids of step b3 are added water, be warming up to 60 DEG C, insulated and stirred to material dissolved clarification；To reactor
Interior addition activated carbon, stirs 2h；Suction filtration material, removes activated carbon, impurity and accessory substance in filter cake, obtains filtrate；
B5, filtrate neutralized with 10% sodium hydroxide solution, it is uniform be added dropwise sodium hydroxide solution to material PH be 8；Take out
Screening material, it is 7 that material, which is washed with water, to PH in filter cake, dries, crushes, obtain p-Leuconiline；Principle equation is as follows：
HC(C6H4NH2·HCl)3+3NaOH→HC(C6H4NH2)3+3NaCl+3H2O
Step a can use existing process, can specifically include：
A1, prepare sodium polysulfide
28.8~25.2wt% sodium hydroxide solution is configured, 80 DEG C is warming up to, is uniformly added into sulphur, it is warming up to 96~
100 DEG C of insulation reactions 4 hours；Principle equation is as follows：
6NaOH+5S=Na2S2+Na2S+Na2S2O3+3H2O
A2, redox reaction
Ethanol is added into reactor, 40 DEG C of para-nitrotoluene for adding melting is warming up to, is warming up to 83~84 DEG C, keep second
Alcohol reflux uniformly drips sodium polysulfide in 40 minutes, 1~1.5 hour, insulation reaction 3 hours is cooled to 45 DEG C, stands 2 small
When, separate inorganic phase raffinate, heating distillation, recovery ethanol, temperature to 96 DEG C of stoppings；Principle equation is as follows：
A3, condensation reaction
The obtained reducing solutions of step a2 are cooled to 60 DEG C, aniline is added, 80 DEG C are warming up to, hydrochloric acid is added, heating 106~
108 DEG C are reacted 6 hours, are cooled to 80 DEG C, and it is 8.5~9 that caustic soda, which is added dropwise, and is neutralized to PH, is cooled to 40 DEG C, filtrate is distilled to recover benzene
Amine, filter cake washes material to neutrality with more than 40 DEG C of warm water, obtains p-Leuconiline crude product.Principle equation is as follows：
The preparation method for the p-Leuconiline that the present invention is provided, the technique that leading portion prepares p-Leuconiline crude product can
With constant, reduce because technique changes the fluctuation to product quality.Material is not boiled in subtractive process, the usage amount of steam is reduced,
Reduce energy consumption；Without steam water and the gas-condensate liquid for boiling material, the generation of waste liquid is reduced.192 DEG C of finished product fusing point, content
93%, quality is improved.
With reference to embodiment, the present invention is expanded on further：
Embodiment 1
Prepare sodium polysulfide：25.2% diluted alkaline (sodium hydroxide solution) is configured, 80 DEG C are warming up to, sulphur is uniformly added into, risen
Temperature was to 96 DEG C of insulation reactions 4 hours.
Redox reaction：Ethanol is added into reactor, 40 DEG C of para-nitrotoluene for adding melting is warming up to, is warming up to 83
DEG C, the larger backflow of holding ethanol uniformly drips sodium polysulfide in 40 minutes, 1 hour, and insulation reaction 3 hours is cooled to 45
DEG C, 2 hours are stood, inorganic phase raffinate, heating distillation, recovery ethanol, temperature to 96 DEG C of stoppings is separated.
Condensation reaction：Reducing solution is cooled to 60 DEG C, adds aniline, is warming up to 80 DEG C, adds hydrochloric acid, and heat up 106 DEG C of reactions 6
Hour, 80 DEG C are cooled to, caustic soda is added dropwise and is neutralized to PH=8.7,40 DEG C are cooled to, filtrate is distilled to recover aniline, filter cake is used>40℃
Warm water washes material to neutrality, obtains the thick color base of paramagenta, i.e. p-Leuconiline crude product.
It is refined：500ml there-necked flasks are taken, agitator, heating mantle are installed, the thick color base wet feed (moisture 30%) of 100g paramagenta is taken
In addition kettle, 124.7g concentrated hydrochloric acids (30%) are added, yellow solid occurs in stirring, continue to stir to being well mixed, suction filtration is obtained
To yellow solid, solid adds water 410g, is heated to 60 DEG C, 2h is stirred in stirring to solid dissolved clarification, plus activated carbon 5g, and suction filtration is obtained
In filtrate, filtrate diluted alkaline and adjust PH=8, suction filtration, be washed with water material to PH=7, dry i.e. finished product.191 DEG C of finished product fusing point, content
92.5%.
500ml there-necked flasks are taken, agitator, heating mantle are installed, the thick color base wet feed (moisture 30%) of 100g paramagenta is taken, are added
There is yellow solid in 104.8g concentrated hydrochloric acids (36%), stirring, continues to stir to being well mixed, suction filtration obtains yellow solid, Gu
Body adds water 410g, is heated to 60 DEG C, stirring to solid dissolved clarification, plus activated carbon 5g, stirs 2h, suction filtration, obtains filtrate, and filtrate is with dilute
In alkali and adjust PH=8, suction filtration, be washed with water material to PH=7, dry i.e. finished product.192 DEG C of finished product fusing point, content 93.2%.
Embodiment 2
Prepare sodium polysulfide：24.8% diluted alkaline is configured, 80 DEG C is warming up to, is uniformly added into sulphur, 100 DEG C of insulations are warming up to anti-
Answer 4 hours.
Redox reaction：Ethanol is added into reactor, 40 DEG C of para-nitrotoluene for adding melting is warming up to, is warming up to 84
DEG C, the larger backflow of holding ethanol uniformly drips sodium polysulfide in 40 minutes, 1 hour, and insulation reaction 3 hours is cooled to 45 DEG C,
2 hours are stood, inorganic phase raffinate, heating distillation, recovery ethanol, temperature to 96 DEG C of stoppings is separated.
Condensation reaction：Reducing solution is cooled to 60 DEG C, adds aniline, is warming up to 80 DEG C, adds hydrochloric acid, and heat up 107 DEG C of reactions 6
Hour, 80 DEG C are cooled to, caustic soda is added dropwise and is neutralized to PH=8.5-9,40 DEG C are cooled to, filtrate is distilled to recover aniline, filter cake is used>40
DEG C warm water washes material to the neutral i.e. thick color base of paramagenta.
It is refined：500ml there-necked flasks are taken, agitator, heating mantle are installed, the thick color base wet feed (moisture of 100g paramagenta is taken
30%) 104.8g concentrated hydrochloric acids (36%), are added, yellow solid occurs in stirring, continues to stir to being well mixed, suction filtration obtains Huang
Color solid, solid adds water 410g, is heated to 60 DEG C, 2h is stirred in stirring to solid dissolved clarification, plus activated carbon 5g, and suction filtration is filtered
In liquid, filtrate diluted alkaline and adjust PH=8, suction filtration, be washed with water material to PH=7, dry i.e. finished product.192 DEG C of finished product fusing point, content
93.2%.
As shown in the above, p-Leuconiline fusing point prepared by the method provided according to the present invention contains up to 192 DEG C
Amount is up to 93%, and quality is high.
Traditional handicraft feature：Need to make material boil 6~8 hours in subtractive process, using a large amount of steam, cause technique to give birth to
The substantial increase of energy consumption during production.And during material is boiled, original process steam and material directly contact, a large amount of steam become
Into waste liquid, waste liquid amount increase is directly resulted in；And material boils rear gas, directly discharge will result in the dirt of air and production environment
Dye, will be transformed into waste liquid using condensation recycling method, ultimately cause the substantial increase of waste liquid amount in art production process.It is original
Finished product paramagenta mass ratio prepared by technique is relatively low：184 DEG C of the fusing point of procrypsis base, content 87%, quality is low.
The preparation method for the p-Leuconiline that the present invention is provided, the technique that leading portion prepares p-Leuconiline crude product can
With constant, reduce because technique changes the fluctuation to product quality.Improve the quality of paramagenta finished product：Finished product fusing point is reachable
192 DEG C, content 93%, quality is higher.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (2)
1. a kind of preparation method of p-Leuconiline, it is characterised in that comprise the following steps：
Step a, prepare p-Leuconiline crude product；
It is step b, refined, specifically include：
B1, suction filtration p-Leuconiline crude product, improve vacuum to Shui Fen≤30%；
B2, dissolve p-Leuconiline crude product with concentrated hydrochloric acid, stirring is to well mixed；
The material that b3, suction filtration step b2 are obtained, obtains yellow solid；
B4, the obtained yellow solids of step b3 are added water, be warming up to 60 DEG C, insulated and stirred to material dissolved clarification；Add into reactor
Enter activated carbon, stir 2h；Suction filtration material, removes activated carbon, impurity and accessory substance in filter cake, obtains filtrate；
B5, filtrate neutralized with 10% sodium hydroxide solution, it is uniform be added dropwise sodium hydroxide solution to material PH be 8；Suction filtration thing
Material, it is 7 that material, which is washed with water, to PH in filter cake, dries, crushes, obtain p-Leuconiline.
2. preparation method according to claim 1, it is characterised in that the step a is specifically included：
A1, prepare sodium polysulfide
28.8~25.2wt% sodium hydroxide solution is configured, 80 DEG C is warming up to, is uniformly added into sulphur, be warming up to 96~100 DEG C
Insulation reaction 4 hours；
A2, redox reaction
Ethanol is added into reactor, 40 DEG C of para-nitrotoluene for adding melting is warming up to, is warming up to 83~84 DEG C, keep ethanol to return
Stream uniformly drips sodium polysulfide in 40 minutes, 1~1.5 hour, insulation reaction 3 hours is cooled to 45 DEG C, stands 2 hours, point
From inorganic phase raffinate, heating distillation, recovery ethanol, temperature to 96 DEG C of stoppings；
A3, condensation reaction
The obtained reducing solutions of step a2 are cooled to 60 DEG C, aniline is added, 80 DEG C are warming up to, hydrochloric acid, heating 106~108 is added
DEG C reaction 6 hours, is cooled to 80 DEG C, it is 8.5~9 that caustic soda, which is added dropwise, and is neutralized to PH, is cooled to 40 DEG C, filtrate is distilled to recover aniline,
Filter cake washes material to neutrality with more than 40 DEG C of warm water, obtains p-Leuconiline crude product.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108892620A (en) * | 2018-08-01 | 2018-11-27 | 上海同毅化工有限公司 | 4,4 ' of one kind, the 4 " preparation methods of-triaminotriphenyl-methane |
| CN108929239A (en) * | 2018-08-10 | 2018-12-04 | 辽宁红山化工股份有限公司 | A kind of preparation method of sodium polysulfide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1265206A1 (en) * | 1984-06-29 | 1986-10-23 | Предприятие П/Я А-7253 | Method of purifying leucoparafuchsin |
| CN1876625A (en) * | 2005-06-10 | 2006-12-13 | 拜尔材料科学股份公司 | Preparation method of 4, 4' -diphenylmethane diisocyanate |
-
2017
- 2017-04-19 CN CN201710256856.9A patent/CN106977408A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1265206A1 (en) * | 1984-06-29 | 1986-10-23 | Предприятие П/Я А-7253 | Method of purifying leucoparafuchsin |
| CN1876625A (en) * | 2005-06-10 | 2006-12-13 | 拜尔材料科学股份公司 | Preparation method of 4, 4' -diphenylmethane diisocyanate |
Non-Patent Citations (3)
| Title |
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| LESLIE M. WERBEL ET AL.: "Trisarylmethane. Synthesis of Diarylcarbinol Precursors by Controlled Catalytic Hydrogenation", 《J. ORG. CHEM.》 * |
| 宋丽凤 等: "三氨基三苯甲烷定量分析方法", 《染料与染色》 * |
| 彭倩: "新型炭质固体酸催化剂的制备及其应用", 《华东理工大学硕士论文》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108892620A (en) * | 2018-08-01 | 2018-11-27 | 上海同毅化工有限公司 | 4,4 ' of one kind, the 4 " preparation methods of-triaminotriphenyl-methane |
| CN108929239A (en) * | 2018-08-10 | 2018-12-04 | 辽宁红山化工股份有限公司 | A kind of preparation method of sodium polysulfide |
| CN108929239B (en) * | 2018-08-10 | 2021-03-02 | 辽宁红山化工股份有限公司 | Preparation method of sodium polysulfide |
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Application publication date: 20170725 |