CN104086442A - Preparation method of 2,5-diaminotoluene sulfate - Google Patents
Preparation method of 2,5-diaminotoluene sulfate Download PDFInfo
- Publication number
- CN104086442A CN104086442A CN201410335147.6A CN201410335147A CN104086442A CN 104086442 A CN104086442 A CN 104086442A CN 201410335147 A CN201410335147 A CN 201410335147A CN 104086442 A CN104086442 A CN 104086442A
- Authority
- CN
- China
- Prior art keywords
- diaminotoluene
- tdas
- preparation
- product
- sulfuric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of 2,5-diaminotoluene sulfate, which mainly relates to effective separation of reaction products 2,5-diaminotoluene and o-toluidine and removal technique of o-toluidine in a 2,5-diaminotoluene sulfate product. The method comprises the following steps: by using 2-aminoazotoluene as the raw material, carrying out reducing metallic iron, zinc or other azo bond rupture reduction one-step reaction or distilling off the byproduct o-toluidine and filtering out the metal sludge, carrying out alkaline extraction, adsorbing and decolorizing to trace amounts of OT, and reacting with sulfuric acid to obtain the high-quality 2,5-TDAS, wherein the yield is 70-86%; or distilling off the byproduct o-toluidine, filtering out the metal sludge, adding sulfuric acid into the filtrate, filtering, taking out the 2,5-TDAS crude product, and repeatedly adsorbing and decolorizing with acidic/alkaline activated carbon to remove the OT in the product, wherein the total yield is 65-76%. The product 2,5-TDAS is preferably used in cosmetics due to high quality and low toxicity, and the o-toluidine content is less than 10 ppm. The alkaline extraction and activated carbon adsorption and decolorization techniques can lower the energy consumption, enhance the productivity and greatly reduce the wastewater amount.
Description
Technical field
The present invention relates to chemical field, particularly a kind of preparation method of 2,5-diaminotoluene sulphate.Mainly reaction product 2,5-diaminotoluene and Ortho Toluidine effective separate and 2,5-diaminotoluene sulphate product in the removal technology of Ortho Toluidine.
Background technology
2,5-diaminotoluene (2,5-TDA), for containing the two amino aromatic hydrocarbon substances of contraposition in molecular structure, except substituted p-phenylenediamine is as hair dye, also can be used for the field of new such as straight polyamide, polyimide and urethane.Its structure is as shown in the formula shown in (I):
From 20 beginnings of the century 2,5-TDA material occur to the eighties, because the narrow and demand of its range of application is few, therefore synthetic and application report is very few to it.The nineties rises along with cosmetology rise in the world, 2,5-diaminotoluene is made the effective color development composition of hair dye and than Ursol D, the discovery of the advantage such as the injury that when use, human body caused is lower, make 2, the research and development of 5-diaminotoluene comes into one's own day by day, in addition ensure that from storage and transportation product has many-sided considerations such as satisfactory stability, the series product of 2,5-diaminotoluene also start in succession to occur and are studied and application person's attention and exploitation.2,5-diaminotoluene series product mainly comprise 2,5-diaminotoluene (2,5-TDA) and the aqueous solution, 2,5-diaminotoluene sulphate (2,5-TDAS) and 2, the products such as 5-diaminotoluene dihydrochloride (2,5-TDAH).Wherein 2, 5-diaminotoluene sulphate is 2, 5-TDAS, it is as high-grade hair dye generation composition precursor, the use that is coupling component is very extensive, there is black, purple, purple-hydrazone look, palm fibre-orange color and luster cream rinse that waits, be now substituted p-phenylenediamine for the main component of the popular dyeing of high-grade hair cosmetic composition, wherein world-renowned cosmetics company is as German Wella, all kinds of brand hair dyes that the P & G of Henkel and the U.S. etc. produce are all with 2, 5-TDAS is main component, current needs amount exceedes 600t/, and domestic 2, the consumption of 5-TDAS on hair dye also increasing year by year, market outlook are wide.But since entering 21 century, along with the understanding to hair dye specialty chemicals and the technology degree that becomes more meticulous constantly rise, abroad to 2,5-TDAS quality requirements is very high, extremely tight (be mainly the carcinogenic arylamine such as Ortho Toluidine, require content <10ppm) of poisonous and harmful Control of Impurities.Therefore, in the urgent need to reaching the international standard of world-renowned cosmetics company.
Basis prepared by 2,5-diaminotoluene sulphate is first to make 2,5-diaminotoluene, then in its aqueous solution, adds sulfuric acid conveniently to make.The preparation method of at present relevant 2,5-diaminotoluene mainly can be divided into following several large class by starting raw material and process:
1) taking meta-aminotoluene (MT) as starting raw material; after amino protection; make phenylmethylamine between 6-nitro through nitrated, hydrolysis again; make product 2 finally by reduction; 5-diaminotoluene, this method reaction process step is more complicated, causes the yield of product lower; only have 38.6-57.3%, industrial economy is poor.And the nitrating agent adopting in the route that directly carries out restoring after nitrated taking meta-aminotoluene is as Guanidinium nitrate or urea nitrate, this class nitrating agent price is high and industrial source is rare, has limited its application in industrialization.After making intermediate azo-compound, diazo coupling makes through scission of link reduction again with meta-aminotoluene and also have, the key of this method is the preparation of azo-compound, but although meta-aminotoluene also self diazo coupling make corresponding azo-compound, but the total recovery of its diazo coupling in Virahol-acetic acid solvent is only 70%, that process is polluted is large, raw material availability is low and should not select, the price of adding meta-aminotoluene is far above Ortho Toluidine more than one times, is difficult to economically reach requirement and loses the advantage of industrialization competition.
2), taking Ortho Toluidine (OT) as raw material, make 4-nitro-o-toluidine (rb-RL also claims fast red rl) through amido protecting, nitrated, deprotection, then through the technique of reduction, this method is the conventional method of early stage industry.The key of this route is the synthetic of fast red rl, there are classical way and its improved technique of B.I.O.S about it is synthetic, traditional classical way be adopt Tosyl chloride and OT carry out after condensation amido protecting, again through nitrated, hydrolysis and neutralize, yield is 95%, but the supplementary material of its use approximately has 11 kinds; And the process using formic acid that improves synthetic fast red rl be amino protection source to replace Tosyl chloride, other step is with B.I.O.S classical approach, yield is about 70%, the supplementary material of use is reduced to six kinds.The fast red rl making can make target product 2,5-diaminotoluene after reduction.The method of reduction mainly contains shortening and iron powder reducing method, it respectively has relative merits, and the technique side reaction of shortening is few, good product quality, yield are high, but its catalyzer price is high, in addition reaction needed is carried out under the conditions such as pressurization, and its manufacturing condition is harsher.Technique with iron powder reducing is simple ripe, and cost is low, equipment routine, but it is due to discharge iron mud and a large amount of waste water, and therefore environmental pollution is larger.
3) make 2 taking azo intermediate as raw material through azo bond fracture reduction hydrogenolysis; 5-TDA, the azo intermediate of report mainly contains two kinds at present, and one is through p-methyl benzene sulfonic chloride protection gained intermediate with OT; carry out coupling with Diazosalt of sulfanilic acid, then through Na
2s
2o
4reduction, H again
2sO
4hydrolysis first makes 2,5-TDAS, and the technology of last alkali neutralization makes 2,5-TDA.Although it is good 2 that this technological line can make quality, 5-TDA, because its synthetic route is long, it is many to relate to raw and auxiliary material, pollute and raw material expend very large, industrialization aspect economy and environmental protection all without advantage.
Another kind is to make 2,5-TDA taking 2-amido-azotoluene as raw material through reductive cleavage, and 2-amido-azotoluene makes through self diazo coupling taking Ortho Toluidine as raw material, but for not having bibliographical information for catalyzer and the result of cracking reduction.One of this patent inventor discloses a kind of 2 in patent CN101450904, the synthetic method of 5-diaminotoluene and vitriol thereof, but relevant its do not removed carcinogenic substance Ortho Toluidine (OT) after reaction finishes in last handling process, make it reach OT content 10ppm the following description of demand on current world market, metallic reducing under the hydrogenation of the RaneyNi that it adopts and Pd/C catalyzer and hydrazine hydrate and acidic conditions, operation is all from reclaiming OT angle, when oil droplet disappears substantially in liquid water to be distillated, stopping steam distillation (approximately needing 4h) filtrate repeatedly repeatedly decolours and adsorbs after impurity through gac, add sulfuric acid salify, after cold filtration, washing, dry 2, the lab scale technology of 5-TDAS product, do not relate to the removal of OT in product.In addition, also not other document and Patents were not reported the objectionable impuritiess such as relevant removal OT, required the explanation of standard to meet Cosmetic Market etc.And industrial adopted method is approximately to need behind 18-20h left and right to adopt gac multiple adsorb (generally needing left and right 5 times) can make the approximately product 2 containing OT amount 500ppm left and right by long steam distillation again, 5-TDAS, this is with respect to the in addition larger gap of market demands, each decolouring product loss is about 1-2% left and right simultaneously, and rate of loss is large.
Therefore, select route and the post processing mode of suitable synthetic 2, a 5-diaminotoluene to remove the wherein content of Ortho Toluidine, to make the high-quality 2 of the standard of according with the demands of the market, 5-diaminotoluene sulphate has become the task of top priority.
Summary of the invention
The problem existing for solving above-mentioned prior art, the object of the present invention is to provide a kind of high-quality 2, the preparation method of 5-diaminotoluene sulphate, relate generally to reaction product 2,5-diaminotoluene and Ortho Toluidine effective separate and 2,5-diaminotoluene sulphate product in the removal technology of Ortho Toluidine.The present invention selects 2-amido-azotoluene (C.I.11160) for raw material, through reduction such as reducing metal iron or zinc, adopts reductive agent to exist lower steam to steam after most of OT, reductive agent removal,
Or through alkali organic solvent extraction, and charcoal absorption decolouring is to the aftertreatments such as micro-OT, then makes with sulfuric acid reaction and meet 2 of current Cosmetic Market standard, 5-diaminotoluene sulphate (2,5-TDAS), yield is between 70～86%;
Or first take out the wet crude product of 2,5-TDAS with sulfuric acid, then carry out ammonia solvent, gac repeatedly adsorption bleaching to the acid-alkali refining legal system of micro-OT, sulfuric acid salify for high-quality 2,5-TDAS, total recovery is between 65～76%;
This technique has reaction raw materials and is easy to get, and side reaction is few, and the by-product Ortho Toluidine of production can be used for the required raw material C.I.11160 of self diazo coupling preparation feedback, and loss less, reaction conditions gentleness, be easy to industrialization.The wherein special post-processing technology of alkaline extraction and charcoal absorption decolouring, has more and reduces energy consumption, raising production capacity, and greatly reduce the features such as wastewater flow rate; Product 2,5-TDAS taking high-quality, low toxicity type (OT content 10ppm is following) preferentially for makeup as feature.
In order to reach object of the present invention, the present invention is achieved through the following technical solutions:
A kind of suc as formula the compound 2 shown in I, the preparation method of 5-diaminotoluene sulphate,
Reaction formula of the present invention is as follows,
Adopt C.I.11160 reduction scission of link mode, making a part 2, when 5-TDA, regenerate in the reaction product of a part OT, carry out 2,5-TDA and separate with the effective of OT, both made OT obtain efficient recovery, make again 2 of preparation, in 5-TDAS product, OT content is less than 10ppm.
Especially high-quality 2, the preparation of 5-diaminotoluene sulphate, specifically comprises that following two kinds are removed OT technique and step:
One, directly extraction absorption removes OT technique and step:
Step 1, in glass reactor, add aqueous solvent, and reducing metal, stirring is warming up to 85-90 DEG C of left and right, slowly adds a certain amount of mineral acid to activate 30 minutes to catalyzer, then adds raw material 2-amido-azotoluene (C.I.11160), be warming up to 95-102 DEG C, carry out the reduction hydrogenolysis of azo bond fracture; In reaction process, having by product Ortho Toluidine generates, adopt the method for limit coronite steam distillation, after being removed from reaction system, it recycles, in this process, need constantly to supplement the water yield steaming, after question response is reached home, reaction solution is cooled to behind 70 DEG C of left and right, adds behind mineral alkali regulation system pH to 8.5 left and right stand-by;
Step 2, get in a filter flask and add after a small amount of vat powder, by the aqueous solution filtering iron mud of gained in step 1, adopt mineral alkali to regulate filtrate pH to 10 left and right transparent light yellowish brown filtrate, the Ortho Toluidine that adds again organic solvent extraction not steam, extraction temperature is controlled at 5-60 DEG C, extraction is carried out 1～5 time, extraction finishes rear merging organic phase, adopt sulfuric acid to regulate after PH to 7-8 the water after extraction, add gac after being warming up to 90 DEG C, continue to be warming up to reflux and carry out charcoal absorption decolouring, filtered while hot, filtrate is cooled to room temperature; Adopt after sulfuric acid regulation system pH to 5.5-6.5, repeat charcoal absorption and decolour after 2 times, obtain containing 2 of micro-OT, the 5-diaminotoluene light yellowish brown aqueous solution;
Step 3, to obtain in step 2 containing 2, in the aqueous solution of 5-diaminotoluene, under whipped state, drip sulfuric acid in 0-20 DEG C, after regulation system pH to 2, the cooling white of separating out is with micro-peach solid 2,5-diaminotoluene sulphate, after filtration, washing obtains high-quality target product 2,5-TDAS after being dried.
Two, crude product takes out refining except OT technique and step:
Crude product takes out: by 2 after the reaction mixture filtering iron of gained in step 1 described in claim 2 or zinc mud, in the 5-TDA aqueous solution, add sulfuric acid to separate out 2,5-TDAS and filter taking-up 2,5-TDAS crude product; The most of OT containing in the aqueous solution more than approximately 80% is taken away with filtrate.
Treating process: by make 2, the wet crude product of 5-TDAS stirs and is neutralized to pH5.5 with weak ammonia, add a small amount of gac intensification adsorption bleaching when molten until complete, in the filtrate of the useless charcoal of filtering, be adjusted to slightly acidic with sulfuric acid, add again gac to be warming up to backflow adsorption bleaching, at (its neutral and alkali adsorption bleaching 2 times after continuous circulation adsorption bleaching 6-10 time, slightly acidic adsorption bleaching 4-8 time) filtrate in, finally add sulfuric acid acid out to become to salt out white crystals, after filtration, washing and drying, obtain high-quality target product 2,5-TDAS.
Further, in described step 1, the mineral acid of selecting is technical hydrochloric acid or sulfuric acid (w50%), and its consumption is the 5%-25% of raw material 2-amido-azotoluene (C.I.11160) weight; The molar ratio of reducing metal and 2-amido-azotoluene (C.I.11160) is 1.5～5.5:1.0.
Further, in described step 1, reducing metal is iron or zinc.Reduction hydrogenolysis finishes to add alkaline solution to regulate pH to 7.5～8 with neutralization.Mineral alkali used is ammoniacal liquor or 30% aqueous sodium hydroxide solution of mass concentration 28%,
Further, in described step 1 and two, to the by-product Ortho Toluidine (OT) generating in azo bond rupture reduction reaction, first adopt reduction limit, limit steam to steam and reclaim most of OT, under alkaline condition, extract a small amount of OT, charcoal absorption decolouring removal OT to micro-combination treatment method.
Further, in described step 2, be any of toluene, benzene, hexanaphthene for the organic solvent extracting; Each batch of consumption of extraction agent used is 2-4 times of the theoretical growing amount of by-product Ortho Toluidine, repeatedly extracts 1～5 time.
Further, the organic phase extracting in described step 2 obtains Ortho Toluidine after solvent recuperation, after the Ortho Toluidine of itself and steam distillation gained is merged, the OT that obtains 99% above purity through rectifying is for the preparation of 2-amido-azotoluene (C.I.11160).
Further, 2, the 5-TDAS crude product taking-up required sulfuric acid material of process and 2-amido-azotoluene (C.I.11160) amount of substance ratio are 1.0～1.3:1.0; NH in treating process weak ammonia
3with 2,5-TDAS amount of substance ratio be 1.8～2.1:1.0.
Further, the charcoal absorption decolouring in described step 2 and treating process, by first weakly alkaline charcoal absorption 1～2 time, rear slightly acidic adsorption bleaching 2～8 times, each activated carbon dosage is 0.03-0.05 times of the theoretical growing amount of by-product Ortho Toluidine.
With respect to prior art, beneficial effect of the present invention is:
1) than traditional preparation 2, the operational path of 5-diaminotoluene, the present invention selects 2-amido-azotoluene (C.I.11160) for raw material, after the reduction such as reducing metal iron or zinc, after aftertreatment, make high-quality 2 with sulfuric acid reaction again, 5-diaminotoluene sulphate (2,5-TDAS).This technique has reaction raw materials and is easy to get, and side reaction is few, and the by-product Ortho Toluidine of generation steams, can realize recycled in the required raw material C.I.11160 of preparation feedback after rectifying through water vapor, and loss is few, and reaction conditions gentleness, is easy to industrialization.Its reaction formula is as follows
2) the invention provides combined separation and the effective ways that remove OT, the time that can make water vapour steam OT foreshortens to 4h from original 18h, the effect that rear 14h steam steams OT adopts solvent-extracted method to replace, realize in reducing energy consumption and increase substantially production capacity, and greatly reduce the object of wastewater flow rate.Especially in the extraction of removal trace toxic material Ortho Toluidine and the special last handling process of charcoal absorption decolouring, utilize extraction solvent to by-product Ortho Toluidine and 2, the characteristic of the dissolving selective difference of 5-diaminotoluene, in ensureing that OT content is reduced to below 30ppm, reduce target product 2, the loss of 5-TDAS, and make the purity of 2,5-TDAS product and content reach more than 99.5% high-quality.
3) for realizing high-quality 2, the preparation of 5-TDAS product, be not thought of as raising production capacity minimizing wastewater flow rate and using combined separation and remove under the situation of OT method, adopt and first take out 2,5-TDAS wet crude product, the gac acid-alkali refining technique of adsorption bleaching repeatedly again, can reach equally in 2,5-TDAS product containing the high-quality below OT to 10ppm; But the loss of product and wastewater flow rate increase; For taking out the wet crude product of 2,5-TDAS once, filtrate is taken away the product 2 of dissolving, and 10～12% losses of 5-TDAS can adopt and crude product filtrate is carried out to the loss that technology that 2,5-TDAS reclaims reduces in treating process make up.
According to 2 of preparation provided by the present invention and post-treating method gained, 5-diaminotoluene sulphate (2,5-TDAS) product, purity is more than 99.5%, in the content 30ppm of Ortho Toluidine (OT), even below 10ppm, reach Cosmetic Market international standard, be preferentially used in high-grade hair dye product.
Embodiment
In order to be illustrated more clearly in content of the present invention, below in conjunction with specific embodiment, the present invention program is described in further details.
1 one kind 2 of embodiment, preparation method's (directly extraction absorption is except OT technique) of 5-diaminotoluene sulphate, comprises the following steps successively:
1) thermometer is being housed, in the 500ml there-necked flask of return line and whipping appts, drop into 90g reduced iron powder, after 250ml water, be warming up to after 90 DEG C, start slowly to drip the about 17g of concentrated hydrochloric acid, after dropwising, maintaining this temperature carries out after the about 30min of catalyst activation, in reactor, add 76.9g2-amido-azotoluene (C.I.11160) (0.341mol), about 10min finishes, on reaction unit, install after reaction distillation device, be warming up to back flow reaction, now system temperature is at 95-102 DEG C, in reaction process, there is gradually oily matter to produce, and steam after condensation and flow in receiving flask along with water vapor.Reaction is approximately carried out after 3h, and TLC follows the tracks of detection raw material and reacts completely, and in reaction distillation process, constantly in system, adds water, and add-on is identical with the amount of steaming.Stopped reaction, is cooled to after 70 DEG C a little, stand-by behind employing strong aqua regulation system PH to 8.5 left and right.The aqueous solution containing OT steaming adds a small amount of NaOH to carry out alkali layering, obtains and reclaims Ortho Toluidine, the OT rate of recovery 83.1%.
2) reaction solution of step 1 gained is filtered to filtering iron mud, filtrate filter, to being placed with in the filter flask of 1.2g vat powder in advance, shakes up the settled solution into light yellowish brown.Continue to adopt ammoniacal liquor to regulate behind pH to 10 left and right, after hierarchy of control temperature is 45-50 DEG C, add 73g hexanaphthene to stir lower extraction, stir after 15min, be transferred to separating funnel, leave standstill after 30min, separate the aqueous solution and upper organic phase that 2,5-TDA is contained in lower floor.Water is carried out, after re-extract 3 times, separating water and organic phase again.After organic phase merges, after dried over anhydrous sodium carbonate, filtration, rotary evaporation reclaims solvent hexanaphthene 255g (rate of recovery 87.3%), Ortho Toluidine 18.6g.For water, adopt sulphur acid for adjusting pH to 7-8, after being warming up to 90 DEG C, add gac 4g, continue to be warming up to reflux and carry out charcoal absorption decolouring, filtered while hot, filtrate is cooled to after room temperature, adopt after sulfuric acid regulation system PH to 5.5-6.5, repeat charcoal absorption and decolour after 2 times, obtain containing 2 of micro-OT, the 5-diaminotoluene light yellowish brown aqueous solution.
3) to obtain in step 2 containing 2, in the aqueous solution of 5-diaminotoluene, under stirring, 0 DEG C drips the vitriol oil, behind regulation system PH to 2 left and right, cooling leaving standstill separated out white with micro-peach solid 2,5-diaminotoluene sulphate, after filtration, washing after dry the target product 2 of OT content 9ppm, 5-TDAS64.6g, purity 99.7% (A level product OT≤10ppm), yield 86%.
Change reducing metal in embodiment 1, sour kind and the consumption (the percentage ratio wt% of 2-amido-azotoluene input amount) of activation use, the mol ratio N of reducing metal and raw material 2-amido-azotoluene, all the other steps, with the step 1 in embodiment 1, obtain embodiment 2-5:
Kind and the impact of consumption on product of table 1 metal and acid
The kind, extraction temperature T, Solvent quantity (with the ratio of the growing amount of theoretical by-product Ortho Toluidine) and the extraction times that change extraction agent in embodiment 1, all the other steps, with the step 1 in embodiment 1, obtain embodiment 6-10:
The impact on product of table 2 extraction agent kind and extraction times
To sum up, as shown in table 1,2, in embodiment of the present invention 1-10, except the outer products therefrom purity of embodiment 8,9 is all greater than 99.5%, yield is more than 70%, and OT content is not more than 30ppm.
11 a kind 2 of embodiment, preparation method's (crude product takes out refining except OT technique) of 5-diaminotoluene sulphate, comprises the following steps successively:
1) crude product takes out: with in embodiment 1 1) identically feed intake and operate, reaction solution being filtered in the filtrate of filtering iron mud, after adding a small amount of gac weakly alkaline adsorption bleaching to filter for 2 times, add 37.6g sulfuric acid (20.4ml) to separate out the vitriol of 2,5-TDA, after filtration, wash, 2,5-TDAS wets, and (crude product is given money as a gift 65.6g, purity 98.74%, OT content 851ppm, crude product yield 87.3%).
2) treating process: by make 2, 5-TDAS wets, and (crude product is given money as a gift 65.6g, 0.297mol (136.8g, 0.621mol) join in appropriate process water 300mL, under stirring, slowly add 25% ammoniacal liquor 38.5g (mol ratio is 1.9:1) to be neutralized to pH5.5, add a small amount of charcoal absorption decolouring 10min when molten until complete, in the filtrate that removes by filter useless charcoal, add again charcoal absorption decolouring 10min, in the filtrate of filtering after continuous circulation adsorption bleaching 8 times, finally add 30.1g sulfuric acid (16.4ml) sulfuric acid acid out to become to salt out white crystals, filter, after washing and drying, obtain 2 of OT content 5.2ppm, 5-TDAS highly finished product (A level) 55.2g, purity 99.8%, refining yield 84.36%.
By embodiment 11 amplify 4 times feed intake and according to 1) crude product take out that step obtains 2,5-TDAS crude product (the yield 85.1% after giving money as a gift that wets, OT content 728ppm), change embodiment 112) adsorption bleaching number of times in treating process and the consumption of gac, all the other steps, with the treating process of embodiment 11, obtain embodiment 12-13:
The impact of table 3 treating process decolorizing with activated carbon number of times on product residue OT and yield
Visible, every through primary sorption decolouring operation 2, the refining yield of 5-TDAS product all will reduce, therefore meet under the prerequisite that different foreign traders require and avoid adsorption bleaching operation repeatedly as far as possible at OT, simultaneously can according to adsorption bleaching pass number, product is divided into some ranks: A level (OT≤10ppm), B level (OT≤30ppm), C level (OT≤50ppm) is to improve to greatest extent the synthetic yield of 2,5-TDAS and economy.
Than traditional preparation 2, the operational path of 5-diaminotoluene, it is raw material that the present invention selects 2-amido-azotoluene, after the reduction such as reducing metal iron or zinc, after aftertreatment, make with sulfuric acid reaction again and meet 2 of current Cosmetic Market standard, 5-diaminotoluene sulphate (2,5-TDAS), its OT content is less than 10ppm.This technique has reaction raw materials and is easy to get, and side reaction is few, and the by-product Ortho Toluidine of production can be realized recycled in the required raw material of preparation feedback, and loss is few, and reaction conditions gentleness, is easy to industrialization.And the invention provides two kinds of methods except OT: adopt solvent-extracted method can greatly reduce required energy consumption, save production cycle and product loss, improve production capacity; And selected solvent is to by-product Ortho Toluidine and 2, the dissolving selective difference of 5-diaminotoluene is obvious, and this characteristic reduces target product 2, the loss of 5-TDAS in ensureing to reduce OT content; And crude product takes out the method for acid-alkali refining, can keep away using and reclaiming of organic solvent, can conveniently control according to client the number of times of charcoal absorption decolouring to the requirement of OT content, to improve to greatest extent yield.
The above, be only the specific embodiment of the present invention, but protection scope of the present invention is not limited to this, and any variation of expecting without creative work or replacement, within all should being encompassed in protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain that claims were limited.
Claims (10)
1. one kind suc as formula the compound 2 shown in I, the preparation method of 5-diaminotoluene sulphate,
It is characterized in that, reaction formula of the present invention is as follows:
Specifically comprise the steps:
Step 1, in reactor, add aqueous solvent, and reducing metal, stirring is warming up to 85-90 DEG C of left and right, slowly adds a certain amount of mineral acid to activate 30 minutes to catalyzer, then adds raw material 2-amido-azotoluene (C.I.11160), be warming up to 95-102 DEG C, carry out reduction reaction; In reaction process, having by product Ortho Toluidine (OT) generates, adopt the method for limit coronite steam distillation, after making it remove most of OT from reaction system, recycle, in this process, need constantly to supplement the water yield steaming, after question response is reached home, reaction solution is cooled to behind 70 DEG C of left and right, adds behind mineral alkali regulation system PH to 8.5 left and right stand-by;
Step 2, get in a filter flask and add after a small amount of vat powder, by the aqueous solution filtering iron of gained in step 1 or zinc mud, adopt mineral alkali to regulate filtrate pH to 10 left and right transparent light yellowish brown filtrate, the a small amount of Ortho Toluidine (OT) that adds again organic solvent extraction not steam, extraction temperature is controlled at 5-60 DEG C, extraction is carried out 1～5 time, extraction finishes rear merging organic phase, by the water after extraction with sulphur acid for adjusting pH to 7-8, add gac after being warming up to 90 DEG C, continue to be warming up to reflux and carry out charcoal absorption decolouring, filtered while hot, filtrate is cooled to room temperature; Adopt after sulfuric acid regulation system PH to 5.5-6.5, repeat charcoal absorption and decolour after 2 times, obtain containing 2 of micro-OT, the 5-diaminotoluene light yellowish brown aqueous solution;
Step 3, to obtain in step 2 containing 2, in the aqueous solution of 5-diaminotoluene, under whipped state, drip sulfuric acid in 0-20 DEG C, after regulation system pH to 2, the cooling white of separating out is with micro-peach solid 2,5-diaminotoluene sulphate, after filtration, washing obtains high-quality target product 2,5-TDAS after being dried.
2. according to claim 12, the preparation method of 5-diaminotoluene sulphate, is characterized in that, replaces above-mentioned step 2 and three with following post-processing step:
Crude product takes out: by 2 after the reaction mixture filtering iron of gained in above-mentioned steps one or zinc mud, in the 5-TDA aqueous solution, add sulfuric acid to separate out 2,5-TDAS and filter taking-up 2,5-TDAS crude product; The most of OT containing in the aqueous solution more than approximately 80% is taken away with filtrate;
Treating process: by make 2, the wet crude product of 5-TDAS stirs and is neutralized to pH5.5 with weak ammonia, add a small amount of gac intensification adsorption bleaching when molten until complete, in the filtrate of the useless charcoal of filtering, be adjusted to slightly acidic with sulfuric acid, add again gac to be warming up to backflow adsorption bleaching, in the filtrate after continuous circulation adsorption bleaching 6-10 time, finally add sulfuric acid acid out to become to salt out white crystals, filter, after washing and drying high-quality target product 2,5-TDAS.
3. according to claim 22, the preparation method of 5-diaminotoluene sulphate, is characterized in that, in described treating process, continuous circulation adsorption bleaching comprises its neutral and alkali adsorption bleaching 2 times, slightly acidic adsorption bleaching 4-8 time.
4. according to claim 1-3 arbitrary described 2, the preparation method of 5-diaminotoluene sulphate, it is characterized in that: in described step 1, the mineral acid of selecting is technical hydrochloric acid or sulfuric acid (w50%), and its consumption is the 5%-25% of raw material 2-amido-azotoluene weight; The molar ratio of reducing metal and 2-amido-azotoluene (C.I.11160) is 1.5～5.5:1.0.
5. according to claim 1-3 arbitrary described 2, the preparation method of 5-diaminotoluene sulphate, it is characterized in that: in described step 1, reducing metal is iron or zinc, reduction finishes to add alkaline solution to regulate pH to 7.5～8 with neutralization, and mineral alkali used is ammoniacal liquor or 30% aqueous sodium hydroxide solution of mass concentration 28%.
6. according to claim 1-3 arbitrary described 2, the preparation method of 5-diaminotoluene sulphate, it is characterized in that: to the by-product Ortho Toluidine (OT) generating in azo bond rupture reduction reaction, first adopt reduction limit, limit steam to steam and reclaim most of OT, under alkaline condition, extract a small amount of OT, charcoal absorption decolouring removal OT to micro-combination treatment method.
7. arbitrary described 2 according to claim 1, the preparation method of 5-diaminotoluene sulphate, is characterized in that: in described step 2, be any of toluene, benzene, hexanaphthene for the organic solvent of alkaline extraction; Each batch of consumption of extraction agent used is 2-4 times of the theoretical growing amount of by-product Ortho Toluidine, repeatedly extracts 1～5 time.
8. according to claim 1 arbitrary described 2, the preparation method of 5-diaminotoluene sulphate, it is characterized in that: the organic phase extracting in described step 2 obtains Ortho Toluidine OT after solvent recuperation, after the Ortho Toluidine of itself and steam distillation gained is merged, the OT that obtains 99% above purity through rectifying is for the preparation of 2-amido-azotoluene (C.I.11160).
9. according to claim 22, the preparation method of 5-diaminotoluene sulphate, is characterized in that: 2,5-TDAS crude product takes out the required sulfuric acid of process and 2-amido-azotoluene (C.I.11160) amount of substance ratio is 1.0～1.3:1.0; NH in treating process weak ammonia
3with 2,5-TDAS amount of substance ratio be 1.8～2.1:1.0.
10. according to 2 described in claim 2～3, the preparation method of 5-diaminotoluene sulphate, it is characterized in that: described charcoal absorption is decoloured by first weakly alkaline charcoal absorption 1～2 time, rear slightly acidic adsorption bleaching 2～8 times, each activated carbon dosage is 0.03-0.05 times of the theoretical growing amount of by-product Ortho Toluidine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410335147.6A CN104086442A (en) | 2014-07-14 | 2014-07-14 | Preparation method of 2,5-diaminotoluene sulfate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410335147.6A CN104086442A (en) | 2014-07-14 | 2014-07-14 | Preparation method of 2,5-diaminotoluene sulfate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104086442A true CN104086442A (en) | 2014-10-08 |
Family
ID=51634233
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410335147.6A Pending CN104086442A (en) | 2014-07-14 | 2014-07-14 | Preparation method of 2,5-diaminotoluene sulfate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104086442A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114436857A (en) * | 2022-02-17 | 2022-05-06 | 浙江鼎龙科技股份有限公司 | 2, 5-diaminotoluene sulfate and preparation method of 2, 5-diaminotoluene |
| WO2023282382A1 (en) * | 2021-07-06 | 2023-01-12 | 씨에스아이엠 주식회사 | Method for preparing 2,5-diaminotoluene sulfate |
| CN115838334A (en) * | 2021-09-18 | 2023-03-24 | 深圳有为技术控股集团有限公司 | Preparation method of 2, 5-diaminotoluene sulfate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1718601A1 (en) * | 2004-02-24 | 2006-11-08 | Wella Aktiengesellschaft | (3,5-diaminophenyl)(2,4-dihydroxyphenyl)methanone and its acid adducts, method for the production of the latter and use of said compounds for colouring fibres |
| CN101450904A (en) * | 2007-12-05 | 2009-06-10 | 盐城鼎龙化工有限公司 | Synthetic method of 2,5-diaminotoluene and sulphate thereof |
| US7648535B2 (en) * | 2003-09-04 | 2010-01-19 | Wella Ag | Agent for coloring keratin fibres |
-
2014
- 2014-07-14 CN CN201410335147.6A patent/CN104086442A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7648535B2 (en) * | 2003-09-04 | 2010-01-19 | Wella Ag | Agent for coloring keratin fibres |
| EP1718601A1 (en) * | 2004-02-24 | 2006-11-08 | Wella Aktiengesellschaft | (3,5-diaminophenyl)(2,4-dihydroxyphenyl)methanone and its acid adducts, method for the production of the latter and use of said compounds for colouring fibres |
| CN101450904A (en) * | 2007-12-05 | 2009-06-10 | 盐城鼎龙化工有限公司 | Synthetic method of 2,5-diaminotoluene and sulphate thereof |
Non-Patent Citations (1)
| Title |
|---|
| 郑志国等: "高纯度2，5-二氨基甲苯硫酸盐的清洁合成新工艺", 《精细与专用化学品》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023282382A1 (en) * | 2021-07-06 | 2023-01-12 | 씨에스아이엠 주식회사 | Method for preparing 2,5-diaminotoluene sulfate |
| KR20230007754A (en) | 2021-07-06 | 2023-01-13 | 씨에스아이엠 주식회사 | Method for preparing 2,5-diaminotoluene sulfate |
| KR102604509B1 (en) * | 2021-07-06 | 2023-11-22 | 씨에스아이엠 주식회사 | Method for preparing 2,5-diaminotoluene sulfate |
| CN115838334A (en) * | 2021-09-18 | 2023-03-24 | 深圳有为技术控股集团有限公司 | Preparation method of 2, 5-diaminotoluene sulfate |
| CN114436857A (en) * | 2022-02-17 | 2022-05-06 | 浙江鼎龙科技股份有限公司 | 2, 5-diaminotoluene sulfate and preparation method of 2, 5-diaminotoluene |
| CN114436857B (en) * | 2022-02-17 | 2024-04-23 | 浙江鼎龙科技股份有限公司 | 2, 5-Diaminotoluene sulfate and preparation method of 2, 5-diaminotoluene |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101880780B (en) | Method for separating and extracting tungsten-molybdenum from mixed solution of tungstate-molybdate | |
| CN103803753B (en) | A kind of synthetical recovery treatment process of H acid trade effluent | |
| CN103553138B (en) | Comprehensive utilization method for separating, concentrating and purifying manganese sulfate, magnesium sulfate and calcium sulfate in high-salt waste water | |
| CN102910853B (en) | A kind of method using H acid Sewage treatments liquid production naphthalene series high-efficiency water-reducing agent | |
| CN101323614B (en) | Acidum folicum production method without sewerage discharge | |
| CN101450904B (en) | Synthetic method of 2,5-diaminotoluene and sulphate thereof | |
| CN102863112A (en) | Phenol and ammonia wastewater recycling treatment method by using single tower for performing de-acidification and de-amination simultaneously | |
| CN110590613A (en) | Method and production system for fully recycling taurine mother liquor | |
| CN105523674A (en) | Treatment method for 1-amino-8-naphthol-3,6-disulfonic acid monosodium salt production wastewater and equipment for implementing method | |
| CN101982456A (en) | Production method of environmental-friendly chloroacetic acid-process glycine | |
| CN202016881U (en) | System for producing soda ash and ammonium sulfate | |
| CN105084600A (en) | Method for efficiently treating salt-containing organic wastewater and application of method | |
| CN102320629A (en) | Method for producing reagent grade sodium sulfate by using white carbon black mother solution | |
| CN104086442A (en) | Preparation method of 2,5-diaminotoluene sulfate | |
| CN101244857B (en) | Alkali deweighting wastewater processing method and device | |
| CN101519383B (en) | Process for jointly producing cyanuramide, sodium carbonate and ammonium chloride by using carbamide | |
| CN210736624U (en) | Production system for recycling taurine mother liquor completely | |
| CN104445781B (en) | A kind of administering method of fused ring compound waste water | |
| CN102093441A (en) | After-treatment method for synthesizing neohesperidin dihydrochalcone from neohesperidin | |
| CN215048704U (en) | Process system for separating and recovering sodium sulfate and sodium bromide from wastewater | |
| CN104193061A (en) | Treatment method for paraquat pesticide wastewater | |
| CN105000738A (en) | Method for reducing content of salt in desulfurization waste liquor | |
| CN106277514A (en) | The method of recycling saccharin sodium wastewater | |
| CN105217863B (en) | A kind of handling process of disperse blue 60 production waste water | |
| CN103539285B (en) | The treatment process that a kind of wastewater of N-methylaniline production recycles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20141008 |