CN103772309B - The method of preparation 2,2 '-(4,4 '-diphenylethyllene) dibenzoxazine fine work - Google Patents
The method of preparation 2,2 '-(4,4 '-diphenylethyllene) dibenzoxazine fine work Download PDFInfo
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- CN103772309B CN103772309B CN201410013460.8A CN201410013460A CN103772309B CN 103772309 B CN103772309 B CN 103772309B CN 201410013460 A CN201410013460 A CN 201410013460A CN 103772309 B CN103772309 B CN 103772309B
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- C07—ORGANIC CHEMISTRY
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- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/62—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems having two or more ring systems containing condensed 1,3-oxazole rings
- C07D263/64—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems having two or more ring systems containing condensed 1,3-oxazole rings linked in positions 2 and 2' by chains containing six-membered aromatic rings or ring systems containing such rings
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Abstract
The invention discloses one and prepare 2,2 '-(4,4 '-diphenylethyllene) method of dibenzoxazine fine work, realize through steps such as condensation reaction, vulcanization reaction, crude product refining, solid-liquid separation, thick product refining desulfurization under the effect of 30%NaOH solution in crude product refining, desulfurization degree is high, product OB-1 high purity more than 99%, yield is high, and quality is good, color is vivid, use properties greatly promotes, and after desulfurization washing composition replaces traditional dimethylbenzene by 30%NaOH solution, production safety coefficient is high, operational safety, cost reduces.The present invention can be used for the fluorescent whitening agent OB-1 preparing the batching being used as the materials such as plastics, coating and road mark paint.
Description
Technical field
The invention belongs to industrial chemicals preparation field, particularly a kind of preparation method of white dyes, relate to one specifically and prepare 2, the method for 2 '-(4,4 '-diphenylethyllene) dibenzoxazine fine work.
Background technology
2,2 '-(4,4 '-diphenylethyllene) dibenzoxazine is fluorescent whitening agent OB-1, stable performance, there is the performances such as good high temperature resistant, sun-proof, chlorine-resistant drift and resistance to migration, be widely used as the mixture raw material of plastics, coating, road mark paint etc., play whitening effect.At present, OB-1 production technique have three kinds of modes: sulfur method technique, sodium tert-butoxide technique ， oxazole aldehyde method technique.Wherein, sulfur method production technique is due to production technology comparative maturity, and the quality product of production is better, by domestic and international manufacturer is accepted.
In existing technology, reacted by p-methylbenzoic acid and o-aminophenol and generate 2-(to methylbenzene) benzoxazole, under the effect of sulphur medium, generate the thick product of OB-1, thick product first obtains OB-1 crude product by the washing of xylene solution; OB-1 crude product dimethylbenzene secondary washing is refined, and obtains OB-1 fine work with trichlorobenzene and gac.There is following problem in this method:
1., owing to there is a small amount of sulphur in OB-1 after refining recrystallization, cause the outward appearance of product to shade, without light, crystalline particle size is uneven, in product, OB-1 purity is low.
2. need during crude product secondary washing to adopt a large amount of dimethylbenzene desulfurization, cause organic solvent consumption and equipment investment to strengthen, industrial production cost is high, simultaneously can not the thorough Ex-all by remaining sulphur during washing, and dimethylbenzene washing composition used is poisonous, can damage operator.
3. sulphur remaining in crude product major part in refining process can be left in gac, and refining filtering is high temperature filtration, and the burning-point of sulphur is low, reclaims in the process of charcoal after filtration, remains in the sulphur meeting spontaneous combustion in gac, there is potential safety hazard.
Application number is the Chinese invention patent application of 2013102293445, disclose one " new sulfur method 2; 2 '-(4; 4 '-diphenylethyllene) dibenzoxazine preparation method ", tolyl acid and Ortho-Aminophenol are dissolved in solvent oil by the method, using boric acid as catalyzer, generate 2-(as raw material to methylbenzene) benzoxazole; In 2-(is to methylbenzene) benzoxazole oxidative dimerization process, adopt the organic solvent of aprotic to replace sulphur as reaction medium, temperature of reaction is at 190 ~ 230 DEG C, reaction times controls at 3 ~ 4 hours, the energy consumption of this reaction decreases, yield is improved, but, the yield of product prepared by the method is minimum only has 80%, yield is still on the low side, white dyes crude product still needs to carry out washing desulphurization with dimethylbenzene, the use of dimethylbenzene improves production cost, and can endanger the healthy of operator.
Chinese invention patent CN102070551B discloses a kind of 2,2 '-(4,4 '-diphenylethyllene) dibenzoxazine preparation method, the method is improvements over the prior art methods, namely in vulcanization reaction still, 2-(is heated to 280-300 DEG C to methylbenzene) benzoxazole, utilize feeder to add sulphur by stages and in groups, react after adding sulphur and also complete immediately.During the method is produced, 2-(is excessive to methylbenzene) benzoxazole, because temperature of reaction is higher, reaction is instantaneous reaction, in order to avoid reaction is too fierce, causes danger, sulphur can only add by stages and in groups, the method significantly reduces the consumption of sulphur, but temperature of reaction is high, and the productive rate of 2-(to methylbenzene) benzoxazole and target product OB-1 is affected; The product needed that the method is produced carries out washing desulphurization with a large amount of dimethylbenzene, not only increases production cost, also endangers the health of operator; Dimethylbenzene thoroughly can not wash away the sulphur in product, mixes and have a small amount of sulphur in product, and the outward appearance of product OB-1 is poor, content and purity low.In addition, for sulphur, produce the expense of raw materials of 2-(to methylbenzene) benzoxazole higher, because 2-(is excessive to methylbenzene) benzoxazole, after folding product, need by unreacted 2-(to methylbenzene) benzoxazole Crystallization Separation out, later stage separating technology is more complicated, adds energy consumption and production cost.
Summary of the invention
The technical problem to be solved in the present invention, be to provide one and prepare 2,2 '-(4,4 '-diphenylethyllene) method of dibenzoxazine fine work, reacted by p-methylbenzoic acid and o-aminophenol and generate 2-(to methylbenzene) benzoxazole, the thick product of OB-1 is generated under the effect of sulphur medium, thick product refining desulfurization under the effect of 30%NaOH solution, obtains OB-1 product after solid-liquid separation, product OB-1 high purity more than 99%, yield is high, good product quality, color is vivid, and production safety coefficient is high, operational safety, production cost is low.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
One prepares 2, the method for 2 '-(4,4 '-diphenylethyllene) dibenzoxazine fine work, carries out according to following steps order:
(1) condensation reaction
Be p-methylbenzoic acid and the o-aminophenol mixing of 136:109 by weight proportion in condensation reaction still, add xylene solvent, reaction generates 2-(to methylbenzene) benzoxazole, in 200-250 DEG C, under vacuum state, 2-(is steamed methylbenzene) benzoxazole, obtains A;
(2) vulcanization reaction
Dropped into by A in vulcanization reaction still, drop into the 1.0-3.0 sulphur doubly that weight is A, be warming up to 210-250 DEG C, reaction 16-24h, adds xylene solvent, filters, obtain OB-1 crude product, i.e. B after solution heating;
(3) crude product refining
B and trichlorobenzene are dropped in refining kettle, adds gac and 30%NaOH solution, be warming up to 220 DEG C, insulation 2h, after B dissolves, at 200-210 DEG C, cross and filter gac, filtrate is moved in crystallization kettle, be cooled to 20-30 DEG C, obtain solidliquid mixture C;
(4) solid-liquid separation
Solidliquid mixture C crosses and filters trichlorobenzene mother liquor, dries up filter cake, obtains 2,2 '-(4,4 '-diphenylethyllene) dibenzoxazine fine work; Trichlorobenzene mother liquor directly overlaps to be used in next batch treating process.
One as foregoing invention limits, and the weight proportion of the 30%NaOH solution of step (3) described in crude product refining process and B is 1-4:20.
Another kind as foregoing invention limits, and step, (2) in vulcanization reaction, adds the solution warms to 130 DEG C after dimethylbenzene, and insulation 2h, filters.
Preparation method of the present invention integrally, the product OB-1 purity of preparation and yield high, good product quality, color is vivid, and production process safety coefficient is high, simple to operate, and cost is low.
The product OB-1 comparative result provided in the present invention and Chinese invention patent CN102070551B:
As seen from the above table, the product prepared by the present invention than the purity of the product OB-1 provided in Chinese invention patent CN102070551B and yield high, good product quality, color is vivid, granular size, even thickness.
Owing to have employed above-mentioned technical scheme, the present invention compared with prior art, acquired technical progress is: reacted by p-methylbenzoic acid and o-aminophenol and generate 2-(to methylbenzene) benzoxazole, the thick product of OB-1 is generated under the effect of sulphur medium, in thick product under 30%NaOH effect refining desulfurization, OB-1 product is obtained after solid-liquid separation, , the high purity more than 99% of product OB-1, yield >=92.5%, good product quality, color is vivid, use properties greatly promotes, vulcanization reaction temperature is low, refining desulfurization rate is high, after desulfurization washing composition replaces traditional dimethylbenzene by 30%NaOH solution, production safety coefficient is high, operational safety, cost reduces.
The present invention can be used for the fluorescent whitening agent OB-1 preparing the batching being used as the materials such as plastics, coating and road mark paint.
The present invention is described in further detail below in conjunction with specific embodiment.
Embodiment
embodiment 1 one kinds prepares 2, the method for 2 '-(4,4 '-diphenylethyllene) dibenzoxazine fine work
One prepares 2, the method for 2 '-(4,4 '-diphenylethyllene) dibenzoxazine fine work, and, solid-liquid separation rough through condensation reaction, vulcanization reaction, fine work realizes, and reaction equation is as follows:
Concrete preparation method in accordance with the following steps order carries out:
(1) condensation reaction
Be p-methylbenzoic acid and the o-aminophenol mixing of 136:109 by weight proportion in condensation reaction still, add xylene solvent, reaction generates 2-(to methylbenzene) benzoxazole, in 200 DEG C, under vacuum state, 2-(is steamed methylbenzene) benzoxazole, obtains A;
(2) vulcanization reaction
Dropped into by A in vulcanization reaction still, drop into the sulphur that weight is 1.0 times of A, be warming up to 210 DEG C, reaction 16h, add xylene solvent, solution heated solution is warming up to 130 DEG C, and insulation 2h, filters, obtain OB-1 crude product B;
(3) crude product refining
B and trichlorobenzene are dropped in refining kettle, add gac and 30%NaOH solution, the ratio of weight and number of 30%NaOH solution and B is 1:20, is warming up to 220 DEG C, insulation 2h, after B dissolves, at 200 DEG C, cross and filter gac, filtrate is moved in crystallization kettle, be cooled to 20 DEG C, obtain solidliquid mixture C;
(4) solid-liquid separation
Solidliquid mixture C crosses and filters trichlorobenzene mother liquor, dries up filter cake, obtains OB-1 product; Trichlorobenzene mother liquor directly overlaps to be used in next batch treating process.
The purity of product OB-1 prepared by embodiment 1 is 99%, yield is 93%, the quality of product is good, and crystalline particle thickness, size are even, and color is vivid, use properties greatly promotes, eliminate the process of xylene solvent washing crude product, solvent consumption is low, and production process safety coefficient is high, operational safety, cost reduces.
embodiment 2-6 prepares 2, the method for 2 '-(4,4 '-diphenylethyllene) dibenzoxazine fine work
Embodiment 2-6 is respectively one and prepares 2, the method for 2 '-(4,4 '-diphenylethyllene) dibenzoxazine fine work, and preparation process is identical with embodiment 1, and difference is only that wherein involved parameter is different, specifically as shown in table 1:
Table 1 prepares 2, correlation parameter involved in the method for 2 '-(4,4 '-diphenylethyllene) dibenzoxazine fine work
As shown in Table 1, product OB-1 purity >=99% prepared by embodiment 2-6, yield >=92.5%, good product quality, outward appearance is bright green or bright orange green, bright in colour, inclusion-free, crystallite size is homogeneous, and during refining filtering, temperature does not require too high, and economizes the process of removal xylene washing, solvent consumption is low, production process safety coefficient is high, operational safety, and cost reduces.
the different desulfurization washing composition of embodiment 7 is for the impact of product OB-1
Sulphur remaining in product OB-1 can reduce yield, the purity of product, cause quality product poor, be a bit darkish in color, the grain crystalline of product is not of uniform size, thus, remaining sulphur washed off the quality for improving product OB-1 by different desulfurization washing composition, reduce production cost and have great importance.
Desulfurization washing composition different in treating process has different effects for removing remaining sulphur in product OB-1, the impact of different washing composition for product OB-1 is explored by embodiment 7, the preparation process of product OB-1 is identical with embodiment 1, difference is only that the desulfurization washing composition added in crude product refining process is different, specifically as shown in table 2:
The different desulfurization washing composition of table 2 is for the impact of product OB-1
As seen from the above table, as use weak base CH
3cOOH(30%), when solution is as the sulphur removal of desulfurization washing composition, purity and the yield of product OB-1 are lower, being a bit darkish in color of product, and particle is uneven, and this is mainly due to CH
3cOOH(30%) solution is weak base, can not slough sulphur completely, still there is remaining sulphur in product; When use NaOH(30%) solution time, purity and the yield of product OB-1 are high, and outward appearance is shinny, uniform particles; When using KOH(30%) solution time, purity and the yield of product OB-1 are high, and outward appearance is shinny, uniform particles, but application is in the industrial production, KOH(30%) solution price is higher, condition of storage is high, and the cost of whole production technique can increase; When using highly basic sodium tert-butoxide (30%) solution, purity and the yield of product OB-1 are lower, the Huang that is a bit darkish in color of product, particle is uneven, this is too strong mainly due to sodium tert-butoxide (30%) solution alkaline, destroys the structure of product OB-1 while removing sulphur, and the use properties of product declines; When use dimethylbenzene and methanol solution time, purity and the yield of product OB-1 are lower, the Huang that is a bit darkish in color of product, and particle is uneven, this mainly due to dimethylbenzene and methanol solution not with sulfur reaction, use a large amount of washing composition all can not slough sulphur.
Embodiment 1-6 is only preferred embodiment of the present invention, be not the restriction of other form made for the present invention, any those skilled in the art may utilize above-mentioned technology contents to be changed or be modified as the Equivalent embodiments of equivalent variations as enlightenment.In every case be the technical spirit not departing from the claims in the present invention, to simple modification, equivalent variations and remodeling done by above embodiment, still belong to the scope of the claims in the present invention protection.
Claims (1)
1. prepare 2 for one kind, the method for 2 '-(4,4 '-diphenylethyllene) dibenzoxazine fine work, its
be characterised in thatdescribed preparation method carries out according to following steps order:
(1) condensation reaction
Be p-methylbenzoic acid and the o-aminophenol mixing of 136:109 by weight proportion in condensation reaction still, add xylene solvent, reaction generates 2-(to methylbenzene) benzoxazole, in 200-250 DEG C, under vacuum state, 2-(is steamed methylbenzene) benzoxazole, obtains A;
(2) vulcanization reaction
Dropped into by A in vulcanization reaction still, drop into the 1.0-3.0 sulphur doubly that weight is A, be warming up to 210-250 DEG C, reaction 16-24h, adds xylene solvent, filters, obtain OB-1 crude product, i.e. B after solution heating;
Add the solution warms to 130 DEG C after dimethylbenzene, insulation 2h, filters;
(3) crude product refining
B and trichlorobenzene are dropped in refining kettle, adds gac and 30%NaOH solution, be warming up to 220 DEG C, insulation 2h, after B dissolves, at 200-210 DEG C, cross and filter gac, filtrate is moved in crystallization kettle, be cooled to 20-30 DEG C, obtain solidliquid mixture C;
The weight proportion of described 30%NaOH and B is 1-4:20;
(4) solid-liquid separation
Solidliquid mixture C crosses and filters trichlorobenzene mother liquor, dries up filter cake, obtains 2,2 '-(4,4 '-diphenylethyllene) dibenzoxazine fine work; Trichlorobenzene mother liquor directly overlaps to be used in next batch treating process.
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| CN105111853A (en) * | 2015-09-18 | 2015-12-02 | 浙江顺达新材料股份有限公司 | Road marking paint and production process thereof |
| CN110423236B (en) * | 2019-08-22 | 2020-12-18 | 江苏格罗瑞化学有限公司 | Preparation method of fluorescent whitening agent for whitening textiles |
| CN112457269B (en) * | 2020-11-20 | 2023-01-03 | 河北星宇化工有限公司 | Production process of fluorescent whitening agent OB-1 |
| CN115260115A (en) * | 2022-08-09 | 2022-11-01 | 河南瑞奇特化工有限公司 | Indoor and outdoor color difference-free fluorescent whitening agent and preparation method thereof |
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