CN103483868B - Preparation method for acid resistance type disulfonic acid liquid fluorescent whitening agent - Google Patents
Preparation method for acid resistance type disulfonic acid liquid fluorescent whitening agent Download PDFInfo
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- CN103483868B CN103483868B CN201310412609.5A CN201310412609A CN103483868B CN 103483868 B CN103483868 B CN 103483868B CN 201310412609 A CN201310412609 A CN 201310412609A CN 103483868 B CN103483868 B CN 103483868B
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Abstract
The invention belongs to the technical field of dyeing and printing chemical auxiliary agent preparation methods, and particularly relates to an acid resistance type disulfonic acid liquid fluorescent whitening agent preparation method, wherein problems of complex processes, high cost and poor acid resistance of products in the existing preparation method are mainly solved. According to the preparation method, cyanuric chloride, 4,4-diaminostilbene-2,2-disulfonic acid, aniline, isopropanolamine and diethanolamine are adopted as raw materials, a three-step condensation reaction is performed to synthesize, and a nano-filtration membrane filtration method is adopted to carry out a desalination filtration treatment to obtain the product. The obtained product has advantages of high acid resistance, stability and the like.
Description
Technical field
The invention belongs to printing and dyeing chemical assistant preparation method technical field, be specifically related to a kind of preparation method of anti-acid Disulfonic acid liquid florescence brightener.
Background technology
In recent years, white dyes is widely used in many fields such as printing and dyeing, papermaking, washing, plastics, coating and rubber, plays to brighten, increase effect that is gorgeous and blast.
Along with large-scale printing and dyeing mill is increasing, mainly contain several direction to the demand of white dyes: efficient whitening performance, less addition, stable performance, resistance to acids and bases is good, and be suitable for operate continuously and automatization interpolation, environmental pollution is little.
At present, most cotton fabrics, in the Final finishing course of processing, often needs to carry out shrinkproof, wrinkle resistant and mellowing.In order to enhance productivity, save energy, current most factory adopts brightens the same bath process with resination.Can use metal-salt and citric acid, oxalic acid or phosphoric acid mixed catalyst in general resination working fluid, make working fluid be acid, pH is about 3.Domestic market is mainly two triazine amino-stilbene type for the white dyes that natural fiber brightens, and by the quantity containing sulfonic acid group, can be divided into two, four, six sulphur three kinds.Wherein for the mainly disulfonic acid fluorescent bleaches VBL that cotton fabric brightens, BA, CXT, 4BK and six sulfonic acid white dyes MST.
Disulfonic acid class whitening agent has higher whitening performance, be mainly used in cotton, fiber crops, the brightening of cellulose base fiber fabric, brightening of the gorgeous and paper pulp of the increasing of light fibres fabric, but because contained sulfonic acid group comparatively small amt in this body structure, water-soluble poor, acid resistance is also not as six sulphur white dyess, the product of its liquid dosage form, in application process, often require pH >=7.5, namely in neutrality and weakly alkaline environment, result of use is best.When pH=3.0, use can occur to separate out or degradation problem under whiteness, is not suitable for the same bath process brightened with resination.
Although hexa-sulphonic acid white dyes MST is suitable for the same bath process brightened with resination, but due to sulfonic acid group more (6) contained in its structure, good hydrophilic property, but can not show a candle to disulfonic acid series products with cellulose affinity, whitening effect is mutually more far short of what is expected than disulfonic acid fluorescent bleaches.In addition, it produces raw materials used price far above disulfonic acid class whitening agent, and use cost is higher.
Along with China's economy develops and the improving constantly of living standards of the people fast, weaving and printing and dyeing industry obtain flourish, the requirement of people to the various aspects of performance of the products such as clothing improves constantly, when how to use white dyes under slant acidity condition, ensure the result of use of white dyes, be of great practical significance.
CN1287200A reports the special liquid fluorescent whitening agent of a kind of paper industry and synthesis technique thereof, comprises feed purification, organic reaction, work in-process purifying, refines concentrated four steps.Utilize vibratory screening apparatus to grind raw material, purify, be unfavorable for industrialization; And the multiple solubilisation aids such as urea are added in aftertreatment, be unfavorable for environmental protection while raising the cost.
Patent CN102477227A reports a kind of disulfonic acid fluorescent whitening agent not adding extra solubility promoter, but the method needs first to carry out 1-R
1-2-R
2the synthesis of-acrylamide and Monoethanolamine MEA BASF, replace single fat amine with its adduct, improve the stability of product, but the synthetic product of the method to acrylamide and Monoethanolamine MEA BASF requires higher, not easily carry out suitability for industrialized production, and the acid resistance of unreceipted the finished product how.
Patent CN102093750A reports a kind of preparation method of sulfonic acid liquid fluorescent whitening agent of cryostatic stabilization, disulfonic acid fluorescent whitening agent dyestuff, cellosolve, polyoxyethylene glycol compounds, multicomponent alcoholics compound, urea and water are stirred, heating for dissolving, obtains product after cooling, filtration.Though the method is simple to operate, be easily subject to the impact of the quality of disulfonic acid fluorescent whitening agent own, once itself saltiness is higher or containing other impurity, the stable storing phase of the finished product will reduce short greatly, and in addition, the acid resistance of product does not clearly state.
Patent CN101094842A discloses a kind of white dyes of improvement, improved white dyes height is water-soluble, and there is the anionic charge of minimizing, it has higher stable row to environment such as acid, salt, serve positive effect, but its technique is complicated to the problem solving " anionic trash " in printing and dyeing application, desired raw material not easily obtains, and in final finished, also can add conventional solubilisation aids, as urea etc., environmental protection is made a big impact.
Patent CN101547968A reports the white dyes/PVOH aqueous solution of the low viscosity shelf-stable that a kind of papermaker can directly use, but this product only has 5 days the stable staging life of 50 DEG C, and acid resistance test has no relevant report; Patent US6660705 reports a kind of liquid fluorescent whitening agent formula being mixed solvent with fatty alcohol-polyoxyethylene ether and glycerine; Patent CN1687348 disclose a kind of with fatty alcohol-polyoxyethylene ether, polyoxyethylene glycol, Diethylene Glycol and water for the formula of liquid fluorescent whitening agent prepared by mixed solvent; Patent CN101932567A discloses the preparation method of a kind of whitening agent and organic acid storage stable solution.But the acid resistance of these methods above-mentioned its finished product all undeclared, has some limitations.
Summary of the invention
The object of this invention is to provide a kind of preparation method of anti-acid toluylene triazine Disulfonic acid liquid florescence brightener.
The preparation method of a kind of anti-acid disulfonic acid body white dyes of the present invention, comprises the following steps:
(1) mixture of ice and water is made according to water and ice part by weight 1:1 ~ 1.5, by mixture of ice and water and cyanuric chloride part by weight 1:15 ~ 20, cyanuric chloride is dispersed in mixture of ice and water, in mixture of ice and water, emulsifying agent is added according to cyanuric chloride and emulsifying agent part by weight 2800 ~ 3000:1, according to cyanuric chloride and 4, 4-diaminobenzil-2, 2-sodium disulfonate adds 4 with the mol ratio of 1:0.4 ~ 0.5 in above-mentioned solution, 4-diaminobenzil-2, 2-sodium disulfonate, pH value of reaction system is controlled for 2 ~ 4 with acid binding agent, at 0 ~ 10 DEG C, carry out the first step condensation reaction to disappear to amino value, the first step condensation reaction terminates, obtain condensation product I, its structural formula is as follows:
(2) according to condensation product I: aniline is the mol ratio of 1:1.8 ~ 2, terminate to the first step condensation reaction to add aniline in the reaction solution formed, pH value of reaction system is controlled for 5 ~ 7 with acid binding agent, react at being warming up to 15 ~ 45 DEG C, with amino disappearance for reaction end, carry out second step condensation reaction, obtain condensation product (II), its structural formula is as follows:
(3) step (2) is generated the mixture that condensation product (II) adds α-amino isopropyl alcohol and diethanolamine, condensation product (II) controls in 1:1.4 ~ 1.7 with the mol ratio of α-amino isopropyl alcohol and diethanolamine mixture, pH value of reaction system is controlled for 7.5 ~ 11.0 with acid binding agent, carry out at being warming up to 80 ~ 120 DEG C reacting constant to pH value, carry out the 3rd step condensation reaction, obtain three kind of three contracting product III, IV and V, its structural formula is as follows:
(4) nanofiltration membrane method desalting and filtering process three contracting product III, IV and V is adopted, preparation Disulfonic acid liquid florescence brightener.
Described acid binding agent is NaHCO
3solution, Na
2cO
3solution or NaOH solution.
Described emulsifying agent is fatty alcohol-polyoxyethylene ether or polyoxyethylene glycol compounds, comprises PEG-300, one or more in PEG-400, PEG-600.
The mol ratio of described α-amino isopropyl alcohol and diethanolamine is 1:1.4 ~ 1.7.
In the present invention in the first step condensation reaction, control pH value less than 4.0, temperature 0 ~ 10 DEG C, reaction end disappears with amino and is as the criterion; Second step condensation reaction, control ph 5.0 ~ 7.0, temperature 15 ~ 45 DEG C is best, and reaction end disappears with amino and is as the criterion; 3rd step condensation reaction, control ph is 7.5 ~ 11.0, and temperature 80 ~ 120 DEG C is best, and reaction end is not changed to standard with pH, if temperature or pH too high, all can produce a large amount of by products, thus reduce the main content of product, affect the effect of product.
Described α-amino isopropyl alcohol and the mol ratio of diethanolamine are 1.0:0.7, carry out the 3rd step condensation reaction after mixing, what both ensured to generate is the effect that the white dyes of three kinds of different structures plays compound synergic, and whiteness is higher, can ensure that again product is better water-soluble, acid resistance is better.
For liquid-type white dyes, the bonding force of disulfonic acid series products and fabric fibre is strong, and dye uptake is high, and with four, compared with hexa-sulphonic acid product, same addition, can obtain higher whiteness, has comparatively obvious advantage in cost performance.But due to the limitation of this body structure of disulfonic acid series products, poor to the adaptability of system pH, under strong acid or basic conditions, application performance is obviously deteriorated, and product there will be slight precipitation, affects the final effect of dyeing and finishing.
The present invention is mainly for the limitation of two triazine amino-stilbene type disulfonic acid fluorescent whitening agent structure, cause it water-soluble poor, resistance to acids and bases is bad, in actual application, be subject to the impact of system environment, especially the impact of pH, whitening performance declines to some extent, affect result of use, the aliphatic amide adopting the compound of α-amino isopropyl alcohol and diethanolamine to replace reacts, thus produce the toluylene triazine liquid fluorescent brightener of three kinds of different structures, after the reaction of this toluylene triazine liquid fluorescent brightener relative single fat amine obtain toluylene triazine liquid fluorescent brightener, mainly contain following three kinds of advantages:
1, the multiple oh groups introduced by three-step reaction considerably increase the water-soluble of toluylene triazine liquid fluorescent brightener, when preparing liquid dosage form toluylene triazine liquid fluorescent brightener, as long as the inorganic salts in system is removed to lower level by postprocessing working procedures, at a small amount of hydrotropy stablizer of interpolation, namely Absorbable organic halogens is deposited;
2, toluylene triazine liquid fluorescent brightener is in actual application, comparatively strong to system Adaptability of medium, in slant acidity system, still can play good whitening effect;
3, symmetrical and asymmetric three kinds of disulfonic acid class I liquid I white dyess are obtained after reaction, there is the effect of compound synergic, white dyes is brightening on matrix mainly with the set of unit molecule state, the relative concentration of composite rear each component declines, the fluorescence quantum yield of each component is increased, fluorescence intensity strengthens, produce the fluorescent brightening effect higher than one-component, fundamentally change the deficiency of simple synthetics in whiteness, the quality of remarkable lifting toluylene triazine liquid fluorescent brightener, the significantly raising of toluylene triazine liquid fluorescent brightener whiteness also can make client's in use consumption minimizing, reduce production cost.
The present invention, from the structure changing white dyes, inherently improves the water-soluble of disulfonic acid type liquid brightener, and wait after postorder process through filtration, product stability is good, and resistance to acids and bases significantly improves.
The present invention has following beneficial effect: obtain symmetrical and asymmetric three components disulfonic acid class I liquid I white dyes, it is amber color liquid, soluble in water, odorlessness, stable performance, its maximum absorption wavelength is 348nm, and maximum emission wavelength is 434nm, has hyperfluorescenceZeng Yongminggaoyingguang, it is the liquid fluorescent whitening agent that a kind of resistance to acids and bases is good, solve disulfonic acid class I liquid I whitening agent to system pH sensitive issue, use in stronger acid system, still can obtain good whitening effect.Meanwhile, this product has the effect of compound synergic, solves the problem of one-component poor stability, reduces client's usage quantity, has saved production cost.
Embodiment
Embodiment 1
(1), in 2000ml beaker, 300g water is added, 350g trash ice, ice bath cools, add 30g cyanuric chloride and 0.01gPEG-400, stirring to pulp 1.5 hours, by 27g4,4-diaminobenzil-2,2-sodium disulfonate at the uniform velocity joined in above-mentioned solution in 1.5 ~ 2.0 hours, was the NaHCO of 7% with massfraction
3solution regulates pH to be 2.5 ~ 3.0, keeps this pH value 1.5 hours, and control temperature is below 10 DEG C, and reaction is until amino value disappears, and the first step condensation reaction terminates;
(2), in step (1) adding 15g aniline, is the Na of 10% with massfraction
2cO
3regulate pH to be 6.5, be warming up to 40 DEG C, reaction is until amino value disappears, and second step condensation terminates;
(3), in step (2) solution add the α-amino isopropyl alcohol of 25g and the diethanolamine of 14g, be warming up to 95 ~ 100 DEG C, regulate pH to be 8 ~ 9 by the NaOH solution that massfraction is 30%, react 3 hours;
(4), reaction solution stirring is cooled to less than 55 DEG C, use Büchner funnel suction filtration, except the insoluble impurity that anhydrates, filtrate through WTM-1812D type nanofiltration membrane at 10 DEG C, carry out desalination and concentration under the pressure of 1.3MPa, specific conductivity, when 350-200 μ S/cm (diluting 200 times), stops nanofiltration, be concentrated into prescribed strength, obtain Disulfonic acid liquid florescence brightener.
By liquid chromatographic detection, the liquid fluorescent whitening agent prepared is the mixture of three components, and its retention time is respectively 7.953,8.216 and 8.598min.And then measured by each component ratio of high performance liquid chromatography to mixture, the ratio of three components is (III): (IV): (V)=19:23:17.
Embodiment 2
Add the α-amino isopropyl alcohol of 20g and the diethanolamine of 18g in step (3), other operating process are with embodiment 1.Adopt the ratio of each component of high-performance liquid chromatogram determination, the mass ratio of three components is (V): (VI): (VII)=7:16:25.
Embodiment 3
Using massfraction be 30% NaOH solution regulate the pH value of each step as acid binding agent.Add the α-amino isopropyl alcohol of 25g and the diethanolamine of 14g in step (3), other operating process are with embodiment 1.Adopt the ratio of each component of high-performance liquid chromatogram determination, the mass ratio of three components is (V): (VI): (VII)=3:11:17.
Embodiment 4
According to the relevant regulations of " white dyes brightens the assay method of intensity and coloured light " in GB/T 23979.2-2009, under identical dye level and bath raio, condition of different pH, the above each embodiment of test prepares the whitening effect of whitening agent.
Get each two parts of the representative sample at present in printing and dyeing and paper industry widely used liquid fluorescent whitening agent CI.83 again, test its whitening performance equally according to above method, the white dyes obtained with various embodiments of the present invention compares, and its test data is as follows:
As can be seen from the above data, the liquid fluorescent whitening agent prepared by the present invention is better than at present at the whitening effect of the widely used liquid fluorescent whitening agent CI.83 of dyeing the whitening effect of fabric in slant acidity system.
Embodiment 5
In following brightener solution, add citric acid, adjust ph, temperature 25 DEG C, observe pH to the impact of brightener solutions stability.
As can be seen from the above data, the stability of the liquid fluorescent whitening agent prepared by the present invention in slant acidity system is better than at present at dyeing other white dyess widely used.
Claims (4)
1. a preparation method for anti-acid Disulfonic acid liquid florescence brightener, is characterized in that comprising the following steps:
(1) mixture of ice and water is made according to water and ice part by weight 1:1 ~ 1.5, by mixture of ice and water and cyanuric chloride part by weight 1:15 ~ 20, cyanuric chloride is dispersed in mixture of ice and water, in mixture of ice and water, emulsifying agent is added according to cyanuric chloride and emulsifying agent part by weight 2800 ~ 3000:1, according to cyanuric chloride and 4, 4-diaminobenzil-2, 2-sodium disulfonate adds 4 with the mol ratio of 1:0.4 ~ 0.5 in above-mentioned solution, 4-diaminobenzil-2, 2-sodium disulfonate, pH value of reaction system is controlled for 2 ~ 4 with acid binding agent, at 0 ~ 10 DEG C, carry out the first step condensation reaction to disappear to amino value, the first step condensation reaction terminates, obtain condensation product I, its structural formula is as follows:
(2) according to condensation product I: aniline is the mol ratio of 1:1.8 ~ 2, terminate to the first step condensation reaction to add aniline in the reaction solution formed, pH value of reaction system is controlled for 5 ~ 7 with acid binding agent, react at being warming up to 15 ~ 45 DEG C, with amino disappearance for reaction end, carry out second step condensation reaction, obtain condensation product (II), its structural formula is as follows:
(3) step (2) is generated the mixture that condensation product (II) adds diisopropanolamine (DIPA) and diethanolamine, condensation product (II) controls in 1:1.4 ~ 1.7 with the mol ratio of diisopropanolamine (DIPA) and diethanolamine mixture, pH value of reaction system is controlled for 7.5 ~ 11.0 with acid binding agent, carry out at being warming up to 80 ~ 120 DEG C reacting constant to pH value, carry out the 3rd step condensation reaction, obtain three kind of three contracting product III, IV and V, its structural formula is as follows:
(4) nanofiltration membrane method desalting and filtering process three contracting product III, IV and V is adopted, preparation Disulfonic acid liquid florescence brightener.
2. the preparation method of a kind of anti-acid Disulfonic acid liquid florescence brightener according to claim 1, is characterized in that described acid binding agent is NaHCO
3solution, Na
2cO
3solution or NaOH solution.
3. the preparation method of a kind of anti-acid Disulfonic acid liquid florescence brightener according to claim 1, it is characterized in that described emulsifying agent is fatty alcohol-polyoxyethylene ether or polyoxyethylene glycol compounds, comprise PEG-300, one or more in PEG-400, PEG-600.
4. the preparation method of a kind of anti-acid Disulfonic acid liquid florescence brightener according to claim 1, is characterized in that the mol ratio of described diisopropanolamine (DIPA) and diethanolamine is 1:1.4 ~ 1.7.
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| CN105400229A (en) * | 2015-10-23 | 2016-03-16 | 山西青山化工有限公司 | Preparation method of liquid fluorescent whitening agent used for papermaking |
| CN112724094A (en) * | 2020-12-25 | 2021-04-30 | 山西晋光化工有限公司 | Novel environment-friendly disulfonic acid liquid fluorescent whitening agent and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5948153A (en) * | 1998-04-24 | 1999-09-07 | Milliken & Company | Water-soluble complexes of optical brighteners and quaternary ammonium compounds which are substantially free from unwanted salts |
| CN1287200A (en) * | 1999-09-03 | 2001-03-14 | 俎涛 | Fluorescent liquid brightener and its synthesis |
| CN101096367A (en) * | 2005-10-17 | 2008-01-02 | 山东大学 | Triazine radical amido diphenyl ethylene fluorescent bleaches |
| CN101654894A (en) * | 2009-09-11 | 2010-02-24 | 山西青山化工有限公司 | Preparation method of toluylene triazine liquid fluorescent brightener composite |
| CN102477227A (en) * | 2011-11-11 | 2012-05-30 | 山西青山化工有限公司 | Method for preparing liquid fluorescent brightener composition of diphenylvinyl triazine compounds |
| CN102926279A (en) * | 2012-11-08 | 2013-02-13 | 山西青山化工有限公司 | Method for preparing liquid fluorescent brightener combination capable of being steadily stored |
| CN102993774A (en) * | 2011-09-15 | 2013-03-27 | 日本化药株式会社 | Stable thick aqueous composition for stilbene derivative |
-
2013
- 2013-09-11 CN CN201310412609.5A patent/CN103483868B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5948153A (en) * | 1998-04-24 | 1999-09-07 | Milliken & Company | Water-soluble complexes of optical brighteners and quaternary ammonium compounds which are substantially free from unwanted salts |
| CN1287200A (en) * | 1999-09-03 | 2001-03-14 | 俎涛 | Fluorescent liquid brightener and its synthesis |
| CN101096367A (en) * | 2005-10-17 | 2008-01-02 | 山东大学 | Triazine radical amido diphenyl ethylene fluorescent bleaches |
| CN101654894A (en) * | 2009-09-11 | 2010-02-24 | 山西青山化工有限公司 | Preparation method of toluylene triazine liquid fluorescent brightener composite |
| CN102993774A (en) * | 2011-09-15 | 2013-03-27 | 日本化药株式会社 | Stable thick aqueous composition for stilbene derivative |
| CN102477227A (en) * | 2011-11-11 | 2012-05-30 | 山西青山化工有限公司 | Method for preparing liquid fluorescent brightener composition of diphenylvinyl triazine compounds |
| CN102926279A (en) * | 2012-11-08 | 2013-02-13 | 山西青山化工有限公司 | Method for preparing liquid fluorescent brightener combination capable of being steadily stored |
Non-Patent Citations (1)
| Title |
|---|
| 混合型二苯乙烯类新荧光增白剂的简易合成与性能;陶武松等;《中华纸业》;20090223(第04期);16-21 * |
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