CN102477227A - Method for preparing liquid fluorescent brightener composition of diphenylvinyl triazine compounds - Google Patents
Method for preparing liquid fluorescent brightener composition of diphenylvinyl triazine compounds Download PDFInfo
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Abstract
The present invention relates to a production process of a chemical additive special for papermaking, in particular to a method for preparing a liquid fluorescent brightener composition of diphenylvinyl triazine compounds. The invention mainly solves the problems of low fluorescence intensity and low brightness of a single-component liquid fluorescent brightener. The method adopts cyanuric chloride, 4,4'-diamino-2,2'-stilbenedisulfonic acid (DSD acid), aniline, monoethanolamine and 1-R1-2-R2-acrylamide as raw material, and employs four-step reaction. The inventive liquid fluorescent brightener composition has convenient usage, good acid resistance, and good storage stability at a room temperature, and is suitable for continuous adding and metering during automatic production.
Description
Technical field
The present invention relates to the production technique of the special-purpose chemical assistant of a kind of papermaking, be specifically related to a kind of preparation method of toluylene triazine liquid fluorescent brightener composite.
Background technology
Nowadays, white dyes is known by people, is applied to many fields such as papermaking, washing, printing and dyeing, plastics, coating and rubber in a large number, is added the back fabric or paper etc. is played the effect of brightening, increase gorgeous and blast.Wherein, papermaking is one of topmost Application Areas of whitening agent, and continually developing new prescription of the special-purpose high whiteness white dyes of papermaking and novel process is research focus in the last few years.
In theory, the fluorescence of molecule refers to that molecule self has absorbing ultraviolet light and sends the ability of blue light in the visible region, and such molecule is called as white dyes.After white dyes was added in the paper, it can absorb the UV-light of 350nm-360nm, and concurrent efferent echo is grown up and is about the visible blue of 440nm, and what this blue color can the compensation fibre material is light yellow, thereby increased the apparent whiteness of paper.
Two triazine amino-stilbene type white dyess are one type of research and use white dyes kind the earliest; What the paper-making industry consumption was maximum at present also is the type white dyes; Though it is at present various in style; But its shortcoming is separately all arranged, low such as poorly water-soluble, yellowing point, brighten intensity difference and narrow in application range etc.For overcoming above-mentioned shortcoming, people have developed a series of paper grade (stock) liquid fluorescent whitening agent in succession.
The patent No. is the water-soluble title complex that the patent of CN1303424A discloses a kind of white dyes and quarternary ammonium salt compound; Basically do not contain inorganic salt; Its compound is to select for use white dyes sulfonated bodies and quaternary ammonium salt to carry out complex reaction; The purification technique that adopts subsequently has SX, is separated, high pressure ultrafiltration and other filter methods, removes the nearly all excessive salt that generates in this reaction process, generates a kind of water-soluble complexes.
The patent No. is that the patent of CN1411452A discloses a kind of soluble amphoteric white dyes; Radical X comprising a whitening agent characteristic; X comprises at least one anion substituent; And at least one tertiary amine groups Z with at least one not color development, be aliphatic polyquaternary amine-hydroxyl radical Y covalent attachment basically, Y comprises more than one quaternary ammonium group, wherein each hydroxyl radical is optional is broken off or replaces by one or more other heteroatomss.
More than two pieces of disclosed toluylene triazine white dyess that are single structure of patent, yet the white dyes of single structure in use exists sweet thatch whiteness and colour fastness is relatively poor, easy problem such as deposition under acidic conditions.Therefore people develop the white dyes kind of having synthesized some mixed types again, attempt to improve through composite method the fluorescence intensity and the Gan Ci whiteness of whitening agent unit's consumption.
The patent No. is the preparation method that the patent of CN101429344A discloses a kind of mixed type liquid fluorescent whitening agent, adopts cyanuric chloride, DSD acid, aniline sulfonic acid and diethylolamine three step condensations to obtain white dyes.Aniline-2 is at first used in this invention, 4-disulfonic acid and aniline-2, and the mixture and the cyanuric chloride of 5-disulfonic acid react; Obtain benzene-2,4-(4,6-dichlorotriazine-2-is amino) disulfonic acid and benzene-2; The mixture of 5-(4,6-dichlorotriazine-2-is amino) disulfonic acid, this mixture is earlier with 4; 4 '-diaminobenzil-2; 2 '-sulfonic acid carry out second the step condensation reaction, the product that obtains again with morpholine carry out the 3rd the step condensation reaction, obtain a kind of mixed type composition of liquid fluorescent bleaching agent that contains two compounds at last.
The patent No. is the preparation method that the patent of CN101654894A discloses a kind of toluylene triazine liquid fluorescent brightener composite; It is with cyanuric chloride, Sulphanilic Acid, 4; 4 '-diaminobenzil-2,2 '-disulfonic acid, morpholine and diethylolamine are raw material, and be synthetic through three-step reaction; And adopting the processing of nf membrane filter method desalting and filtering to obtain, this method has made a kind of symmetry and asymmetric toluylene triazine liquid fluorescent brightener composite of containing.
More than the white dyes of two pieces of disclosed these two kinds of mixed types of patent, on whitening effect, be greatly improved than the white dyes of single kind really, but these products are when being applied to papermaking, occurred still that whiteness is not high, shortcoming such as be a bit darkish in color.Along with the increase of market to the demand of high-grade paper product, synthetic a kind of high whiteness, highly active polycomponent papermaking dedicated liquid white dyes have crucial meaning.
Summary of the invention
The present invention is primarily aimed at the shortcoming that one-component liquid fluorescent whitening agent fluorescence intensity is lower, whiteness is not high, and a kind of preparation method of toluylene triazine liquid fluorescent brightener composite is provided.
The preparation method of toluylene triazine liquid fluorescent brightener composite according to the invention be with cyanuric chloride, 4,4 '-diaminobenzil-2,2 '-disulfonic acid (DSD acid), aniline, Monoethanolamine MEA BASF and 1-R
1-2-R
2-acrylic amide is a raw material, and through the synthetic preparation of four-step reaction, concrete preparation method is following:
1) cyanuric chloride is dispersed in the frozen water solution, the mol ratio according to 1: 0.43～0.5 adds 4,4 '-diaminobenzil-2,2 '-sodium disulfonate solution; Using the pH value of acid binding agent conditioned reaction system is 4.0～7.0, under 0～15 ℃, reacts stopped reaction when amino disappears to reaction system; Make compound I, promptly 4,4 '-two (4; 6-dichlorotriazine-2-is amino) toluylene-2,2 '-sodium disulfonate, its structural formula is following:
2) according to aniline: the mol ratio of compound I is that 1: 0.45～0.55 ratio adds aniline in the reaction solution of step (1); Using the pH value of acid binding agent conditioned reaction system is 7.0～8.0; Being warming up to 25～50 ℃ reacts; Stopped reaction when amino disappears to reaction system makes compound I I, and its structural formula is following:
3) with 1-R
1-2-R
2-acrylic amide and Monoethanolamine MEA BASF carry out addition reaction, make the mixture of compound III and compound IV, i.e. midbody, and the structural formula of compound III and compound IV is following:
R wherein
1, R
2Be H or C
1～C
2The representative examples of saturated aliphatic substituting group;
4) according to compound I I: the mol ratio of midbody is that 1: 1.2～1.5 ratio adds midbody in the reaction solution of step (2); Using the pH value of acid binding agent regulation system is 8.5～12.0, is warming up to 60～110 ℃, reacts stopped reaction when the pH value of system does not change; Filtering reacting liquid; Make compound V, compound VI and compound VI I, i.e. toluylene triazine liquid fluorescent brightener composite, wherein the structure of compound V, compound VI and compound VI I is following:
Wherein preferred acid binding agent is that massfraction is 10～30% the sodium hydroxide or the aqueous solution of yellow soda ash.
Preferred 1-R
1-2-R
2The mol ratio of-acrylic amide and Monoethanolamine MEA BASF is 1: 0.98～1.02.
Preferably being filtered into the employing nf membrane, is under 0.2～2.OMpa condition at pressure, reaction solution is permeated desalting and filtering repeatedly handle.
Preferred nf membrane is a NFM series membranes core.
The present invention tests the whitening effect of the whitening agent of the present invention's preparation according to the relevant regulations of " white dyes brightens the mensuration-paper coloring method of intensity and coloured light " among the GB/T 23979.2-2009, and is specific as follows:
Extract 7 samples of the present invention, paper adopts φ 7cm fast qualitative filter paper, dyes with dip method; Dye level 0.5% (owf), bath raio: 1: 150, dyeing time 15min; The dry back whiteness value of measuring each outturn that finishes dyes; Get at present two parts of the representative samples of the widely used liquid fluorescent whitening agent CI.220 of paper industry, according to above its whitening performance of method test, its test data is following equally again:
| Instance | The test whiteness |
| Sample 1 | 98.4 |
| Sample 2 | 99.0 |
| Sample 3 | 98.7 |
| Sample 4 | 98.0 |
| Sample 5 | 98.7 |
| Sample 6 | 98.2 |
| Sample 7 | 97.8 |
| White dyes 220 samples 1 | 97.6 |
| White dyes 220 samples 2 | 97.2 |
Can find out that from above data the prepared liquid fluorescent whitening agent of the present invention is superior at present the whitening effect at the widely used liquid fluorescent whitening agent CI.220 of paper industry to the whitening effect of paper.
The present invention is strict control reaction conditions in the process of four-step reaction, in the first step condensation reaction, and control pH value 4.0～7.0,0～15 ℃ of temperature, reaction end disappears with amino and is as the criterion; The second step condensation reaction, control pH value 7.0～8.0,25～50 ℃ of temperature, reaction end disappears with amino and is as the criterion; The 3rd step condensation reaction is controlled the pH value 8.5～12.0,60～110 ℃ of temperature, and reaction end is not changed to standard with pH, has guaranteed the content of principal product to greatest extent, has reduced the generation of by product, has guaranteed the generation of ultimate aim product.
The present invention adopts 1-R
1-2-R
2-acrylic amide and Monoethanolamine MEA BASF adduct replace single aliphatic amide to react; The compound that produces different structure is participated in subsequent reactions; Both guaranteed that product was water-soluble, and made the white dyes of three kinds of different structures of generation play synergistic effect again, whiteness is higher; Thereby further improve the stability of product, promote product quality.
Selecting massfraction when selecting acid binding agent for use among the preparation method of the present invention for use is 10～30% the sodium hydroxide or the aqueous solution of yellow soda ash; Through the adjustment speed of response, prevented hydrolysis reaction, compare with the technology of making acid binding agent of caustic soda; The quality of product is better, and cost is lower.
Because white dyes is a liquid product, the stability of product is very important, adopts acid out technology can not guarantee the stability of product.Through discovering that the principal element that influences product stability is to react the salt (NaCl) of generation, salts contg is low more, and the stability of liquid fluorescent whitening agent is good more.Using nanofiltration membrane filtration mode method of the present invention replaces the salting-out process that step is many, waste of raw materials is serious; This method not only can improve the quality of white dyes, and can save a large amount of raw materials consumptions, increases product yield; Reduce difficulty of post-processing, alleviate pollution environment.
Concentrate main purpose with dialysis procedure and be for the given dialysis water yield salt that will be mingled in the white dyes as much as possible impurity that grades and get in the filtrating, just film is more little good more to the rejection of inorganic salt, and promptly ratio of desalinization is high more good more.Select the nf membrane core of NFM type among the present invention for use, the whole salts contg of dialyzate can be reduced to below 0.2%, and chromatogram master's content can reach more than 95%.
Preparing method of the present invention obtains symmetry and asymmetric three component disulfonic acid class I liquid I white dyess, is amber color liquid, and is soluble in water; Odorlessness, stable performance, its maximum absorption wavelength is 348nm; Maximum emission wavelength is 434nm; Have hyperfluorescence, have the effect of compound synergic, solved the problem of one-component poor stability and improved the yellowing point; Solved the problem that acid gas produces in the production process, the nanofiltration of adopting new technology is handled, and yield reaches more than 85%; The liquid fluorescent whitening agent product is easy to use, uses with automatic production and adds metering continuously, and good acid resistance is arranged, and at normal temperatures, has better package stability.
Embodiment
Embodiment 1
A kind of preparation method of toluylene triazine liquid fluorescent brightener composite may further comprise the steps:
1) in the beaker of 500 ml waters, add 100 gram trash ices, the use massfraction is 30% salt acid for adjusting pH value to 2.0, stirs and is cooled to 0 ± 2 ℃, adds 20.0 gram cyanuric chlorides; Open and stir, pulled an oar 1 hour, slowly add with 19 grams 4,4 '-diaminobenzil-2; 2 '-disulfonic acid be made into 4,4 '-diaminobenzil-2,2 '-sodium disulfonate aqueous solution adds after 20 minutes; Using massfraction is that 10% sodium hydroxide solution regulation system pH value is 4, and keeps this pH value to react 1.5 hours, and re-adjustment pH is 6, keeps this pH value; Be reacted to amino disappearance the in the amino reagent detection architecture, stopped reaction makes compound I, and promptly 4; 4 '-two (4,6-dichlorotriazine-2-is amino) toluylene-2,2 '-sodium disulfonate, its structural formula is following:
2) 10.3 gram aniline are joined rapidly in the above-mentioned reaction solution; Using massfraction is that the pH of 10% sodium hydroxide solution conditioned reaction liquid is 7.0; Keep system temperature at 25 ℃, stirring reaction is to disappearing stopped reaction with amino in the amino reagent detection architecture; Make compound I I, its structural formula is following:
3) acrylic amide with 14.2 grams slowly joins in the Monoethanolamine MEA BASF of 12.2 grams; Joining day was controlled at about 2 hours, 50 ℃ of temperature of reaction, reinforced finishing; Continued insulation reaction 4～5 hours; Make the mixture of compound III-1 and compound IV-1, i.e. midbody, the structural formula of compound III-1 and compound IV-1 is following:
4) at the uniform velocity add 17.4 gram midbodys in the reaction solution of the inherent step of following 10 minutes of agitation condition (2), beginning to heat up and using massfraction is 10% sodium hydroxide solution, and the pH value of conditioned reaction liquid is 8.5; Hierarchy of control temperature is between 80 ℃, and insulation reaction 2 hours continues to be warming up to 105 ℃ of backflows; Continue insulation and refluxed 3 hours, using massfraction is that 10% sodium hydroxide solution regulation system pH value is 8.5, stopped reaction; When reaction system is cooled to below 65 ℃; Use the B vacuum filtration, remove water-insoluble, gained filtrating is carried out the nanofiltration desalination and concentration through NP series ceramic nf membrane under 60 ℃, the pressure of 0.2Mpa; Finish when arriving between specific conductivity 1820～1880S/m; Make compound V-1, compound VI-2 and compound VI I-3, i.e. toluylene triazine liquid fluorescent brightener composite, wherein the structure of compound V-1, compound VI-2 and compound VI I-3 is following:
Adopt performance liquid chromatography that each component ratio of compsn is measured, the collection of illustrative plates demonstration truly has 3 main chromatographic peaks, and quantitative with normalization method, the mass ratio of three components is (V): (VI): (VII)=3: 10: 7.
Embodiment 2
A kind of preparation method of toluylene triazine liquid fluorescent brightener composite may further comprise the steps:
1) in the beaker of 500 ml waters, add 100 gram trash ices, the use massfraction is 30% salt acid for adjusting pH value to 2.0, stirs and is cooled to 0 ± 2 ℃, adds 20.0 gram cyanuric chlorides; Open and stir, pulled an oar 1 hour, slowly add with 19.6 grams 4,4 '-diaminobenzil-2; 2 '-disulfonic acid be made into 4,4 '-diaminobenzil-2,2 '-sodium disulfonate aqueous solution adds after 20 minutes; Using massfraction is that 20% sodium carbonate solution regulation system pH value is 5, and keeps this pH value to react 1.5 hours, and re-adjustment pH is 6, keeps this pH value; Be reacted to amino disappearance the in the amino reagent detection architecture, stopped reaction makes compound I, and promptly 4; 4 '-two (4,6-dichlorotriazine-2-is amino) toluylene-2,2 '-sodium disulfonate, its structural formula is following:
2) 10.3 gram aniline are joined rapidly in the above-mentioned reaction solution, using massfraction is that the pH of 20% sodium carbonate solution conditioned reaction liquid is 7.5, keeps system temperature at 40 ℃; Stirring reaction is to disappearing with amino in the amino reagent detection architecture; Stopped reaction makes compound I I, and its structural formula is following:
3) acrylic amide with 14.2 grams slowly joins in the Monoethanolamine MEA BASF of 12.5 grams; Joining day was controlled at about 2 hours, 50 ℃ of temperature of reaction, reinforced finishing; Continued insulation reaction 4～5 hours; Make the mixture of compound III-1 and compound IV-1, i.e. midbody, the structural formula of compound III-1 and compound IV-1 is following:
4) at the uniform velocity add 19.6 gram midbodys in the reaction solution of the inherent step of following 10 minutes of agitation condition (2), beginning to heat up and using massfraction is that the pH value of 20% sodium carbonate solution conditioned reaction liquid is 10, and hierarchy of control temperature is between 80 ℃; Insulation reaction 2 hours continues to be warming up to 105 ℃ of backflows, continues insulation and refluxes 3 hours; Using massfraction is that 20% sodium carbonate solution regulation system pH value is 10; Stopped reaction when reaction system is cooled to below 65 ℃, is used the B vacuum filtration; Remove water-insoluble; Gained filtrating is carried out the nanofiltration desalination and concentration through NP series ceramic nf membrane under 60 ℃, the pressure of 1.0Mpa, finish to time between specific conductivity 1820～1880S/m, makes compound V-1, compound VI-1 and compound VI I-1
Adopt the ratio of each component of high-performance liquid chromatogram determination, the mass ratio of three components is (V): (VI): (VII)=3: 10: 5.6.
Embodiment 3
A kind of preparation method of toluylene triazine liquid fluorescent brightener composite may further comprise the steps:
1) in the beaker of 500 ml waters, add 100 gram trash ices, the use massfraction is 30% salt acid for adjusting pH value to 2.0, stirs and is cooled to 0 ± 2 ℃, adds 20.0 gram cyanuric chlorides; Open and stir, pulled an oar 1 hour, slowly add with 19.6 grams 4,4 '-diaminobenzil-2; 2 '-disulfonic acid be made into 4,4 '-diaminobenzil-2,2 '-sodium disulfonate aqueous solution adds after 20 minutes; Using massfraction is that 30% sodium carbonate solution regulation system pH value is 6, and keeps this pH value reaction 1.5 hours, is reacted to amino disappearance in the amino reagent detection architecture, stopped reaction; Make compound I, promptly 4,4 '-two (4; 6-dichlorotriazine-2-is amino) toluylene-2,2 '-sodium disulfonate, its structural formula is following:
2) 10.3 gram aniline are joined rapidly in the above-mentioned reaction solution, using massfraction is that the pH of 30% sodium carbonate solution conditioned reaction liquid is 8, keeps system temperature at 40 ℃; Stirring reaction is to disappearing with amino in the amino reagent detection architecture; Stopped reaction makes compound I I, and its structural formula is following:
3) crotonamide with 17.0g slowly joins in the Monoethanolamine MEA BASF of 12.2g gram; Joining day was controlled at about 2 hours, 50 ℃ of temperature of reaction, reinforced finishing; Continued insulation reaction 4～5 hours; Make the mixture of compound III and compound IV, i.e. midbody, the structural formula of compound III-2 and compound IV-2 is following:
4) at the uniform velocity add 21.7 gram midbodys in the reaction solution of the inherent step of following 10 minutes of agitation condition (2), beginning to heat up and using massfraction is that the pH value of 30% sodium carbonate solution conditioned reaction liquid is 12, and hierarchy of control temperature is between 80 ℃; Insulation reaction 2 hours continues to be warming up to 105 ℃ of backflows, continues insulation and refluxes 3 hours; Using massfraction is that 30% sodium carbonate solution regulation system pH value is 12; Stopped reaction when reaction system is cooled to below 65 ℃, is used the B vacuum filtration; Remove water-insoluble; Gained filtrating is carried out the nanofiltration desalination and concentration through NP series ceramic nf membrane under 60 ℃, the pressure of 2.0Mpa, finish to time between specific conductivity 1820～1880S/m, makes compound V-2, compound VI-2 and compound VI I-2; Be toluylene triazine liquid fluorescent brightener composite, wherein the structure of compound V-2, compound VI-2 and compound VI I-3 is following:
Adopt the ratio of each component of high-performance liquid chromatogram determination, the mass ratio of three components is (V): (VI): (VII)=3: 10: 6.
Embodiment 4
Sodium hydroxide solution with 20% adds the 20.5g midbody as the pH value of each step of acid binding agent adjusting in step (4), other operating process are with embodiment 3.Adopt the ratio of each component of high-performance liquid chromatogram determination, the mass ratio of three components is (V): (VI): (VII)=4: 5: 5.6.
Embodiment 5
Sodium hydroxide solution with 30% adds the 19.6g midbody as the pH value of each step of acid binding agent adjusting in step (4), other operating process are with embodiment 3.Adopt the ratio of each component of high-performance liquid chromatogram determination, the mass ratio of three components is (V): (VI): (VII)=3: 6.5: 7.6.
Claims (5)
1. the preparation method of a toluylene triazine liquid fluorescent brightener composite is characterized in that may further comprise the steps:
1) cyanuric chloride is dispersed in the frozen water solution, the mol ratio according to 1: 0.43～0.5 adds 4,4 '-diaminobenzil-2,2 '-disulfonic acid solution; Using the pH value of acid binding agent conditioned reaction system is 4.0～7.0, under 0～15 ℃, reacts stopped reaction when amino disappears to reaction system; Make compound I, promptly 4,4 '-two (4; 6-dichlorotriazine-2-is amino) toluylene-2,2 '-sodium disulfonate, its structural formula is following:
2) according to aniline: the mol ratio of compound I is that 1: 0.45～0.55 ratio adds aniline in the reaction solution of step (1); Using the pH value of acid binding agent conditioned reaction system is 7.0～8.0; Being warming up to 25～50 ℃ reacts; Stopped reaction when amino disappears to reaction system makes compound I I, and its structural formula is following:
3) with 1-R
1-2-R
2-acrylic amide and Monoethanolamine MEA BASF carry out addition reaction, make the mixture of compound III and compound IV, i.e. midbody, and the structural formula of compound III and compound IV is following:
R wherein
1, R
2Be H or C
1～C
2The representative examples of saturated aliphatic substituting group;
4) according to compound I I: the mol ratio of midbody is that 1: 1.2～1.5 ratio adds midbody in the reaction solution of step (2); Using the pH value of acid binding agent regulation system is 8.5～12.0, is warming up to 60～110 ℃, reacts stopped reaction when the pH value of system does not change; Filtering reacting liquid; Make compound V, compound VI and compound VI I, i.e. toluylene triazine liquid fluorescent brightener composite, wherein the structure of compound V, compound VI and compound VI I is following:
2. the preparation method of a kind of toluylene triazine liquid fluorescent brightener composite according to claim 1 is characterized in that described acid binding agent is that massfraction is 10～30% the sodium hydroxide or the aqueous solution of yellow soda ash.
3. according to the preparation method of the described a kind of toluylene triazine liquid fluorescent brightener composite of claim, it is characterized in that said 1-R
1-2-R
2The mol ratio of-acrylic amide and Monoethanolamine MEA BASF is 1: 0.98～1.02.
4. the preparation method of a kind of toluylene triazine liquid fluorescent brightener composite according to claim 1; It is characterized in that the described employing nf membrane that is filtered into, is under 0.2～2.0Mpa condition reaction solution to be permeated desalting and filtering repeatedly to handle at pressure.
5. according to the preparation method of a kind of toluylene triazine liquid fluorescent brightener composite under the claim 4, it is characterized in that described nf membrane is a NFM series membranes core.
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| CN103421346A (en) * | 2013-08-21 | 2013-12-04 | 山西青山化工有限公司 | Disulfonic acid liquid florescence brightener and preparation method thereof |
| CN103436050A (en) * | 2013-09-16 | 2013-12-11 | 山西青山化工有限公司 | Liquid fluorescent whitening agent and preparation method thereof |
| CN103483868A (en) * | 2013-09-11 | 2014-01-01 | 山西青山化工有限公司 | Acid resistance type disulfonic acid liquid fluorescent whitening agent preparation method |
| 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 |
| CN112778229A (en) * | 2019-11-05 | 2021-05-11 | 上海合丽亚化工科技有限公司 | Method for continuously preparing fluorescent whitening agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103421346A (en) * | 2013-08-21 | 2013-12-04 | 山西青山化工有限公司 | Disulfonic acid liquid florescence brightener and preparation method thereof |
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| CN103483868B (en) * | 2013-09-11 | 2015-05-27 | 山西青山化工有限公司 | Preparation method for acid resistance type disulfonic acid liquid fluorescent whitening agent |
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| CN112955245A (en) * | 2018-10-30 | 2021-06-11 | 巴斯夫欧洲公司 | Removal of aluminum salts, HCl, NaCl and organic by-products from strongly alkaline DIOPAT suspensions by means of alkaline stable nanofiltration and then separation of salts and by-products by means of ultrafiltration after neutralization of the DIOPAT solution |
| CN112955245B (en) * | 2018-10-30 | 2023-10-20 | 巴斯夫欧洲公司 | Removal of aluminum salts, HCl, naCl, and organic byproducts from a strongly basic diopta suspension |
| US11904279B2 (en) | 2018-10-30 | 2024-02-20 | Basf Se | Removal of Al-salts, HCl, NaCl and organic by-product from strong alkaline DIOPAT suspension by means of alkaline stable nanofiltration followed by separation of salts and byproducts after neutralization of DIOPAT solution by means of ultrafiltration |
| CN112778229A (en) * | 2019-11-05 | 2021-05-11 | 上海合丽亚化工科技有限公司 | Method for continuously preparing fluorescent whitening agent |
| CN112778229B (en) * | 2019-11-05 | 2022-07-29 | 上海合丽亚化工科技有限公司 | Method for continuously preparing fluorescent whitening agent |
| 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 |
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