CN102924971A - Mixed toluylene biphenyl type fluorescent whitening agent and preparation method thereof - Google Patents
Mixed toluylene biphenyl type fluorescent whitening agent and preparation method thereof Download PDFInfo
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- CN102924971A CN102924971A CN2012104628326A CN201210462832A CN102924971A CN 102924971 A CN102924971 A CN 102924971A CN 2012104628326 A CN2012104628326 A CN 2012104628326A CN 201210462832 A CN201210462832 A CN 201210462832A CN 102924971 A CN102924971 A CN 102924971A
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Abstract
The invention discloses a mixed toluylene biphenyl type fluorescent whitening agent and a preparation method thereof, relates to a fluorescent whitening agent used in industries of printing and dyeing, synthetic detergent and the like, and solves the problems that the current product is easy to layer and liquid is easy to precipitate. The method comprises the following steps of dissolving 4, 4'-diethoxy phosphonic methyl diphenyl, o-sulfonic acid sodium benzaldehyde and 2, 4-disulfonic acid sodium benzaldehyde into an organic solvent DMF (Dimethyl Formamide), dropwise adding sodium methoxide at 43-47 DEG C to react, and conducting a thermal reaction for a period of time; warming, reducing pressure, and steaming out the solvent DMF; and after a filter cake is dissolved and filtered with water to remove impurities, the filter cake is concentrated and filtered and dried to obtain a finished product. The product can be stored stably and has high solubility. After the product is put for 100 days at the room temperature, the product is still clear, colorless and deposit-free. During the temperature of 25 DEG C, the solubility in water can achieve 38 g/L.
Description
Technical field
The present invention relates to print and dye, close the white dyes of industry uses such as washing, be specifically related to a kind of mixed type stilbene biphenyl fluorescent brightener and preparation method thereof.
Background technology
Contain biphenyl, precursor group and styrene group in 4, the 4 ′ – stilbene biphenyl fluorescent brightener structures, very stable to light, wash, dye little loss in the solarization process, whitening effect is remarkable, and nondiscoloration in the storage process is described as super white dyes, and development in recent years is very fast.Along with the accelerated development of light and textile industries, washing composition and plastics industry, the demand of domestic white dyes further increases.
Fluorescent brightener CBS is 4,4 ′ – stilbene biphenyl fluorescent brighteners a kind of, have that good anti-chlorine floats, acid and alkali-resistance, sun-resistant performance, it is the perfect additive of light industry, weaving and daily use chemicals industry, in particular for various washing powder, soap and liquid washing agent, the use properties of product be can improve, product inner quality and visual appearance improved.Being specially adapted to cold washing and brightening, is the white dyes kind that is used in the world at present the detergent industry best results.At present, domestic this fluorescent bleaches mainly contains CBS – 120, CBS – 127 etc., mostly is greatly old product, and new product development is slow, the expensive goods shortcoming.Therefore, strengthen that the study on the synthesis of 4,4 ′ – distyry-biphenyls high-efficiency fluorescence whitening agent is had practical significance.
In the existing method, disclose a kind of 4, the synthetic method of two (dimethoxy phosphonomethyl) biphenyl of 4 ′ –: in the 250ML four-hole boiling flask, add 4,4 ′ – dichloromethyl biphenyl, with a small amount of phosphonous acid triethyl, be warmed up to 105 ~ 115 ℃, be incubated 20 minutes, after all dissolving, be warmed up to 120 ~ 130 ℃, and in 1 hour, evenly drip remaining phosphonous acid triethyl, and in 1 hour, be warming up to 155 ~ 165 ℃ after adding, be incubated 8 ~ 10 hours, sampling detects, content〉95%, unreacted phosphonous acid triethyl is reclaimed in underpressure distillation, then cools 110 ℃, discharging, be cooled to crystallizing at room temperature, the white solid of separating out is two (dimethoxy phosphonomethyl) biphenyl of 4,4 ′ –.Because the raw material phosphonous acid trimethyl that the method is used not only has pungent odour, boiling point is low, meets water capacity facile hydrolysis, in the synthetic intermediate process, consumes large; Also to add the toluene crystallization in the intermediate reaction process, increase production cost.
CBS is 4,4 ′ – stilbene biphenyl fluorescent brighteners, makes CBS soup compound, high score liquid, after placement for some time, and the easy layering of soup compound, precipitation appears in high score liquid easily.The present invention is from considering that in this respect made a kind of stilbene biphenyl fluorescent brightener of mixed type, the solvability of this white dyes is better than CBS.
Summary of the invention
The present invention is in order to be two sulphur classes 4 for CBS, 4 ′ – stilbene biphenyl fluorescent brighteners, make CBS soup compound, high score liquid, after placing for some time, the easy layering of soup compound, the problem that precipitates appears in liquid easily, and a kind of mixed type stilbene biphenyl fluorescent brightener and preparation method thereof is provided.
A kind of mixed type stilbene biphenyl fluorescent brightener comprises the component with following three kinds of structures:
The present invention is achieved by the following technical solutions:
A kind of preparation method of mixed type stilbene biphenyl fluorescent brightener may further comprise the steps:
With 4,4 ′ – diethoxy phosphonium mesitoyl methyl diphenyls, ortho-sulfonic acid sodium phenyl aldehyde, 2,4 – sodium disulfonate dissolution of benzaldehyde are in organic solvent DMF, dripping sodium methylate at 43 ~ 47 ℃ reacts, insulation reaction for some time, the decompression that heats up steams solvent DMF, after filter cake water dissolution filter is removed impurity, thickening filtration, oven dry gets product.
Further, the mol ratio of described 4,4 ’ – diethoxy phosphonium mesitoyl methyl diphenyl and ortho-sulfonic acid sodium phenyl aldehyde, 2,4 – sodium disulfonate phenyl aldehydes and sodium methylate is 1:1.2:1.2:1.1.
Temperature when described sodium methylate drips is 43 ~ 47 ℃; Holding temperature is 43 ~ 47 ℃, and soaking time is 10 hours, then is warmed up to 95 ℃, is incubated 2 hours.
The temperature of described vacuum distillation recovered solvent DMF is 120 ~ 125 ℃.
When described filter cake was used water dissolution, the adding water yield was 1.5 times of filter cake dry weight, and filter cake dissolving, filtration temperature are 90 ℃.
Product storage-stable of the present invention, solubleness is high, at room temperature, places 100 days still clears, and without precipitation, temperature is in the time of 25 ℃, and the solubleness in water can reach 38 gram/L.
Embodiment
The present invention will be further described below in conjunction with specific embodiment.
Embodiment 1
Synthesizing of two (dimethoxy phosphonomethyl) biphenyl of (1) 4,4 ′ –:
In the 250ML four-hole boiling flask, add 25.1 grams 4,4 ′ – dichloromethyl biphenyl, phosphonous acid triethyl 7.4 grams are warmed up to 105 ~ 115 ℃, are incubated 20 minutes, after all dissolving, be warmed up to 120 ~ 130 ℃, and in 1 hour, evenly drip remaining 34 gram phosphonous acid triethyls, in 1 hour, be warming up to 155 ~ 165 ℃ after adding, be incubated 8 ~ 10 hours, sampling detects, content〉95%, unreacted phosphonous acid triethyl is reclaimed in underpressure distillation, then be cooled to cool to 110 ℃, discharging is cooled to crystallizing at room temperature, and the white solid of separating out is 4, two (dimethoxy phosphonomethyl) biphenyl 41 grams of 4 ′ –, yield is 90.3%.
(2) the mixed type stilbene biphenyl fluorescent brightener is synthetic:
In the there-necked flask of 250ML, add successively 4,4 ’ – diethoxy phosphonium mesitoyl methyl diphenyl of 30 grams, the ortho-sulfonic acid sodium phenyl aldehyde of 16.5 grams, 2,4 – sodium disulfonate phenyl aldehydes of 24.6 grams, the DMF of 160 grams.After dissolving about 60 ℃, temperature drops to 45 ℃, begins to drip 33 gram sodium methylates, in 1.5 hours, drip off, after dripping off, 45 ℃ of insulation reaction 10 hours, be warmed up to 95 ℃, after the insulation reaction 2 hours, temperature is raised to 125 ℃, underpressure distillation, after solvent steams 90%, add the pure water of 35 grams 90 ℃ of dissolvings, obtain the yellow-green soln of clear, after the filtration, solution has been concentrated into solid separates out, cooling, temperature drops to suction filtration below 5 ℃, and filter cake is 100 ℃ of oven dry, pulverize, obtain yellow-green colour powder 32.8 grams, yield 93.8% comprises the component with following three kinds of structures:
(3) CBS, the preparation of 30 minutes liquid:
1, in the 2000ML there-necked flask that cleans up, add first tensio-active agent 20 gram R1 – 9,7.8 gram Diethylene Glycols, 8 gram PE grams, 300,1.1 emulsifying agents, 13.3 solubility promoter N.S, start stirring, in situation about stirring, add 30 grams and amount to 100% CBS filter cake, add 0.2 gram defoamer, simultaneously, according to the height of filter cake content, replenish corresponding pure water again, begin to heat up dissolving.
2, when being warming up to more than 80 ℃, check at any time the dissolving situation of filter cake, be reacted to filter cake dissolving 95 ℃ of 90 –, remake and use half an hour, sample examination also concentrates with heating or is till 30 minutes with pure water-reducible way adjustment solution to score value.Stablized again 20 minutes, and suitably cooled to 80 ℃, the beginning suction filtration, separating impurity is removed the salable product of impurity, is cooled to room temperature, in the sample bottle of packing into, preserves.
(4) mixed type stilbene biphenyl fluorescent brightener, the preparation of 30 minutes liquid:
1, in the 2000ML there-necked flask that cleans up, add first tensio-active agent 20 gram R1 – 9,7.8 gram Diethylene Glycols, 8 gram PE grams, 300,1.1 emulsifying agents, 13.3 solubility promoter N.S, start stirring, in situation about stirring, add 30 grams and amount to 100% mixed type stilbene biphenyl fluorescent brightener filter cake, add 0.2 gram defoamer, simultaneously, according to the height of filter cake content, replenish corresponding pure water again, begin to heat up dissolving.
2, when being warming up to more than 80 ℃, check at any time the dissolving situation of filter cake, be reacted to filter cake dissolving at 90 ~ 95 ℃, remake and use half an hour, sample examination also concentrates with heating or is till 30 minutes with pure water-reducible way adjustment solution to score value.Stablized again 20 minutes, and suitably cooled to 80 ℃, the beginning suction filtration, separating impurity is removed the salable product of impurity, is cooled to room temperature, in the sample bottle of packing into, preserves.
The contrast of 30 minutes liquid of (5) two kinds of white dyess:
At room temperature, 30 minutes CBS liquid was placed after 50 days, precipitation namely occurred; Mixed type stilbene biphenyl fluorescent brightener, 30 minutes liquid are placed 100 days still clears, without precipitation.
The solubleness of (6) two kinds of white dyess in water:
Temperature is in the time of 25 ℃, and the solubleness of CBS in water can reach 25 gram/L, and the solubleness of mixed type stilbene biphenyl fluorescent brightener in water can reach 38 gram/L.
Embodiment 2
A kind of preparation method of mixed type stilbene biphenyl fluorescent brightener may further comprise the steps:
Be that 4, the 4 ′ – diethoxy phosphonium mesitoyl methyl diphenyls, ortho-sulfonic acid sodium phenyl aldehyde, 2,4 – sodium disulfonate dissolution of benzaldehyde of 1:1.2:1.2:1.1 are in organic solvent DMF with mol ratio, wherein drip sodium methylate at 43 ℃, then 43 ℃ of insulation reaction 10 hours are warmed up to 95 ℃, are incubated 2 hours, be warmed up to 120 ℃, decompression steams solvent DMF, adds 1.5 times water of filter cake dry weight in the filter cake, after 90 ℃ of dissolution filters are removed impurity, thickening filtration, oven dry gets product.
Embodiment 3
A kind of preparation method of mixed type stilbene biphenyl fluorescent brightener may further comprise the steps:
Be that 4, the 4 ′ – diethoxy phosphonium mesitoyl methyl diphenyls, ortho-sulfonic acid sodium phenyl aldehyde, 2,4 – sodium disulfonate dissolution of benzaldehyde of 1:1.2:1.2:1.1 are in organic solvent DMF with mol ratio, wherein drip sodium methylate at 45 ℃, then 45 ℃ of insulation reaction 10 hours are warmed up to 95 ℃, are incubated 2 hours, be warmed up to 125 ℃, decompression steams solvent DMF, adds 1.5 times water of filter cake dry weight in the filter cake, after 90 ℃ of dissolution filters are removed impurity, thickening filtration, oven dry gets product.
Embodiment 4
A kind of preparation method of mixed type stilbene biphenyl fluorescent brightener may further comprise the steps:
Be that 4, the 4 ′ – diethoxy phosphonium mesitoyl methyl diphenyls, ortho-sulfonic acid sodium phenyl aldehyde, 2,4 – sodium disulfonate dissolution of benzaldehyde of 1:1.2:1.2:1.1 are in organic solvent DMF with mol ratio, wherein drip sodium methylate at 47 ℃, then 47 ℃ of insulation reaction 10 hours are warmed up to 95 ℃, are incubated 2 hours, be warmed up to 122 ℃, decompression steams solvent DMF, adds 1.5 times water of filter cake dry weight in the filter cake, after 90 ℃ of dissolution filters are removed impurity, thickening filtration, oven dry gets product.
Claims (6)
1. mixed type stilbene biphenyl fluorescent brightener is characterized in that comprising the component with following three kinds of structures:
2. the preparation method of mixed type stilbene biphenyl fluorescent brightener claimed in claim 1 is characterized in that may further comprise the steps:
With 4,4 ′ – diethoxy phosphonium mesitoyl methyl diphenyls, ortho-sulfonic acid sodium phenyl aldehyde, 2,4 – sodium disulfonate dissolution of benzaldehyde are in organic solvent DMF, dripping sodium methylate at 43 ~ 47 ℃ reacts, insulation reaction for some time, the decompression that heats up steams solvent DMF, after filter cake water dissolution filter is removed impurity, thickening filtration, oven dry gets product.
3. the preparation method of mixed type stilbene biphenyl fluorescent brightener according to claim 2, it is characterized in that described 4, the mol ratio of 4 ’ – diethoxy phosphonium mesitoyl methyl diphenyl and ortho-sulfonic acid sodium phenyl aldehyde, 2,4 – sodium disulfonate phenyl aldehydes and sodium methylate is 1:1.2:1.2:1.1.
4. the preparation method of mixed type stilbene biphenyl fluorescent brightener according to claim 2 is characterized in that the temperature when described sodium methylate drips is 43 ~ 47 ℃; Holding temperature is 43 ~ 47 ℃, and soaking time is 10 hours, then is warmed up to 95 ℃, is incubated 2 hours.
5. the preparation method of mixed type stilbene biphenyl fluorescent brightener according to claim 2, the temperature that it is characterized in that described vacuum distillation recovered solvent DMF is 120 ~ 125 ℃.
6. the preparation method of mixed type stilbene biphenyl fluorescent brightener according to claim 2 when it is characterized in that described filter cake is used water dissolution, adds the water yield and is 1.5 times of filter cake dry weight, and filter cake dissolving, filtration temperature are 90 ℃.
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| CN2012104628326A CN102924971A (en) | 2012-11-16 | 2012-11-16 | Mixed toluylene biphenyl type fluorescent whitening agent and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105063991A (en) * | 2015-08-31 | 2015-11-18 | 山西青山化工有限公司 | Fluorescent whitening agent for chinlon |
| CN109912465A (en) * | 2019-04-17 | 2019-06-21 | 沈阳新纪化学有限公司 | A kind of synthetic method of the stilbene biphenyl fluorescent brightener of micro- blue cast |
| CN113025111A (en) * | 2021-03-11 | 2021-06-25 | 河南瑞奇特化工有限公司 | Whitening agent for paint and ink and preparation method thereof |
| CN114163834A (en) * | 2021-12-13 | 2022-03-11 | 陕西省石油化工研究设计院 | CBS-351 liquid whitening agent and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CA823683A (en) * | 1969-09-23 | Weber Kurt | Bis-stilbene compounds | |
| JPS5213522A (en) * | 1975-07-24 | 1977-02-01 | Nippon Kayaku Co Ltd | Preparation of styryls |
| US5332861A (en) * | 1992-09-03 | 1994-07-26 | Ciba-Geigy Corporation | Process for preparing distyrylbiphenyl compounds |
| CN101845233A (en) * | 2010-05-24 | 2010-09-29 | 山西青山化工有限公司 | Preparation method of 4,4'-distyryl biphenyl-2,2'-disulfonic acid fluorescent whitening agent |
| CN102517178A (en) * | 2011-11-24 | 2012-06-27 | 浙江宏达化学制品有限公司 | Preparing method of stilbene biphenyl fluorescent brightener |
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2012
- 2012-11-16 CN CN2012104628326A patent/CN102924971A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA823683A (en) * | 1969-09-23 | Weber Kurt | Bis-stilbene compounds | |
| JPS5213522A (en) * | 1975-07-24 | 1977-02-01 | Nippon Kayaku Co Ltd | Preparation of styryls |
| US5332861A (en) * | 1992-09-03 | 1994-07-26 | Ciba-Geigy Corporation | Process for preparing distyrylbiphenyl compounds |
| CN101845233A (en) * | 2010-05-24 | 2010-09-29 | 山西青山化工有限公司 | Preparation method of 4,4'-distyryl biphenyl-2,2'-disulfonic acid fluorescent whitening agent |
| CN102517178A (en) * | 2011-11-24 | 2012-06-27 | 浙江宏达化学制品有限公司 | Preparing method of stilbene biphenyl fluorescent brightener |
Non-Patent Citations (1)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105063991A (en) * | 2015-08-31 | 2015-11-18 | 山西青山化工有限公司 | Fluorescent whitening agent for chinlon |
| CN109912465A (en) * | 2019-04-17 | 2019-06-21 | 沈阳新纪化学有限公司 | A kind of synthetic method of the stilbene biphenyl fluorescent brightener of micro- blue cast |
| CN109912465B (en) * | 2019-04-17 | 2021-08-24 | 沈阳新纪化学有限公司 | Synthesis method of distyrylbiphenyl fluorescent whitening agent with bluish tone |
| CN113025111A (en) * | 2021-03-11 | 2021-06-25 | 河南瑞奇特化工有限公司 | Whitening agent for paint and ink and preparation method thereof |
| CN114163834A (en) * | 2021-12-13 | 2022-03-11 | 陕西省石油化工研究设计院 | CBS-351 liquid whitening agent and preparation method thereof |
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Application publication date: 20130213 |