CN109912465B - Synthesis method of distyrylbiphenyl fluorescent whitening agent with bluish tone - Google Patents
Synthesis method of distyrylbiphenyl fluorescent whitening agent with bluish tone Download PDFInfo
- Publication number
- CN109912465B CN109912465B CN201910309767.5A CN201910309767A CN109912465B CN 109912465 B CN109912465 B CN 109912465B CN 201910309767 A CN201910309767 A CN 201910309767A CN 109912465 B CN109912465 B CN 109912465B
- Authority
- CN
- China
- Prior art keywords
- fluorescent whitening
- whitening agent
- bluish
- biphenyl
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000006081 fluorescent whitening agent Substances 0.000 title claims abstract description 32
- 238000001308 synthesis method Methods 0.000 title claims abstract description 18
- ZMLPKJYZRQZLDA-UHFFFAOYSA-N 1-(2-phenylethenyl)-4-[4-(2-phenylethenyl)phenyl]benzene Chemical group C=1C=CC=CC=1C=CC(C=C1)=CC=C1C(C=C1)=CC=C1C=CC1=CC=CC=C1 ZMLPKJYZRQZLDA-UHFFFAOYSA-N 0.000 title claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 63
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 32
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 28
- 239000007787 solid Substances 0.000 claims abstract description 28
- 239000011734 sodium Substances 0.000 claims abstract description 24
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 19
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 15
- NDFJBDVZJYCYJK-UHFFFAOYSA-N 1-[bis(ethylperoxy)phosphorylmethyl]-4-[4-[bis(ethylperoxy)phosphorylmethyl]phenyl]benzene Chemical group C1=CC(CP(=O)(OOCC)OOCC)=CC=C1C1=CC=C(CP(=O)(OOCC)OOCC)C=C1 NDFJBDVZJYCYJK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011780 sodium chloride Substances 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000001704 evaporation Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- PIGKXHAIBGNREV-UHFFFAOYSA-N C1=CC=CC=C1C1=CC=CC=C1.C=1C=CC=CC=1C=CC1=CC=CC=C1 Chemical group C1=CC=CC=C1C1=CC=CC=C1.C=1C=CC=CC=1C=CC1=CC=CC=C1 PIGKXHAIBGNREV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 239000012065 filter cake Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 26
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 7
- 239000000047 product Substances 0.000 abstract description 25
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 abstract description 22
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 238000004321 preservation Methods 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 16
- 238000004821 distillation Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 235000010290 biphenyl Nutrition 0.000 description 8
- 239000004305 biphenyl Substances 0.000 description 8
- 238000004043 dyeing Methods 0.000 description 7
- 238000004811 liquid chromatography Methods 0.000 description 7
- 239000003599 detergent Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- OQWBLDGADMLCSE-UHFFFAOYSA-N 2-[2-[4-phenyl-1-[2-(2-sulfophenyl)ethenyl]cyclohexa-2,4-dien-1-yl]ethenyl]benzenesulfonic acid Chemical group OS(=O)(=O)C1=CC=CC=C1C=CC1(C=CC=2C(=CC=CC=2)S(O)(=O)=O)C=CC(C=2C=CC=CC=2)=CC1 OQWBLDGADMLCSE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- JFLKFZNIIQFQBS-FNCQTZNRSA-N trans,trans-1,4-Diphenyl-1,3-butadiene Chemical group C=1C=CC=CC=1\C=C\C=C\C1=CC=CC=C1 JFLKFZNIIQFQBS-FNCQTZNRSA-N 0.000 description 1
Abstract
The invention discloses a synthesis method of a bluish stilbene biphenyl fluorescent whitening agent, which comprises the steps of firstly stirring and mixing sodium o-sulfonate benzaldehyde and 4,4' -bis (diethoxyphosphonomethyl) biphenyl by using a solvent, then adding solid potassium hydroxide for multiple times, carrying out heat preservation reaction, then evaporating the solvent under reduced pressure, rapidly adding a sodium chloride aqueous solution, cooling, filtering, and drying a filter cake to obtain a yellowish green solid, namely the bluish stilbene biphenyl fluorescent whitening agent. The synthesis method is simple, the operation is safe, the synthesized product has high yield and good quality, and compared with the traditional process using sodium methoxide, the yield of the product prepared by the method is improved by 4.5 percent, the purity is improved by 2 percent, and the cost is saved.
Description
Technical Field
The invention belongs to the technical field of fluorescent whitening agents, and particularly relates to a synthesis method of a bluish distyrylbiphenyl fluorescent whitening agent.
Background
4, 4-bis (2-disulfonate sodium styryl-) biphenyl (fluorescent whitening agent CBS-X for short) is one of important fluorescent whitening agents in a distyryl derivative structure, is mainly applied to industries such as textile, papermaking and detergents, is an ideal additive for light industry and daily chemical industry, and is particularly suitable for low-temperature washing and whitening. The fluorescent whitening agent has blue fluorescence with slight bluish color, has good whitening effect, has the advantages of high temperature resistance, alkali resistance, chlorine bleaching resistance, illumination resistance and the like, and is the fluorescent whitening agent variety with the best effect in the washing industry in the world at present.
Patents CN 103755601B and CN 102126691a report a synthesis method of 4, 4-bis (2-sulfostyryl) -1, 1-biphenyl. The method comprises the steps of feeding, heating, preserving heat, cooling, dripping, preserving heat again, continuously heating, distilling, rectifying and separating, solid-liquid separating, treating saturated brine and refining a CBS-X crude product. The condensation catalyst used in the method is liquid (solid) sodium methoxide, the liquid sodium methoxide is a solution of sodium methoxide dissolved in methanol, the content of the sodium methoxide is 27.5-31.0%, the methanol solution of the sodium methoxide is explosive and explosive, and the production and operation safety is low. The solvent after the condensation reaction contains a large amount of methanol solution, and the normal progress of the main reaction is influenced by the methanol solution, so that the side reaction is increased. In the process of distilling to remove the solvent, the distillation time is prolonged, part of the product is damaged, and the purity and the yield of the product are influenced. In addition, liquid sodium methoxide is used as a catalyst, liquid obtained in the rectification separation step is a mixed solution of DMF and methanol, further separation treatment is needed, the liquid cannot be directly recycled in process production, and the process operation cost is increased. In addition, the temperature rise and the heat preservation temperature after the method is fed are higher, and the energy consumption is higher. The condensation and dropwise addition reaction time is as long as about 12 hours, and the production period is long due to the time for heating and cooling.
As the fluorescent whitening agent market is expanding, its color range is increasingly showing its limitation, so that new fluorescent whitening agents adapted to the market demand are required. Among them, the fluorescent whitening agent with blue light has great demand in the aspects of liquid detergent and polyvinyl chloride plates, and the research at home and abroad is still in a blank state at present.
Disclosure of Invention
A synthesis method of a stilbene biphenyl fluorescent whitening agent with a bluish color tone is characterized by comprising the following steps:
(1) sodium o-sulfonate benzaldehyde and 4,4' -bis (diethoxyphosphonomethyl) biphenyl are mixed by a solvent and stirred for 0.5 h.
(2) Adding solid potassium hydroxide 2-10 times at 15-50 deg.C, and keeping the temperature for 6-8 h.
(3) And (3) decompressing and distilling out the solvent, quickly adding a sodium chloride aqueous solution, cooling, filtering, and drying a filter cake to obtain a light yellow green solid.
The synthesis method of the distyrylbiphenyl fluorescent whitening agent with the bluish color tone is characterized in that the solvent is one or two of dimethylformamide and dimethyl sulfoxide.
The synthesis method of the distyrylbiphenyl fluorescent whitening agent with the bluish color tone is characterized in that the mass ratio of the sodium o-sulfonate benzaldehyde to the 4,4' -bis (diethoxyphosphonomethyl) biphenyl is 0.94-1.02; when the mass ratio of the sodium o-sulfonate benzaldehyde to the 4,4' -bis (diethoxyphosphonomethyl) biphenyl is 0.94, the product yield and purity are optimal.
The synthesis method of the distyrylbiphenyl fluorescent whitening agent with the bluish hue is characterized in that in the step (2), the time for adding the solid potassium hydroxide is 1-3 h; the process of the small test and the pilot test shows that if the time for adding the solid potassium hydroxide is less than 1 hour, the impurities of the final product are increased, and the purity is reduced; the time for adding the solid potassium hydroxide is longer than 3 hours, so that the yield and the purity are not improved.
The synthesis method of the bluish stilbene biphenyl fluorescent whitening agent is characterized in that in the step (2), the mass ratio of the solid potassium hydroxide to the o-sodium sulfonate benzaldehyde is 0.29.
The synthesis method of the distyrylbiphenyl fluorescent whitening agent with the bluish hue is characterized in that in the step (3), the temperature for evaporating the solvent is 150-160 ℃.
The synthesis method of the bluish distyrylbiphenyl fluorescent whitening agent is characterized in that the concentration of the sodium chloride aqueous solution is 3%.
The synthesis method of the bluish distyrylbiphenyl fluorescent whitening agent is characterized in that the mass of the sodium chloride aqueous solution is 4 times of that of 4,4' -bis (diethoxyphosphonomethyl) biphenyl.
The synthesis method of the distyrylbiphenyl fluorescent whitening agent with the bluish hue is characterized in that in the step (3), the temperature is reduced to 0-5 ℃ and then the distyrylbiphenyl fluorescent whitening agent is filtered.
The synthesis method of the bluish distyrylbiphenyl fluorescent whitening agent is characterized in that in the step (3), the filter cake is dried at 100 ℃ to obtain a yellowish green solid.
The invention has the beneficial effects that:
(1) according to the invention, the solid potassium hydroxide is used for replacing liquid (solid) sodium methoxide, so that the operation safety is improved, and the potential safety hazard is reduced; methanol is not generated in the reaction process, so that side reactions are reduced, and the product quality is improved; methanol is not required to be distilled in the distillation process, so that the energy consumption can be reduced; the low-temperature reaction is adopted, the raw materials do not need to be heated and kept at high temperature, and the energy consumption can be reduced.
(2) The product produced by the synthesis process has a bluish hue, and can meet the requirements of products such as liquid laundry detergent and the like.
(3) The synthesis method is simple, the product yield is high, the quality is good, the operation is safe, and the cost of the potassium hydroxide is 30 percent of the cost of the sodium methoxide in the prior art; compared with the traditional process using sodium methoxide, the product yield of the invention is improved by 4.5%, and the purity is improved by 2%.
Detailed Description
Example 1.
In a dry 500ml four-necked flask, 130g of dimethylformamide, 34g of 4,4' -bis (diethoxyphosphonomethyl) biphenyl and 31.96g of sodium o-sulfonate benzaldehyde were sequentially added; then stirring is started, and the temperature is kept for 0.5h at room temperature; adding 9.2g of solid potassium hydroxide into the mixture by evenly dividing the mixture into 4 times under stirring at the temperature of 30 ℃, wherein the adding time is 2 hours in total; after the addition, heating to 50 ℃, and keeping the temperature for 8 hours; after the reaction is finished, evaporating the solvent at the temperature of 150 ℃ and 160 ℃; after the distillation is finished, 136g of sodium chloride aqueous solution with the concentration of 3 percent is added, the temperature is reduced to 5 ℃, then the filtration is carried out, and the drying is carried out at 100 ℃ to obtain 42.08g of the target product 4, 4-bis (2-sodium disulfonate styryl-) biphenyl. The percentage of the target product determined by liquid chromatography was: 98.7 percent.
The whiteness and shade data are identified by an infrared dyeing machine (model DL-6000P) and a desk type expert-grade spectrocolorimeter (X _ Rite CE 7000A) in the following table 1:
example 2.
In a dry 500ml four-necked flask, 130g of dimethylformamide, 34g of 4,4' -bis (diethoxyphosphonomethyl) biphenyl and 31.96g of sodium o-sulfonate benzaldehyde were sequentially added; then stirring is started, and the temperature is kept for 0.5h at room temperature; stirring at 15 ℃, adding 9.2g of solid potassium hydroxide evenly for 4 times, wherein the adding time is 2 hours; after the addition, heating to 50 ℃, and keeping the temperature for 8 hours; after the reaction is finished, evaporating the solvent at the temperature of 150 ℃ and 160 ℃; after the distillation is finished, 136g of sodium chloride aqueous solution with the concentration of 3 percent is added, the temperature is reduced to 5 ℃, then the filtration is carried out, and the drying is carried out at 100 ℃ to obtain 42.01g of the target product 4, 4-bis (2-sodium disulfonate styryl-) biphenyl. The percentage of the target product determined by liquid chromatography was: 98.8 percent.
The whiteness and shade data are identified in Table 2 using an infrared dyeing machine (model DL-6000P) and a desk type expert-grade spectrocolorimeter (X _ Rite CE 7000A):
example 3.
In a dry 500ml four-necked flask, 130g of dimethylformamide, 34g of 4,4' -bis (diethoxyphosphonomethyl) biphenyl and 31.96g of sodium o-sulfonate benzaldehyde were sequentially added; then stirring is started, and the temperature is kept for 0.5h at room temperature; under the stirring at 50 ℃, 9.2g of solid potassium hydroxide is added in 4 times on average, and the adding time is 2 hours in total; after the addition is finished, the heat preservation is continued for 8 hours; after the reaction is finished, evaporating the solvent at the temperature of 150 ℃ and 160 ℃; after the distillation, 136g of sodium chloride aqueous solution with the concentration of 3 percent is added, the temperature is reduced to 5 ℃, then the filtration and the drying are carried out, and 42.12g of the target product 4, 4-bis (2-sodium disulfonate styryl-) biphenyl is obtained. The percentage of the target product determined by liquid chromatography was: 98.5 percent.
The whiteness and shade data are identified in Table 3 using an infrared dyeing machine (model DL-6000P) and a desk type expert-grade spectrocolorimeter (X _ Rite CE 7000A):
example 4.
In a dry 500ml four-necked flask, 130g of dimethylformamide, 34g of 4,4' -bis (diethoxyphosphonomethyl) biphenyl and 31.96g of sodium o-sulfonate benzaldehyde were sequentially added; then stirring is started, and the temperature is kept for 0.5h at room temperature; under the condition of stirring at the temperature of 30 ℃, 9.2g of solid potassium hydroxide is added for 4 times on average, and the adding time is 1 hour in total; after the addition, heating to 50 ℃, and keeping the temperature for 8 hours; after the reaction is finished, evaporating the solvent at the temperature of 150 ℃ and 160 ℃; after the distillation is finished, 136g of sodium chloride aqueous solution with the concentration of 3 percent is added, the temperature is reduced to 5 ℃, then the filtration is carried out, and the drying is carried out at 100 ℃ to obtain 42.15g of the target product 4, 4-bis (2-sodium disulfonate styryl-) biphenyl. The percentage of the target product determined by liquid chromatography was: 98.4 percent.
The whiteness and shade data are identified in Table 4 using an infrared dyeing machine (model DL-6000P) and a desk type expert-grade spectrocolorimeter (X _ Rite CE 7000A):
example 5.
In a dry 500ml four-necked flask, 130g of dimethylformamide, 34g of 4,4' -bis (diethoxyphosphonomethyl) biphenyl and 31.96g of sodium o-sulfonate benzaldehyde were sequentially added; then stirring is started, and the temperature is kept for 0.5h at room temperature; under the stirring at 30 ℃, 9.2g of solid potassium hydroxide is added for 4 times on average, and the adding time is 3 hours in total; after the addition, heating to 50 ℃, and keeping the temperature for 8 hours; after the reaction is finished, evaporating the solvent at the temperature of 150 ℃ and 160 ℃; after the distillation is finished, 136g of sodium chloride aqueous solution with the concentration of 3 percent is added, the temperature is reduced to 5 ℃, then the filtration and the drying are carried out, and 41.91g of the target product 4, 4-bis (2-sodium disulfonate styryl-) biphenyl are obtained. The percentage of the target product determined by liquid chromatography was: 99.1 percent.
The whiteness and shade data are identified in Table 5 using an infrared dyeing machine (model DL-6000P) and a desk type expert-grade spectrocolorimeter (X _ Rite CE 7000A):
example 6.
In a dry 500ml four-necked flask, 130g of dimethyl sulfoxide, 34g of 4,4' -bis (diethoxyphosphonomethyl) biphenyl and 31.96g of sodium o-sulfonate benzaldehyde were sequentially added; then stirring is started, and the temperature is kept for 0.5h at room temperature; under the stirring at 30 ℃, 9.2g of solid potassium hydroxide is added for 2 times on average, and the adding time is 2 hours in total; after the addition, heating to 50 ℃, and keeping the temperature for 8 hours; after the reaction is finished, evaporating the solvent at the temperature of 150 ℃ and 160 ℃; after the distillation is finished, 136g of sodium chloride aqueous solution with the concentration of 3 percent is added, the temperature is reduced to 10 ℃, the filtration is carried out, and 42.03g of the target product 4, 4-bis (2-sodium disulfonate styryl-) biphenyl is obtained after the drying. The percentage of the target product determined by liquid chromatography was: 98.8 percent.
The whiteness and shade data are identified by an infrared dyeing machine (model DL-6000P) and a desk type expert-grade spectrocolorimeter (X _ Rite CE 7000A) in the following table 6:
example 7.
In a dry 500ml four-necked flask, 80g of dimethylformamide, 50g of dimethyl sulfoxide, 34g of 4,4' -bis (diethoxyphosphonomethyl) biphenyl and 31.96g of sodium o-sulfonate benzaldehyde were added in this order; then stirring is started, and the temperature is kept for 0.5h at room temperature; under the stirring at 30 ℃, 9.2g of solid potassium hydroxide is added for 10 times on average, and the adding time is 2 hours in total; after the addition, heating to 50 ℃, and keeping the temperature for 8 hours; after the reaction is finished, evaporating the solvent at the temperature of 150 ℃ and 160 ℃; after the distillation, 136g of sodium chloride aqueous solution with the concentration of 3 percent is added, the temperature is reduced to 5 ℃, then the filtration and the drying are carried out, thus obtaining 42.17g of the target product 4, 4-bis (2-sodium disulfonate styryl-) biphenyl. The percentage of the target product determined by liquid chromatography was: 98.6 percent.
The whiteness and shade data are identified in Table 7 using an infrared dyeing machine (model DL-6000P) and a desk type expert-grade spectrocolorimeter (X _ Rite CE 7000A):
example 8.
The procedure is as in example 1 except that 36.68g of sodium o-sulfonate benzaldehyde and 10.06g of solid potassium hydroxide are added.
Example 9.
The procedure is as in example 1 except that 33.32g of sodium o-sulfonate benzaldehyde and 9.66g of solid potassium hydroxide are added.
Comparative example 1.
The experiment was identical to example 1 in all component masses and process parameters, except that solid potassium hydroxide was replaced with solid sodium methoxide. The product obtained in example 1 was compared with that of comparative example 1, the results of which are shown in Table 8:
Claims (8)
1. a synthesis method of a stilbene biphenyl fluorescent whitening agent with a bluish color tone is characterized by comprising the following steps:
(1) sodium o-sulfonate benzaldehyde and 4,4' -bis (diethoxyphosphonomethyl) biphenyl are mixed by a solvent according to the mass ratio of (0.94-1.02): 1, mixing and stirring for 0.5 h;
(2) adding solid potassium hydroxide 2-10 times at 15-50 deg.C, the mass ratio of solid potassium hydroxide to o-sodium sulfonate benzaldehyde is 0.29:1, and keeping the temperature for 6-8 hr;
(3) and (3) decompressing and distilling out the solvent, quickly adding a sodium chloride aqueous solution, cooling, filtering, and drying a filter cake to obtain a light yellow green solid.
2. The method for synthesizing a distyrylbiphenyl fluorescent whitening agent of bluish color according to claim 1, wherein the solvent is one or both of dimethylformamide and dimethylsulfoxide.
3. The method for synthesizing distyrylbiphenyl fluorescent whitening agent of bluish color according to claim 1, wherein the time for adding solid potassium hydroxide in the step (2) is 1 to 3 hours.
4. The method for synthesizing distyrylbiphenyl fluorescent whitening agent with bluish hue according to claim 1, wherein the temperature for evaporating the solvent in the step (3) is 150-160 ℃.
5. The method for synthesizing a bluish stilbene biphenyl fluorescent whitening agent according to claim 1, wherein the concentration of the aqueous sodium chloride solution is 3%.
6. The method for synthesizing a bluish stilbene biphenyl fluorescent whitening agent according to claim 1, wherein the mass of the aqueous sodium chloride solution is 4 times the mass of 4,4' -bis (diethoxyphosphonomethyl) biphenyl.
7. The method for synthesizing distyrylbiphenyl fluorescent whitening agent of bluish color according to claim 1, wherein in the step (3), the temperature is reduced to 0 to 5 ℃ and then the mixture is filtered.
8. The method for synthesizing distyrylbiphenyl fluorescent whitening agents with bluish color tone according to claim 1, wherein in the step (3), the filter cake is dried at 100 ℃ to obtain yellowish green solid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910309767.5A CN109912465B (en) | 2019-04-17 | 2019-04-17 | Synthesis method of distyrylbiphenyl fluorescent whitening agent with bluish tone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910309767.5A CN109912465B (en) | 2019-04-17 | 2019-04-17 | Synthesis method of distyrylbiphenyl fluorescent whitening agent with bluish tone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109912465A CN109912465A (en) | 2019-06-21 |
| CN109912465B true CN109912465B (en) | 2021-08-24 |
Family
ID=66977567
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910309767.5A Active CN109912465B (en) | 2019-04-17 | 2019-04-17 | Synthesis method of distyrylbiphenyl fluorescent whitening agent with bluish tone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109912465B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112409220B (en) * | 2020-11-20 | 2023-03-14 | 河北星宇化工有限公司 | Production process of fluorescent brightener CBS-351 |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1247934A (en) * | 1967-10-03 | 1971-09-29 | Ciba Geigy Ag | Bis-stilbene compounds, their manufacture and use |
| CH560736A5 (en) * | 1968-08-20 | 1975-04-15 | Ciba Geigy Ag | Stilbene optical brighteners - for natural, synthetic and semi-synthetic textiles and as scintillators in photography |
| US3984399A (en) * | 1967-10-03 | 1976-10-05 | Ciba-Geigy Ag | Bis-stilbene compounds |
| CN1778783A (en) * | 2004-11-26 | 2006-05-31 | 上海化学试剂研究所 | Production of 4,4'-di(2-methoxyl-styrene) biphenyl |
| CN102126991A (en) * | 2010-12-29 | 2011-07-20 | 河北星宇化工有限公司 | Preparation method of 4,4-bis(2-sulfostyryl)-1,1-biphenyl |
| CN102911509A (en) * | 2012-10-26 | 2013-02-06 | 山西青山化工有限公司 | Environment-friendly preparation method of toluylene-based biphenyl type fluorescent brightener |
| CN102924971A (en) * | 2012-11-16 | 2013-02-13 | 山西青山化工有限公司 | Mixed toluylene biphenyl type fluorescent whitening agent and preparation method thereof |
| CN102924959A (en) * | 2012-11-17 | 2013-02-13 | 山西青山化工有限公司 | Synthesis method of reddish distyrylbiphenyl fluorescent whitening agent |
| CN103755601A (en) * | 2014-01-13 | 2014-04-30 | 河北星宇化工有限公司 | Preparation method of 4,4-bi(2-sulfostyryl)-1,1-biphenyl |
| CN107746706A (en) * | 2017-10-19 | 2018-03-02 | 山西青山化工有限公司 | A kind of environment-friendly preparation method of fluorescent whitening agent |
| CN109206750A (en) * | 2018-09-13 | 2019-01-15 | 湖南工程学院 | A method of improving distyryl biphenyl class brightening agent and PP Compatibility in Plastics |
-
2019
- 2019-04-17 CN CN201910309767.5A patent/CN109912465B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1247934A (en) * | 1967-10-03 | 1971-09-29 | Ciba Geigy Ag | Bis-stilbene compounds, their manufacture and use |
| US3984399A (en) * | 1967-10-03 | 1976-10-05 | Ciba-Geigy Ag | Bis-stilbene compounds |
| CH560736A5 (en) * | 1968-08-20 | 1975-04-15 | Ciba Geigy Ag | Stilbene optical brighteners - for natural, synthetic and semi-synthetic textiles and as scintillators in photography |
| CN1778783A (en) * | 2004-11-26 | 2006-05-31 | 上海化学试剂研究所 | Production of 4,4'-di(2-methoxyl-styrene) biphenyl |
| CN102126991A (en) * | 2010-12-29 | 2011-07-20 | 河北星宇化工有限公司 | Preparation method of 4,4-bis(2-sulfostyryl)-1,1-biphenyl |
| CN102911509A (en) * | 2012-10-26 | 2013-02-06 | 山西青山化工有限公司 | Environment-friendly preparation method of toluylene-based biphenyl type fluorescent brightener |
| CN102924971A (en) * | 2012-11-16 | 2013-02-13 | 山西青山化工有限公司 | Mixed toluylene biphenyl type fluorescent whitening agent and preparation method thereof |
| CN102924959A (en) * | 2012-11-17 | 2013-02-13 | 山西青山化工有限公司 | Synthesis method of reddish distyrylbiphenyl fluorescent whitening agent |
| CN103755601A (en) * | 2014-01-13 | 2014-04-30 | 河北星宇化工有限公司 | Preparation method of 4,4-bi(2-sulfostyryl)-1,1-biphenyl |
| CN107746706A (en) * | 2017-10-19 | 2018-03-02 | 山西青山化工有限公司 | A kind of environment-friendly preparation method of fluorescent whitening agent |
| CN109206750A (en) * | 2018-09-13 | 2019-01-15 | 湖南工程学院 | A method of improving distyryl biphenyl class brightening agent and PP Compatibility in Plastics |
Non-Patent Citations (1)
| Title |
|---|
| 荧光增白剂CBS合成研究及300t/a初步方案设计;郭仲;《中国优秀硕士学位论文 工程科技I辑》;20050515(第02期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109912465A (en) | 2019-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100543012C (en) | Preparation 1,4-diamino-2, the method for 3-dicyan anthraquinone | |
| CN109912465B (en) | Synthesis method of distyrylbiphenyl fluorescent whitening agent with bluish tone | |
| CN101591249A (en) | " waste residue " of producing the 1-aminoanthraquinone is processed into the method for producing 1,5 (1,8)-dinitroanthraquinone raw material | |
| CN103539707A (en) | Preparation process of 2-naphthylamine-3,6,8-trisulfonic acid | |
| CN110194729B (en) | Preparation method of m-nitro-beta-hydroxyethyl sulfone | |
| CN102399153A (en) | Method for preparing alpha,alpha'-dinitroanthraquinone refined substance by using waste residue generated during production of 1-nitroanthraquinone through solvent method | |
| CN102311348A (en) | Production and refining method of alpha, alpha'-dinitroanthraquinone | |
| CN109608354B (en) | Method for refining aniline dye intermediate | |
| DE3711984C2 (en) | ||
| EP2630119A1 (en) | Use of an acetic acid wash to prepare low-sulfate 5-sulfoisophthalic acid, mono-lithium salt | |
| CN110512213B (en) | Purification method of long-chain mixed dibasic acid | |
| US8884045B2 (en) | Use of an acetic acid wash to prepare low-sulfate 5-sulfoisophthalic acid, mono-lithium salt | |
| CN113956147A (en) | Decolorizing process of 2-ethyl anthraquinone crude product | |
| CN104086430A (en) | Method for synthesizing 1-aminoanthraquinone | |
| CN102924959B (en) | Synthesis method of reddish distyrylbiphenyl fluorescent whitening agent | |
| CN102924976B (en) | Novel method of vat yellow GCN postprocessing technology | |
| CN1026232C (en) | Process for preparing 2-hydroxy-3-naphthoic acid with 99% concentration | |
| US4041053A (en) | Process for the preparation of anthraquinone compounds | |
| CN110981737A (en) | Preparation method of 2, 4-dinitro-6-bromoaniline | |
| CN106146357B (en) | A kind of preparation method of DSD acid | |
| CN108997773A (en) | A kind of synthetic method of disperse yellow dye | |
| CN116621885B (en) | Recycling treatment method of 2-amino-4-acetamido anisole production wastewater | |
| CN115160292B (en) | Synthesis method of 3-perfluoroalkyl thioflavone | |
| CN111423329B (en) | Resource utilization method of waste residues generated in production of 1-nitroanthraquinone by solvent method | |
| EP0090278B1 (en) | Process for the preparation of anthrimide carbazole dyes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231109 Address after: No.10 Xihe Qibei Street, Economic and Technological Development Zone, Shenyang City, Liaoning Province, 110000 Patentee after: SINOCHEM (SHENYANG) ADVANCED MATERIALS TECHNOLOGY CO.,LTD. Address before: No.4 Hangzhou West Road, Shenbei New District, Shenyang City, Liaoning Province Patentee before: Shenyang Xinji Chemistry Co.,Ltd. |