CN102517178B - Preparing method of stilbene biphenyl fluorescent brightener - Google Patents
Preparing method of stilbene biphenyl fluorescent brightener Download PDFInfo
- Publication number
- CN102517178B CN102517178B CN201110378197.9A CN201110378197A CN102517178B CN 102517178 B CN102517178 B CN 102517178B CN 201110378197 A CN201110378197 A CN 201110378197A CN 102517178 B CN102517178 B CN 102517178B
- Authority
- CN
- China
- Prior art keywords
- sodium
- biphenyl
- filter cake
- fluorescent brightener
- bis
- 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
- -1 stilbene biphenyl fluorescent brightener Chemical compound 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title abstract description 7
- 239000012065 filter cake Substances 0.000 claims abstract description 68
- 239000002245 particle Substances 0.000 claims abstract description 23
- 239000000047 product Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000007670 refining Methods 0.000 claims abstract description 15
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 58
- 239000011734 sodium Substances 0.000 claims description 55
- 229910052708 sodium Inorganic materials 0.000 claims description 55
- 239000004305 biphenyl Substances 0.000 claims description 37
- 239000002002 slurry Substances 0.000 claims description 36
- 238000002360 preparation method Methods 0.000 claims description 33
- 235000010290 biphenyl Nutrition 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000470 constituent Substances 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- LCRMGUFGEDUSOG-UHFFFAOYSA-N naphthalen-1-ylsulfonyloxymethyl naphthalene-1-sulfonate;sodium Chemical compound [Na].C1=CC=C2C(S(=O)(OCOS(=O)(=O)C=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 LCRMGUFGEDUSOG-UHFFFAOYSA-N 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- 238000010009 beating Methods 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000010612 desalination reaction Methods 0.000 claims description 9
- 235000019600 saltiness Nutrition 0.000 claims description 9
- 239000000975 dye Substances 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 229920000858 Cyclodextrin Polymers 0.000 claims description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 150000002191 fatty alcohols Chemical group 0.000 claims description 5
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- 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 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 235000010755 mineral Nutrition 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 3
- HVUMOYIDDBPOLL-UHFFFAOYSA-N 2-(3,4-Dihydroxyoxolan-2-yl)-2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)C1OCC(O)C1O HVUMOYIDDBPOLL-UHFFFAOYSA-N 0.000 claims description 2
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- HEBRGEBJCIKEKX-UHFFFAOYSA-M sodium;2-hexadecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HEBRGEBJCIKEKX-UHFFFAOYSA-M 0.000 claims description 2
- YURJBQIXCLCEKT-UHFFFAOYSA-M sodium;2-octadecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O YURJBQIXCLCEKT-UHFFFAOYSA-M 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 abstract 1
- 239000000084 colloidal system Substances 0.000 abstract 1
- 238000011033 desalting Methods 0.000 abstract 1
- 238000004537 pulping Methods 0.000 abstract 1
- 238000001694 spray drying Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 238000001914 filtration Methods 0.000 description 15
- 239000012153 distilled water Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- 230000002087 whitening effect Effects 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- CMJUNAQINNWKAU-KTKRTIGZSA-N 2-[[(z)-2-oxononadec-10-enyl]amino]ethanesulfonic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)CNCCS(O)(=O)=O CMJUNAQINNWKAU-KTKRTIGZSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Landscapes
- Detergent Compositions (AREA)
Abstract
A preparing method of a stilbene biphenyl fluorescent brightener comprises performing desalting secondary refining to a filter cake containing the stilbene biphenyl fluorescent brightener; pulping the filter cake; homogenizing serosity through a colloid mill or a high-pressure homogenizer so as to guarantee that fineness of particles in the serosity is 10-100mum; and finally performing spray drying to the serosity to obtain a product. Effective component(s) of the filter cake containing the stilbene biphenyl fluorescent brightener is/are one of or a mixture of a plurality of sulfonyl styryl biphenyl compounds. The preparing method enables the fluorescent brightener having high water solubility at a normal temperature to be obtained, and has the effects of saving energy and reducing production cost.
Description
Technical field
The present invention relates to a kind of preparation method of stilbene biphenyl fluorescent brightener.
Background technology
Along with improving constantly of living standard of urban and rural population level, the demand of liquid washing agent is in continuous lifting.At present, in liquid washing agent, white dyes main component used is 4,4 '-bis--(2-sodium sulfonate styryl) biphenyl, its solubleness (25 ℃) is at 15g/l-25g/l, in liquid washing agent production process, require the strength of solution of preparation greatly between 45-50g/l, because the solubleness of the white dyes of selling is in the market lower, this just requires to need to be warmed up to 60-70 ℃ in the process of its solution of preparation, the heat retaining property that the container of the solution preparing also requires, in order to avoid temperature declines, rear solute is separated out in solution.
Summary of the invention
The object of this invention is to provide a kind of preparation method of stilbene biphenyl fluorescent brightener, it can obtain the white dyes with highly water-soluble under normal temperature, thereby in the process of preparation whitening agent solution just without intensification, store the container of aimed concn whitening agent solution also without taking Insulation, the object that reach energy-conservation, reduces production costs.
For this reason, the invention provides a kind of preparation method of stilbene biphenyl fluorescent brightener, it is characterized in that: described preparation method comprises the following steps:
(1) by the filter cake containing stilbene biphenyl fluorescent brightener, the secondary refining that carries out desalination: first by this filter cake recrystallization in the aqueous solution of pH8-10; Then refining for the first time filter cake is continued to recrystallizing and refining in lower aliphatic alcohols, finally obtain the filter cake of saltiness < 0.5wt%;
(2) by the filter cake making beating stage in upper step: filter cake is water-soluble, make the aqueous solution, first add 1-10wt% dispersion agent to stir, and then add 1-10wt% stopping composition, continue to stir 30 minutes;
(3) again slurries are passed through to colloidal mill or high pressure homogenizer homogenizing, the particle fineness of guaranteeing particle in slurries is 10-100 μ m; In preferred described slurries, the particle fineness of particle is 20-40 μ m.
(4) final slurries are by the dry liquid washing agent white dyes product that obtains highly water-soluble of spraying;
Wherein the effective constituent of the filter cake of stilbene biphenyl fluorescent brightener is one or more mixture of the represented 4,4'-Bis[2-(2-sulfophenyl)ethenyl compound of Formula I:
The effective constituent of filter cake is the mixture of 4,4 '-bis--(2-sodium sulfonate styryl) biphenyl and 4,4 '-bis--(4-sodium sulfonate styryl) biphenyl, and both blending ratios are 1/4-4/1.
The effective constituent of filter cake is 4-(2-sodium sulfonate styryl)-4 '-(4-sodium sulfonate styryl)-biphenyl 40-60wt%, 4,4 '-bis--(2-sodium sulfonate styryl) biphenyl 20-30wt%, 4,4 '-bis--(4-sodium sulfonate styryl) biphenyl 20-30wt%.
Preferably the effective constituent of filter cake is 4-(2-sodium sulfonate styryl)-4 '-(4-sodium sulfonate styryl)-biphenyl 45-50wt%, 4,4 '-bis--(2-sodium sulfonate styryl) biphenyl 25-30wt%, 4,4 '-bis--(4-sodium sulfonate styryl) biphenyl 25-30wt%.
Described stopping composition is the mixture of salt, sodium sulfate, sodium carbonate, wilkinite, montmorillonite, zeolite, cyclodextrin or above several stopping composition.
Dispersion agent is negatively charged ion or nonionic type dispersion agent; Anionic dispersing agents is sodium methylene bis-naphthalene sulfonate, Sodium dodecylbenzene sulfonate, hexadecyl benzene sulfonic acid sodium salt, octadecyl benzene sulfonic acid sodium salt, sodium lauryl sulphate, alkyl polyoxyethylene ether sodium sulfate, sodium soap, Alkyl ethoxy carboxylate acid sodium, alkyl sodium sulfonate, oleoyl methyl taurine sodium;
Non-ionic dispersing agent is fatty alcohol and ethylene oxide condensate paregal O 25, high-carbon fatty alcohol (C12-18) polyoxyethylene (n=15-25), lipid acid (C16-18) polyoxyethylene ester, polyoxyethylene amine, sorbitan ester, span 40, sorbester p18 or Polyethylene Glycol-600-2000.
Described dispersion agent and weighting agent adding proportion are 2/3-3/2; Weighting agent is salt, anhydrous sodium sulphate or sodium carbonate; Described dispersion agent is sodium methylene bis-naphthalene sulfonate, paregal O 25 or both mixtures, and wherein sodium methylene bis-naphthalene sulfonate and paregal O 25 blending ratios are 1/4-4/1.
Preferably sodium methylene bis-naphthalene sulfonate and paregal O 25 blending ratios are 2/3-3/2.
The aqueous solution of described alkalescence with alkali be mineral alkali or organic bases; Mineral alkali is potassium hydroxide, sodium hydroxide, sodium carbonate or sodium bicarbonate; Organic bases is Monoethanolamine MEA BASF, diethanolamine or trolamine; Lower aliphatic alcohols is methyl alcohol, ethanol or propyl alcohol.
Should can be commercially available prod or prepare containing the filter cake of stilbene biphenyl fluorescent brightener, the preparation method of this filter cake is: according to needed finished product, in reactor, add ortho-sulfonic acid sodium phenyl aldehyde, the mixture of p-sulfonic acid sodium phenyl aldehyde or ortho-sulfonic acid sodium phenyl aldehyde and p-sulfonic acid sodium phenyl aldehyde, add again 4, 4 '-bis-(diethoxy phosphonium mesitoyl methyl) biphenyl, wherein adjacent (to) sodium sulfonate phenyl aldehyde and 4, 4 '-bis-(diethoxy phosphonium mesitoyl methyl) biphenyl is pressed the mol ratio of 2.3-2.5, add solvent DMF that raw material is fully dissolved, sodium methoxide solution in 40-50 degree dropping 30% fully reacts it, after being added dropwise to complete, continue stirring reaction 8-10 hour, cooling, filtration obtains product.
The method of the present patent application is by repeatedly refining to white dyes filter cake, disperse making beating, high pressure homogenizing, spraying drying and other steps, obtain the white dyes of highly water-soluble, it is at 25 ℃, the water-soluble 50g/l clear that reaches, like this in the process of preparation whitening agent solution just without intensification, the container of storage aimed concn whitening agent solution is also without taking Insulation, the object that reach energy-conservation, reduces production costs.
Embodiment
Embodiment 1
A preparation method for highly water-soluble stilbene biphenyl fluorescent brightener, is characterized in that: described preparation method comprises the following steps:
(1) will be 4 containing effective constituent, 4 '-bis--(2-sodium sulfonate styryl) biphenyl and 4,4 '-bis--secondary refining that 500 kilograms of (4-sodium sulfonate styryl) filter cakes of 1: 1 of biphenyl (wherein solid content 55%) carry out desalination: first this filter cake is placed in to reactor, add 1500 kilograms of distilled water, and add 40 kilograms of Monoethanolamine MEA BASFs, after being heated to dissolve completely, heat filtering, be refrigerated to 5 ℃, crystallization body, press filtration obtains cake filter; Again this cake filter is put into reactor, add 2000 kilograms of ethanol, first reflux 1 hour, then be refrigerated to 5 ℃, and crystallize out, being press-filtered out filter cake is 450 kilograms (solid contents 52%), the saltiness of this filter cake is 0.4%;
(2) by the filter cake making beating stage in upper step: this filter cake is dropped in defibrination still, and add 200 kilograms of distilled water to make solution, then add 25 and 6 kilograms of sodium methylene bis-naphthalene sulfonates of 4 kilograms of paregal Os, grinding made it even after 2 hours, add again 10 kilograms of salt, grind again after 30 minutes, form slurries;
(3) again slurries are passed through to high pressure homogenizer homogenizing, by high pressure homogenizer, the particle fineness that makes particle in described slurries is 30 μ m;
(4) final slurries are dry by spraying in spray tower, obtain the product of 252 kilograms, and the solubleness of this product at 25 ℃ reaches 45g/L after testing, becomes clear liquid.
Embodiment 2
A preparation method for highly water-soluble stilbene biphenyl fluorescent brightener, is characterized in that: described preparation method comprises the following steps:
(1) will be 4-(2-sodium sulfonate styryl)-4 '-(4-sodium sulfonate styryl)-biphenyl 50wt% containing effective constituent, 4, 4 '-bis--(2-sodium sulfonate styryl) biphenyl 25wt%, 4, the secondary refining that the filter cake 500 kilograms (wherein solid content 55%) of 4 '-bis--(4-sodium sulfonate styryl) biphenyl 25wt% carries out desalination: first this filter cake is placed in to reactor, add 1500 kilograms of distilled water, and add 40 kilograms of di-alcohol, after being heated to dissolve completely, heat filtering, be refrigerated to 5 ℃, crystallization body, press filtration obtains cake filter, again this cake filter is put into reactor, add 2000 kilograms of ethanol, first reflux 1 hour, then be refrigerated to 5 ℃, and crystallize out, is press-filtered out 445 kilograms of filter cakes (solid content 53%), and the saltiness of this filter cake is 0.35%,
(2) by the filter cake making beating stage in upper step: this filter cake is dropped in defibrination still, and add 205 kilograms of distilled water to make solution, then add 25 and 4 kilograms of sodium methylene bis-naphthalene sulfonates of 6 kilograms of paregal Os, grinding made it even after 2 hours, add again 10 kilograms of anhydrous sodium sulphate, grind again after 30 minutes, form slurries;
(3) again slurries are passed through to high pressure homogenizer homogenizing, by high pressure homogenizer, the particle fineness that makes particle in described slurries is 30 μ m;
(4) final slurries are dry by spraying in spray tower, obtain the product of 254 kilograms (E=1156), and the solubleness of this product at 25 ℃ reaches 50g/L after testing, becomes clear liquid.
Embodiment 3
A preparation method for highly water-soluble stilbene biphenyl fluorescent brightener, is characterized in that: described preparation method comprises the following steps:
(1) by effective constituent be 4-(2-sodium sulfonate styryl)-4 '-(4-sodium sulfonate styryl)-biphenyl 40wt%, 4, 4 '-bis--(2-sodium sulfonate styryl) biphenyl 30wt%, 4, the secondary refining that the filter cake 500 kilograms (wherein solid content 55%) of 4 '-bis--(4-sodium sulfonate styryl) biphenyl 30wt% carries out desalination: first this filter cake is placed in to reactor, add 1500 kilograms of distilled water, and add 40 kilograms of Monoethanolamine MEA BASFs, after being heated to dissolve completely, heat filtering, be refrigerated to 5 ℃, crystallization body, press filtration obtains cake filter, again this cake filter is put into reactor, add 2000 kilograms of methyl alcohol, first reflux 1 hour, then be refrigerated to 5 ℃, and crystallize out, being press-filtered out filter cake is 450 kilograms (solid contents 52%), the saltiness of this filter cake is 0.4%,
(2) by the filter cake making beating stage in upper step: this filter cake is dropped in defibrination still, and add 200 kilograms of distilled water to make solution, then add 6 kilograms of Polyethylene Glycol-600s and 4 kilograms of sodium methylene bis-naphthalene sulfonates, grinding made it even after 2 hours, add again 10 kilograms of sodium carbonate, grind again after 30 minutes, form slurries;
(3) again slurries are passed through to high pressure homogenizer homogenizing, by high pressure homogenizer, the particle fineness that makes particle in described slurries is 30 μ m;
(4) final slurries are dry by spraying in spray tower, obtain the product of 248 kilograms, and the solubleness of this product at 25 ℃ reaches 52g/L after testing, becomes clear liquid.
Embodiment 4
A preparation method for highly water-soluble stilbene biphenyl fluorescent brightener, is characterized in that: described preparation method comprises the following steps:
(1) will be 4 containing effective constituent, 4 '-bis--(2-sodium sulfonate styryl) biphenyl and 4,4 '-bis--secondary refining that 500 kilograms of (4-sodium sulfonate styryl) filter cakes of 4: 1 of biphenyl (wherein solid content 55%) carry out desalination: first this filter cake is placed in to reactor, add 1500 kilograms of distilled water, and add 38 kilograms of trolamines, after being heated to dissolve completely, heat filtering, be refrigerated to 5 ℃, crystallization body, press filtration obtains cake filter; Again this cake filter is put into reactor, add 2000 kilograms of ethanol, first reflux 1 hour, then be refrigerated to 5 ℃, and crystallize out, being press-filtered out filter cake is 456 kilograms (solid contents 52%), the saltiness of this filter cake is 0.4%;
(2) by the filter cake making beating stage in upper step: this filter cake is dropped in defibrination still, and add 200 kilograms of distilled water to make solution, then add 25 and 7.5 kilograms of sodium methylene bis-naphthalene sulfonates of 2.5 kilograms of paregal Os, grinding made it even after 2 hours, add again 10 kilograms of salt, grind again after 30 minutes, form slurries;
(3) again slurries are passed through to high pressure homogenizer homogenizing, by high pressure homogenizer, the particle fineness that makes particle in described slurries is 30 μ m;
(4) final slurries are dry by spraying in spray tower, obtain the product of 252 kilograms, and this product solubleness at 25 ℃ reaches 50g/L after testing, becomes clear liquid.
Embodiment 5
A preparation method for highly water-soluble stilbene biphenyl fluorescent brightener, is characterized in that: described preparation method comprises the following steps:
(1) will be 4 containing effective constituent, 4 '-bis--(2-sodium sulfonate styryl) biphenyl and 4,4 '-bis--secondary refining that 500 kilograms of (4-sodium sulfonate styryl) filter cakes of 1: 4 of biphenyl (wherein solid content 55%) carry out desalination: first this filter cake is placed in to reactor, add 1500 kilograms of distilled water, and add 38 kilograms of trolamines, after being heated to dissolve completely, heat filtering, be refrigerated to 5 ℃, crystallization body, press filtration obtains cake filter; Again this cake filter is put into reactor, add 2000 kilograms of ethanol, first reflux 1 hour, then be refrigerated to 5 ℃, and crystallize out, being press-filtered out filter cake is 456 kilograms (solid contents 52%), the saltiness of this filter cake is 0.4%;
(2) by the filter cake making beating stage in upper step: this filter cake is dropped in defibrination still, and add 200 kilograms of distilled water to make solution, then add 25 and 7.5 kilograms of sodium methylene bis-naphthalene sulfonates of 2.5 kilograms of paregal Os, grinding made it even after 2 hours, add again 10 kilograms of cyclodextrin, grind again after 30 minutes, form slurries;
(3) again slurries are passed through to high pressure homogenizer homogenizing, by high pressure homogenizer, the particle fineness that makes particle in described slurries is 30 μ m;
(4) final slurries are dry by spraying in spray tower, obtain the product of 249 kilograms, and this product solubleness at 25 ℃ reaches 50g/L after testing, becomes clear liquid.
Embodiment 6
A preparation method for highly water-soluble stilbene biphenyl fluorescent brightener, is characterized in that: described preparation method comprises the following steps:
(1) will be 4-(2-sodium sulfonate styryl)-4 '-(4-sodium sulfonate styryl)-biphenyl 60wt% containing effective constituent, 4, 4 '-bis--(2-sodium sulfonate styryl) biphenyl 20wt%, 4, the secondary refining that the filter cake 500 kilograms (wherein solid content 55%) of 4 '-bis--(4-sodium sulfonate styryl) biphenyl 20wt% carries out desalination: first this filter cake is placed in to reactor, add 1500 kilograms of distilled water, and add 20 kilograms of potassium hydroxide, after being heated to dissolve completely, heat filtering, be refrigerated to 5 ℃, crystallization body, press filtration obtains cake filter, again this cake filter is put into reactor, add 2000 kilograms of ethanol, first reflux 1 hour, then be refrigerated to 5 ℃, and crystallize out, being press-filtered out filter cake is 451 kilograms (solid contents 51%), the saltiness of this filter cake is 0.4%,
(2) by the filter cake making beating stage in upper step: this filter cake is dropped in defibrination still, and add 200 kilograms of distilled water to make solution, then add 10 kilograms of sodium lauryl sulphate, grinding made it even after 2 hours, add again 10 kilograms of cyclodextrin, then grind after 30 minutes, form slurries;
(3) again slurries are passed through to high pressure homogenizer homogenizing, by high pressure homogenizer, the particle fineness that makes particle in described slurries is 30 μ m;
(4) final slurries are dry by spraying in spray tower, obtain the product of 252 kilograms, and this product solubleness at 25 ℃ reaches 48g/L after testing, becomes clear liquid.
Embodiment 7
A preparation method for highly water-soluble stilbene biphenyl fluorescent brightener, is characterized in that: described preparation method comprises the following steps:
(1) will be 4-(2-sodium sulfonate styryl)-4 '-(4-sodium sulfonate styryl)-biphenyl 45wt% containing effective constituent, 4, 4 '-bis--(2-sodium sulfonate styryl) biphenyl 25wt%, 4, the secondary refining that the filter cake 500 kilograms (wherein solid content 55%) of 4 '-bis--(4-sodium sulfonate styryl) biphenyl 30wt% carries out desalination: first this filter cake is placed in to reactor, add 1500 kilograms of distilled water, and add 20 kilograms of sodium hydroxide, after being heated to dissolve completely, heat filtering, be refrigerated to 5 ℃, crystallization body, press filtration obtains cake filter, again this cake filter is put into reactor, add 2000 kilograms of methyl alcohol, first reflux 1 hour, then be refrigerated to 5 ℃, and crystallize out, being press-filtered out filter cake is 450 kilograms (solid contents 51%), the saltiness of this filter cake is 0.4%,
(2) by the filter cake making beating stage in upper step: this filter cake is dropped in defibrination still, and add 200 kilograms of distilled water to make solution, then add 25 and 2 kilograms of sodium methylene bis-naphthalene sulfonates of 8 kilograms of paregal Os, grinding made it even after 2 hours, add again 10 kilograms of cyclodextrin, grind again after 30 minutes, form slurries;
(3) again slurries are passed through to high pressure homogenizer homogenizing, by high pressure homogenizer, the particle fineness that makes particle in described slurries is 30 μ m;
(4) final slurries are dry by spraying in spray tower, obtain the product of 250 kilograms, and this product solubleness at 25 ℃ reaches 48g/L after testing, becomes clear liquid.
Claims (8)
1. a preparation method for highly water-soluble stilbene biphenyl fluorescent brightener, is characterized in that: described preparation method comprises the following steps:
(1) by the secondary refining that carries out desalination containing the filter cake of stilbene biphenyl fluorescent brightener: recrystallization in the aqueous solution that is first 8-10 by this filter cake in pH value; Then refining for the first time filter cake is continued to recrystallizing and refining in lower aliphatic alcohols, finally obtain the filter cake of saltiness < 0.5wt%;
(2) by the filter cake making beating stage in upper step: filter cake is water-soluble, make the aqueous solution, first add 1-10wt% dispersion agent to stir, and then add 1-10wt% stopping composition, continue to stir 30 minutes;
(3) again slurries are passed through to colloidal mill or high pressure homogenizer homogenizing, the particle fineness of guaranteeing particle in slurries is 10-100 μ m;
(4) final slurries are by the dry liquid washing agent white dyes product that obtains highly water-soluble of spraying;
Wherein the effective constituent of the filter cake of stilbene biphenyl fluorescent brightener is one or more mixture of the represented 4,4'-Bis[2-(2-sulfophenyl)ethenyl compound of chemical formula I:
Described dispersion agent is negatively charged ion or nonionic type dispersion agent; Anionic dispersing agents is sodium methylene bis-naphthalene sulfonate, Sodium dodecylbenzene sulfonate, hexadecyl benzene sulfonic acid sodium salt, octadecyl benzene sulfonic acid sodium salt, sodium lauryl sulphate, alkyl polyoxyethylene ether sodium sulfate, sodium soap, Alkyl ethoxy carboxylate acid sodium, alkyl sodium sulfonate or oleoyl N-methyltaurine sodium;
Non-ionic dispersing agent is fatty alcohol and ethylene oxide condensate, C16-18 polyoxyethylene carboxylate, polyoxyethylene amine, sorbitan ester, span 40, sorbester p18 or Polyethylene Glycol-600-2000;
Described stopping composition is salt, sodium sulfate, sodium carbonate, wilkinite, montmorillonite, zeolite or cyclodextrin, or the mixture of above several stopping composition.
2. the preparation method of stilbene biphenyl fluorescent brightener according to claim 1, it is characterized in that: the effective constituent of filter cake is 4,4 '-bis--(2-sodium sulfonate styryl) biphenyl and 4, the mixture of 4 '-bis--(4-sodium sulfonate styryl) biphenyl, both weight blending ratios are 1/4-4/1.
3. the preparation method of stilbene biphenyl fluorescent brightener according to claim 1, it is characterized in that: the effective constituent of filter cake is 4-(2-sodium sulfonate styryl)-4 '-(4-sodium sulfonate styryl)-biphenyl 40-60wt%, 4,4 '-bis--(2-sodium sulfonate styryl) biphenyl 20-30wt%, 4,4 '-bis--(4-sodium sulfonate styryl) biphenyl 20-30wt%.
4. the preparation method of stilbene biphenyl fluorescent brightener according to claim 3, it is characterized in that: the effective constituent of filter cake is 4-(2-sodium sulfonate styryl)-4 '-(4-sodium sulfonate styryl)-biphenyl 45-50wt%, 4,4 '-bis--(2-sodium sulfonate styryl) biphenyl 25-30wt%, 4,4 '-bis--(4-sodium sulfonate styryl) biphenyl 25-30wt%.
5. the preparation method of stilbene biphenyl fluorescent brightener according to claim 1, is characterized in that: the part by weight that described dispersion agent and weighting agent add is 2/3-3/2; Weighting agent is salt, anhydrous sodium sulphate or sodium carbonate; Described dispersion agent is sodium methylene bis-naphthalene sulfonate or fatty alcohol and ethylene oxide condensate, or both mixtures, and wherein the weight blending ratio of sodium methylene bis-naphthalene sulfonate and fatty alcohol and ethylene oxide condensate is 1/4-4/1.
6. the preparation method of stilbene biphenyl fluorescent brightener according to claim 5, is characterized in that: the weight blending ratio of sodium methylene bis-naphthalene sulfonate and fatty alcohol and ethylene oxide condensate is 2/3-3/2.
7. the preparation method of stilbene biphenyl fluorescent brightener according to claim 1, is characterized in that: the alkaline matter in the aqueous solution that described pH value is 8-10 is mineral alkali or organic bases; Mineral alkali is potassium hydroxide, sodium hydroxide, sodium carbonate or sodium bicarbonate; Organic bases is Monoethanolamine MEA BASF, diethanolamine or trolamine; Lower aliphatic alcohols is methyl alcohol, ethanol or propyl alcohol.
8. the preparation method of stilbene biphenyl fluorescent brightener according to claim 1, is characterized in that: in described slurries, the particle fineness of particle is 20-40 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110378197.9A CN102517178B (en) | 2011-11-24 | 2011-11-24 | Preparing method of stilbene biphenyl fluorescent brightener |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110378197.9A CN102517178B (en) | 2011-11-24 | 2011-11-24 | Preparing method of stilbene biphenyl fluorescent brightener |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102517178A CN102517178A (en) | 2012-06-27 |
| CN102517178B true CN102517178B (en) | 2014-05-21 |
Family
ID=46288249
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110378197.9A Active CN102517178B (en) | 2011-11-24 | 2011-11-24 | Preparing method of stilbene biphenyl fluorescent brightener |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102517178B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102924959B (en) * | 2012-11-17 | 2014-08-13 | 山西青山化工有限公司 | Synthesis method of reddish distyrylbiphenyl fluorescent whitening agent |
| CN105063991A (en) * | 2015-08-31 | 2015-11-18 | 山西青山化工有限公司 | Fluorescent whitening agent for chinlon |
| CN107012732A (en) * | 2016-01-28 | 2017-08-04 | 德丰铭国际股份有限公司 | Fluorescent whitening agent composition |
| CN112778790B (en) * | 2021-01-04 | 2023-02-17 | 山西晋光化工有限公司 | Processing system and method for improving dissolving performance of fluorescent brightener CBS particles |
| CN114163834A (en) * | 2021-12-13 | 2022-03-11 | 陕西省石油化工研究设计院 | A kind of CBS-351 liquid whitening agent and preparation method thereof |
| CN114181245B (en) * | 2021-12-16 | 2024-04-26 | 陕西省石油化工研究设计院 | Method for separating and recovering diethyl phosphate sodium salt from fluorescent whitening agent synthetic liquid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3984399A (en) * | 1967-10-03 | 1976-10-05 | Ciba-Geigy Ag | Bis-stilbene compounds |
| CN1197065A (en) * | 1997-04-24 | 1998-10-28 | 希巴特殊化学控股公司 | Process for production of distyryl-biphenyl fluorescent whitening agents |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH619336B (en) * | 1975-11-24 | Ciba Geigy Ag | USE OF DISTYRYLBENZENE OR -DIPHENYL COMPOUNDS AS OPTICAL LIGHTENING AGENTS. |
-
2011
- 2011-11-24 CN CN201110378197.9A patent/CN102517178B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3984399A (en) * | 1967-10-03 | 1976-10-05 | Ciba-Geigy Ag | Bis-stilbene compounds |
| CN1197065A (en) * | 1997-04-24 | 1998-10-28 | 希巴特殊化学控股公司 | Process for production of distyryl-biphenyl fluorescent whitening agents |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102517178A (en) | 2012-06-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102517178B (en) | Preparing method of stilbene biphenyl fluorescent brightener | |
| CN101386587B (en) | A kind of production technology of methylnaphthalenesulfonic acid formaldehyde condensate | |
| CN103315919A (en) | Novel acylalkylisethionate esters and applications in consumer products | |
| CN101328037A (en) | Alkali lignin concrete air-entraining water reducer and its preparation method and application | |
| CN101429345A (en) | Process for producing triazine toluylene liquid fluorescent whitening agents | |
| CN102352007A (en) | Method for preparing amino aryl sulfonic acid series high-molecular dispersant utilizing organic component in waste water from CLT acid production | |
| CN102586037A (en) | Composition of water-saving heavy-dirty structure liquid detergent and preparation method | |
| CN102093573A (en) | Method for preparing modified lignosulfonate | |
| CN106368009A (en) | Rapid alkali-resistant penetration agent and compounding method thereof | |
| RU2603392C2 (en) | Fluorescent whitening agent composition | |
| CN102533462B (en) | Low-temperature efficient liquid detergent composition and preparation process thereof | |
| CN102372456B (en) | Method for preparing naphthalene series additive from low-acidity process waste water | |
| CN101474543A (en) | Preparation method of composite dispersant | |
| CN104785159B (en) | A kind of technique for preparing sulfonate and sulfuric acid composite anion surfactant | |
| CN102926279A (en) | Method for preparing liquid fluorescent brightener combination capable of being steadily stored | |
| CN103922974B (en) | One-step method prepares the method for alkyl benzene calcium sulfonate methanol solution | |
| CN102532352A (en) | Preparation method of emulsion-type 50wt% bis-(3,5,5-trimethyl caproyl) peroxide | |
| CN103436050B (en) | Liquid fluorescent whitening agent and preparation method thereof | |
| CN105294513A (en) | Method for continuous production of high-quality alkyl benzene sulfonic acid | |
| CN105482488A (en) | Liquid fluorescent whitener and preparation method thereof | |
| CN102382270A (en) | Oil well cement slurry drag reducer and preparation method thereof | |
| CN100569687C (en) | A cement compound grinding aid | |
| CN102614809B (en) | Method for preparing dispersion-stabilizer from papermaking sludge | |
| JPS604875B2 (en) | Concentrated aqueous surfactant composition | |
| CN102839026B (en) | Method for producing coal water slurry additive by utilizing heterocyclic ring aromatic hydrocarbon-enriched component |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |