CN102979000B - Liquid fluorescent whitening agent used for paper whitening, and preparation method thereof - Google Patents
Liquid fluorescent whitening agent used for paper whitening, and preparation method thereof Download PDFInfo
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- 239000006081 fluorescent whitening agent Substances 0.000 title claims abstract description 38
- 239000007788 liquid Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000002087 whitening effect Effects 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- 239000002253 acid Substances 0.000 claims abstract description 37
- 150000001414 amino alcohols Chemical class 0.000 claims abstract description 22
- -1 amino alkane Chemical class 0.000 claims abstract description 20
- 239000012528 membrane Substances 0.000 claims abstract description 15
- 150000001412 amines Chemical class 0.000 claims abstract description 14
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005457 ice water Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 49
- 150000001875 compounds Chemical class 0.000 claims description 25
- 238000010792 warming Methods 0.000 claims description 25
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 20
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 18
- 241001597008 Nomeidae Species 0.000 claims description 13
- 238000006482 condensation reaction Methods 0.000 claims description 13
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims description 13
- 230000008034 disappearance Effects 0.000 claims description 12
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000012805 post-processing Methods 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 abstract description 19
- 238000001728 nano-filtration Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 238000004513 sizing Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 3
- 238000001914 filtration Methods 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- 238000003756 stirring Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 239000007793 ph indicator Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005282 brightening Methods 0.000 description 4
- PJANXHGTPQOBST-VAWYXSNFSA-N trans-stilbene Chemical group C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 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 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- HPTULVAFZQXKIS-UHFFFAOYSA-N NC1=C(C=CC=C1)C=CC1=CC=CC=C1.N1=NN=CC=C1 Chemical compound NC1=C(C=CC=C1)C=CC1=CC=CC=C1.N1=NN=CC=C1 HPTULVAFZQXKIS-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000010612 desalination reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000010813 municipal solid waste Substances 0.000 description 3
- 238000010606 normalization Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000276489 Merlangius merlangus Species 0.000 description 1
- 208000012826 adjustment disease Diseases 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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Abstract
The invention discloses a liquid fluorescent whitening agent used for paper whitening, and a preparation method thereof, and relates to the specialized auxiliaries for papermaking surface sizing and coating. The preparation method comprises the steps of dispersing cyanuric chloride in an ice water solution, adding an amine derivative having a sulfonic group; controlling a pH value within 3-4 by using an acid-binding agent; heating after a reaction is finished; adding DSD acid; adjusting the pH value to 6-7 by using the acid-binding agent; then heating to a temperature of 40-45 DEG C; adding amino alcohol or amino alkane after the reaction is finished; adjusting the pH value to 8.5-9.3 by using the acid-binding agent; heating to a temperature of 75-100 DEG C, reaction endpoint being determined on unchanged pH value; filtering with a nanofiltration membrane; and performing post treatment to obtain a final product. The liquid fluorescent whitening agent has the advantages of good water-solubility, high yellow point, good acid resistance, high whiteness, good colored light and low usage amount. No acid gas is released during the production process. The liquid fluorescent whitening agent is convenient for use, and has high stability.
Description
Technical field
The present invention relates to paper surface-sizing and coating special assistant, be specifically related to a kind of liquid fluorescent whitening agent brightened for paper and preparation method thereof, a kind of multi-sulfonic toluylene liquid fluorescent whitening agents and preparation method thereof specifically.
Background technology
Along with the raising of people's living standard, people require more and more higher to the whiteness of paper.In order to the whiteness making paper reach people's requirement, except using chemical bleaching, by the method for optical whitening, can also namely add appropriate fluorescent whitening agent, improve the visual whiteness of paper.
Fluorescent whitening agent is a kind of white dye, the paper brightened through fluorescent whitening agent is containing under ultraviolet light source shines, not only can reflect visible light, optical brightener molecules simultaneously on paper absorbs the energy of invisible ultraviolet light consistent with having characteristic frequency, at bluish violet visible region, can emit with extremely bright, gorgeous fluorescent form.Micro-sodium yellow on this bluish violet fluorescence and paper is complementary, obtains white light, paper is brightened.
Two triazine amino-stilbene type fluorescent whitening agent has brightening, increases effect that is gorgeous and blast, is the product that a class is comparatively early applied to the industries such as papermaking, weaving, coating, washing.There is complex manufacturing in traditional two triazine amino-stilbene type fluorescent whitening agents, and the problems such as product water dissolubility is poor, yellowing point is low, whiteness is low, coloured light is poor, poor stability.
Patent CN1180719 describes a series of with two or four sulfonic pair of triazine amino-stilbene type fluorescent whitening agent, but this fluorescent bleaches dissolubility in water is poor, not easily prepares the high liquid fluorescent whitening agent of stability.
A kind of fluorescent whitening agent by sulfonation is described and corresponding quaternary ammonium type compound reacts in CN130342A patent, pass through the methods of purification such as extraction, separation, high pressure ultra again by purifying products, obtain the water-soluble compound thing containing the less fluorescent whitening agent of the impurity salt generated in course of reaction and quaternary ammonium compounds.But production technology is very complicated in this invention, and production cost is higher, be not suitable for large-scale production.
The preparation method of a series of toluylene triazine liquid fluorescent brightener compound is described in the patents such as CN101429344A, CN101654894A, this line fluorescent brightening agent has had obvious raising than single fluorescent whitening agent whitening effect, but when this series products is used for paper industry, whiteness is lower, coloured light is poor, cannot meet the requirement of producing high-grade paper product.
At present, along with the development of paper industry, the requirement of people to paper is also more and more higher.Therefore synthesize a kind of whiteness higher, coloured light is better, and the much higher sulfonic acid toluylene triazine liquid fluorescent brightener of stability to have be the realistic meaning of insignificant.
Summary of the invention
The present invention is the deficiency existed to solve above-mentioned prior art, and provides a kind of liquid fluorescent whitening agent brightened for paper and preparation method thereof.
For the liquid fluorescent whitening agent that paper brightens, there is following general structure:
,
Wherein R
1be selected from following three kinds of one with sulfonic amine derivant residue,
,
R
2be selected from the one of following three kinds of amino alcohols or amino alkane residue,
.
The liquid fluorescent whitening agent brightened for paper of the present invention is a kind of toluylene triazine liquid fluorescent brightener, it prepares thinking is with Cyanuric Chloride, with sulfonic amine derivant, 4,4'-diaminobenzil-2, the derivative of 2'-disulfonic acid (DSD acid), amino alcohol or amino alkane is that raw material obtains semi-finished product by three step organic synthesis, by nanofiltration device, semi-finished product are purified again, obtain multi-sulfonic toluylene liquid fluorescent whitening agents.
The present invention is achieved by the following technical solutions:
For a preparation method for the liquid fluorescent whitening agent that paper brightens, completed by following steps:
(1) by the effect of ice mill, Cyanuric Chloride is dispersed in ice water solution, add with sulfonic amine derivant, wherein Cyanuric Chloride is 1:0.98 ~ 1.01 with the mol ratio with sulfonic amine derivant, at 0 ~ 5 DEG C, make pH value of reaction system control 3 ~ 4 with acid binding agent, until the condensation reaction of amino value disappearance one step terminates in reaction system, obtain compound Ι, its structural formula is as follows:
;
(2) reaction system that step (1) obtains is warming up to 20 ~ 25 DEG C, add DSD acid, wherein the mol ratio of compound Ι and DSD acid is 1:0.49 ~ 0.50, pH value of reaction system is regulated to be 6 ~ 7 with acid binding agent, 40 ~ 45 DEG C are warming up to after 15 ~ 20min, until amino value disappearance end two step condensation reaction in system, obtain compound ii, its structural formula is as follows:
；
(3) amino alcohol or amino alkane is added in reaction system step (2) obtained, wherein compound ii and amino alcohol or amino alkane mol ratio are 1:1.04 ~ 1.23, regulating with acid binding agent makes pH value of reaction system control 8.5 ~ 9.3, be warming up to 75 ~ 100 DEG C, reaction end is not changed to standard with pH, obtain compound III, its structural formula is as follows, wherein R
2for amino alcohol or amino alkane residue:
;
(4) compound III is adopted nanofiltration membrane, after carrying out post processing, get product.
Further, described acid binding agent to be mass fraction be 30% sodium hydrate aqueous solution.
Described NF membrane is NFM series membranes core.
The present invention is according to the pertinent regulations of " fluorescent whitening agent APH " in Q/HHJ 0221-2005, and test the whitening effect of brightening agent prepared by the present invention, concrete grammar is as follows:
Extract 5 inventive samples, according to kaolin: the ratio of coarse whiting=70:30 take a certain amount of white material and phase dialogue material oven-dry weight 18% styrene-acrylic latex in beaker, after fully stirring, brightening agent is added according to 0.6% consumption, namely abundant stirring coating be made into, and with line rod spreader, coating is applied on bodystock paper, puts into drying box and dry, baking temperature 70 DEG C, drying time, 30min, took out after drying, smooth through squeezer, can survey its whiteness and coloured light after taking-up, its test data is as follows:
As can be seen from the above data, the many sulfonic acid toluylene triazine liquid fluorescent brightener whiteness prepared by the present invention, coloured light are all better than at present at the whitening effect of the widely used fluorescent whitening agent 220 of paper industry.
The present invention strictly controls reaction condition in course of reaction, and in a step condensation reaction, control ph is 3.0 ~ 4.0, temperature is 0 ~ 5 DEG C, and reaction end is as the criterion with the disappearance of amino value, in two step condensation reactions, control pH is 6.0 ~ 7.0, and temperature is 40 ~ 45 DEG C, and reaction end is as the criterion with the disappearance of amino value; In three step condensation reactions, control pH is 8.5 ~ 9.3, and temperature is 75 ~ 100 DEG C, and reaction end is not changed to standard with pH, reduces the generation of accessory substance to greatest extent, ensure that the chromatographic purity of target product.
Select in preparation method of the present invention to select during acid binding agent mass fraction be 30% sodium hydrate aqueous solution, by controlling the speed and the reaction time that add acid binding agent, prevent the carrying out of hydrolysis, with make the technique of acid binding agent with caustic soda compared with, product chromatographic purity is higher, better quality.
Fluorescent whitening agent of the present invention is fluid product, therefore the stability of product is most important, traditional production toluylene triazine fluorescent whitening agent is all pass through liquid making technique substantially, the stability of product can not be ensured, research finds, the principal element affecting liquid fluorescent whitening agent stability is the inorganic salts generated in course of reaction, inorganic salt content is lower, the stability of liquid fluorescent whitening agent is better, the present invention adopts NF membrane desalting technology to replace the liquid making technique of complex process, this method not only can improve the stability of product, and the yield of product can be increased, and the pollution that can reduce environment.
Compared with prior art, the present invention has following benefit: product good water solubility, yellowing point is high, acid resistance good, whiteness is high, coloured light is good, and consumption is few; Solve the problem of acid gas discharge in production process, nanofiltration of adopting new technology processes, and makes to discharge without acid gas in production process; Liquid fluorescent whitening agent product is easy to use, is applicable to automated production and adds metering continuously, at normal temperatures, has higher stability.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described.
Embodiment 1
For the preparation method of the liquid fluorescent whitening agent that paper brightens, completed by following steps:
(1) in 2000mL beaker, 500g water, 100g trash ice is added, temperature is made to be down to 0 ~ 5 DEG C, be 1.0 ~ 2.0 with the concentrated hydrochloric acid adjust pH that concentration is 30%, add 40g Cyanuric Chloride, open and stir, ice mill 1h, add 59.6 g with sulfonic amine derivant, stir 1h, temperature remains on 0 ~ 5 DEG C, be 3.0 ~ 4.0 with the sodium hydroxide solution regulation system pH that the time concentration of 5 ~ 6 h is 30%, maintaining reaction system is 0 ~ 5 DEG C, is reacted to amino value in amino pH indicator detection system and disappears, stop reaction, obtained compound Ι, its structural formula is as follows:
;
(2) 20 ~ 25 DEG C are warming up to, 39.6 g DSD acid are joined rapidly in above-mentioned reactant liquor, the pH of reaction system is regulated to be 6.0 ~ 7.0 with the sodium hydroxide solution that concentration is 30%, 40 ~ 45 DEG C are warming up to after 15 ~ 20 min, stirring reaction disappears to by value amino in amino pH indicator detection system, stop reaction, obtained compound ii, its structural formula is as follows:
；
(3) 28 g amino alcohols or amino alkane are added in above-mentioned reactant liquor, with concentration be 30% sodium hydroxide solution adjustment reaction system pH be 8.5 ~ 9.3, be warming up to 75 DEG C, insulation 2h, continues to be warming up to 100 DEG C, is incubated 3 h, stop reaction, continuous in course of reaction is 8.5 ~ 9.3 by 30% sodium hydroxide solution adjusted to ph, obtained compound III, R
2for amino alcohol or amino alkane residue, its structural formula is as follows:
;
(4) when temperature of reaction system is down to after below 65 DEG C, suction filtration, removing water-insoluble, filtrate concentrates by the NF membrane nanofiltration desalination of NFM series membranes core, until terminate when chloride ion content is less than or equal to 0.5, gets product.
Adopt high performance liquid chromatography to analyze compound chromatographic purity, quantitative with normalization method, the content of main peak is 76%.
Embodiment 2
For the preparation method of the liquid fluorescent whitening agent that paper brightens, completed by following steps:
(1) 500g water is added in 2000mL beaker, 100g trash ice, that temperature is down to 0 ~ 5 DEG C, be 1.0 ~ 2.0 with the concentrated hydrochloric acid adjust pH that concentration is 30%, add 40g Cyanuric Chloride, open stirring, ice mill 1h, add 59.6 g with sulfonic amine derivant, stir 15 min, temperature remains on 0 ~ 5 DEG C, be 3.0 ~ 4.0 with the sodium hydroxide solution regulation system pH that the time mass fraction of 2 ~ 2.5 h is 30%, maintaining reaction system is 0 ~ 5 DEG C, be reacted to amino value in amino pH indicator detection system to disappear, stop reaction, obtained compound Ι, its structural formula is as follows:
；
(2) by above-mentioned solution warms to 15 ~ 20 DEG C, 39.6 g DSD acid are added dropwise in above-mentioned reactant liquor with the time of 45 ~ 60 min, the pH of reaction system is regulated to be 6.0 ~ 7.0 with the sodium hydroxide solution that concentration is 30%, 40 ~ 45 DEG C are warming up to after 15 ~ 20 min, stirring reaction disappears to by value amino in amino pH indicator detection system, stop reaction, obtained compound ii, its structural formula is as follows:
；
(3) 28 g amino alcohols or amino alkane are added in above-mentioned reactant liquor, adjusting reaction system pH with 30% sodium hydroxide solution is 8.5 ~ 9.3, be warming up to 75 DEG C, insulation 2h, continues to be warming up to 100 DEG C, is incubated 3 h, stop reaction, continuous in course of reaction is 8.5 ~ 9.3 by 30% sodium hydroxide solution adjusted to ph, obtained compound III, R
2for amino alcohol or amino alkane residue, its structural formula is as follows:
;
(4) when temperature of reaction system is down to after below 65 DEG C, suction filtration, removing water-insoluble, filtrate concentrates by the NF membrane nanofiltration desalination of NFM series membranes core, until terminate when chloride ion content is less than or equal to 0.5, gets product.
Adopt high performance liquid chromatography to analyze compound chromatographic purity, quantitative with normalization method, the content of main peak is 86.4%.
Embodiment 3
For the preparation method of the liquid fluorescent whitening agent that paper brightens, completed by following steps:
A) add 500g water, 100g trash ice in 2000mL beaker, being that temperature is down to 0 ~ 5 DEG C, is 1.0 ~ 2.0 with the concentrated hydrochloric acid adjust pH that concentration is 30%.Add 40g Cyanuric Chloride, open stirring, ice mill 1h, add 62.9 g with sulfonic amine derivant, stir 15 min, temperature remains on 0 ~ 5 DEG C, is 3.0 ~ 4.0 with the sodium hydroxide solution regulation system pH that the time mass fraction of 2 ~ 2.5 h is 30%, and maintaining reaction system is 0 ~ 5 DEG C, be reacted to amino value in amino pH indicator detection system to disappear, stop reaction, obtained compound Ι, its structural formula is as follows:
；
(2) by above-mentioned solution warms to 15 ~ 20 DEG C, 39.8g DSD acid is added dropwise in above-mentioned reactant liquor with the time of 45 ~ 60 min, the pH of reaction system is regulated to be 6.0 ~ 7.0 with the sodium hydroxide solution that concentration is 30%, 40 ~ 45 DEG C are warming up to after 15 ~ 20 min, stirring reaction disappears to by value amino in amino pH indicator detection system, stop reaction, obtained compound ii, its structural formula is as follows:
;
(3) 24.9g amino alcohol or amino alkane are added in above-mentioned reactant liquor, adjusting reaction system pH with 30% sodium hydroxide solution is 8.5 ~ 9.3, be warming up to 75 DEG C, insulation 2h, continues to be warming up to 100 DEG C, is incubated 3 h, stop reaction, continuous in course of reaction is 8.5 ~ 9.3 by 30% sodium hydroxide solution adjusted to ph, obtained compound III, R
2for amino alcohol or amino alkane residue, its structural formula is as follows:
;
(4) when temperature of reaction system is down to after below 65 DEG C, suction filtration, removing water-insoluble, filtrate concentrates by the NF membrane nanofiltration desalination of NFM series membranes core, until terminate when chloride ion content is less than or equal to 0.5, gets product.
Adopt high performance liquid chromatography to analyze compound chromatographic purity, quantitative with normalization method, the content of main peak is 92.1%.
Embodiment 4
For a preparation method for the liquid fluorescent whitening agent that paper brightens, completed by following steps:
(1) by the effect of ice mill, 1mol Cyanuric Chloride is dispersed in ice water solution, add 0.98mol with sulfonic amine derivant, at 0 ~ 5 DEG C, make pH value of reaction system control 3 ~ 4 with acid binding agent, until the condensation reaction of amino value disappearance one step terminates in reaction system, obtain compound Ι, its structural formula is as follows:
;
(2) reaction system that step (1) obtains is warming up to 20 ~ 25 DEG C, adds 0.99molDSD acid, regulate pH value of reaction system to be 6 ~ 7 with acid binding agent, 40 ~ 45 DEG C are warming up to after 15 ~ 20min, until amino value disappearance end two step condensation reaction in system, obtain compound ii, its structural formula is as follows:
；
(3) add 3.3mol amino alcohol or amino alkane in reaction system step (2) obtained, regulate with acid binding agent and make pH value of reaction system control 8.5 ~ 9.3, be warming up to 75 ~ 100 DEG C, reaction end is not changed to standard with pH, obtain compound III, its structural formula is as follows, wherein R
2for amino alcohol or amino alkane residue:
;
(4) compound III is adopted NFM nanofiltration membrane, after carrying out post processing, get product.
Embodiment 5
For a preparation method for the liquid fluorescent whitening agent that paper brightens, completed by following steps:
(1) by the effect of ice mill, 1mol Cyanuric Chloride is dispersed in ice water solution, add 1mol with sulfonic amine derivant, at 0 ~ 5 DEG C, make pH value of reaction system control 3 ~ 4 with acid binding agent, until the condensation reaction of amino value disappearance one step terminates in reaction system, obtain compound Ι, its structural formula is as follows:
;
(2) reaction system that step (1) obtains is warming up to 20 ~ 25 DEG C, adds 1molDSD acid, regulate pH value of reaction system to be 6 ~ 7 with acid binding agent, 40 ~ 45 DEG C are warming up to after 15 ~ 20min, until amino value disappearance end two step condensation reaction in system, obtain compound ii, its structural formula is as follows:
;
(3) add 3.3mol amino alcohol or amino alkane in reaction system step (2) obtained, regulate with acid binding agent and make pH value of reaction system control 8.5 ~ 9.3, be warming up to 75 ~ 100 DEG C, reaction end is not changed to standard with pH, obtain compound III, its structural formula is as follows, wherein R
2for amino alcohol or amino alkane residue:
;
(4) compound III is adopted NFM nanofiltration membrane, after carrying out post processing, get product.
Embodiment 6
For a preparation method for the liquid fluorescent whitening agent that paper brightens, completed by following steps:
(1) by the effect of ice mill, 1mol Cyanuric Chloride is dispersed in ice water solution, add 1.01mol with sulfonic amine derivant, at 0 ~ 5 DEG C, make pH value of reaction system control 3 ~ 4 with acid binding agent, until the condensation reaction of amino value disappearance one step terminates in reaction system, obtain compound Ι, its structural formula is as follows:
;
(2) reaction system that step (1) obtains is warming up to 20 ~ 25 DEG C, adds 1molDSD acid, regulate pH value of reaction system to be 6 ~ 7 with acid binding agent, 40 ~ 45 DEG C are warming up to after 15 ~ 20min, until amino value disappearance end two step condensation reaction in system, obtain compound ii, its structural formula is as follows:
；
(3) add 3.4mol amino alcohol or amino alkane in reaction system step (2) obtained, regulate with acid binding agent and make pH value of reaction system control 8.5 ~ 9.3, be warming up to 75 ~ 100 DEG C, reaction end is not changed to standard with pH, obtain compound III, its structural formula is as follows, wherein R
2for amino alcohol or amino alkane residue:
;
(4) compound III is adopted NFM nanofiltration membrane, after carrying out post processing, get product.
Claims (3)
1. a preparation method for the liquid fluorescent whitening agent brightened for paper, is characterized in that being completed by following steps:
(1) by the effect of ice mill, Cyanuric Chloride is dispersed in ice water solution, add with sulfonic amine derivant, wherein Cyanuric Chloride is 1:0.98 ~ 1.01 with the mol ratio with sulfonic amine derivant, at 0 ~ 5 DEG C, make pH value of reaction system control 3 ~ 4 with the sodium hydrate aqueous solution that mass fraction is 30%, until the condensation reaction of amino value disappearance one step terminates in reaction system, obtain compound Ι, its structural formula is as follows:
；
(2) reaction system that step (1) obtains is warming up to 20 ~ 25 DEG C, add DSD acid, wherein the mol ratio of compound Ι and DSD acid is 1:0.49 ~ 0.50, pH value of reaction system is regulated to be 6 ~ 7 with the sodium hydrate aqueous solution that mass fraction is 30%, 40 ~ 45 DEG C are warming up to after 15 ~ 20min, until amino value disappearance end two step condensation reaction in system, obtain compound ii, its structural formula is as follows:
；
(3) amino alcohol or amino alkane is added in reaction system step (2) obtained, wherein compound ii and amino alcohol or amino alkane mol ratio are 1:1.04 ~ 1.23, regulating with the sodium hydrate aqueous solution that mass fraction is 30% makes pH value of reaction system control 8.5 ~ 9.3, be warming up to 75 ~ 100 DEG C, reaction end is not changed to standard with pH, obtain compound III, its structural formula is as follows, wherein R
2for amino alcohol or amino alkane residue:
；
(4) compound III adopted NFM series membranes core to filter, after carrying out post processing, get product.
2. the preparation method of a kind of liquid fluorescent whitening agent brightened for paper according to claim 1, is characterized in that the Cyanuric Chloride described in step (1) is 1:1 with the mol ratio with sulfonic amine derivant.
3. the preparation method of a kind of liquid fluorescent whitening agent brightened for paper according to claim 1, is characterized in that compound ii described in step (3) and amino alcohol or amino alkane mol ratio are 1:1.1.
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| EP1752453A1 (en) * | 2005-08-04 | 2007-02-14 | Clariant International Ltd. | Storage stable solutions of optical brighteners |
| CN101096367A (en) * | 2005-10-17 | 2008-01-02 | 山东大学 | Triazinyl amino stilbene fluorescent whitening agent |
| CN101654894A (en) * | 2009-09-11 | 2010-02-24 | 山西青山化工有限公司 | Preparation method of toluylene triazine liquid fluorescent brightener composite |
| CN102121209A (en) * | 2010-12-15 | 2011-07-13 | 浙江传化华洋化工有限公司 | Preparation method of polysulfate diphenyl ethylene fluorescent whitening agent |
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| EP1752453A1 (en) * | 2005-08-04 | 2007-02-14 | Clariant International Ltd. | Storage stable solutions of optical brighteners |
| CN101096367A (en) * | 2005-10-17 | 2008-01-02 | 山东大学 | Triazinyl amino stilbene fluorescent whitening agent |
| CN101654894A (en) * | 2009-09-11 | 2010-02-24 | 山西青山化工有限公司 | Preparation method of toluylene triazine liquid fluorescent brightener composite |
| CN102121209A (en) * | 2010-12-15 | 2011-07-13 | 浙江传化华洋化工有限公司 | Preparation method of polysulfate diphenyl ethylene fluorescent whitening agent |
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