CN102311657B - Low-water-solubility fluorescent whitening agent with bactericidal action as well as synthesis method and application thereof - Google Patents
Low-water-solubility fluorescent whitening agent with bactericidal action as well as synthesis method and application thereof Download PDFInfo
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- CN102311657B CN102311657B CN2011101740141A CN201110174014A CN102311657B CN 102311657 B CN102311657 B CN 102311657B CN 2011101740141 A CN2011101740141 A CN 2011101740141A CN 201110174014 A CN201110174014 A CN 201110174014A CN 102311657 B CN102311657 B CN 102311657B
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Abstract
The invention relates to a low-water-solubility fluorescent whitening agent with bactericidal action as well as a synthesis method and application thereof. The low-water-solubility whitening agent contains a dodecyl dimethyl quaternary ammonium salt group with bactericidal action. The synthesis method comprises the following steps of: firstly carrying out condensation reaction on dodecyl dimethyl tertiary amine and cyanuric chloride, and then sequentially carrying out nucleophilic substitution with DSD (diamino 2,2'-stilbene disulphonic) acid and an amino compound to obtain a target product. According to the invention, the characteristics that a sulfonic acid type fluorescent whitening agent containing the quaternary ammonium salt group is an amphoteric compound and has properties of optical fluorescent whitening agent and cation adjuvant are utilized, thus the strong-acid resistance, bonding force with fiber and washing resistance of the whitening agent are improved; and the whitening agent has bactericidal property and is applicable to whitening of plastics, paints, printing inks, synthetic fibers and the like, and practicability is greatly improved.
Description
Technical field
The present invention relates to the fine chemical technology field, a series of low water solubility white dyes and synthetic method and purposes containing the dodecyl dimethyl quaternary ammonium group are provided.
Background technology
Triazine-DSD acids white dyes is triazinylaminodiphenethylenes ethylenes fluorescence brightener, because its higher cost performance is widely used in the industries such as papermaking, weaving, coating, washing composition, becomes domestic and international research and produces maximum a kind of white dyess.Tradition triazine-DSD acids white dyes, due to anionic sulfonic group good water solubility, poor with hydrophobic fabric polyamides fiber, cellulose acetate affinity, dye uptake is not high, and whitening effect is general.Conventional fluorescent whitening agent acid resistance is poor simultaneously, under acidic conditions, easily precipitates, and fluorescence property seriously reduces.And the amphoteric flourescent whitening agents with quaternary ammonium salt group have acid resistance preferably and with the associativity of fiber, therefore, the synthetic amphoteric flourescent whitening agents containing quaternary ammonium salt group has important practical significance.
Before the present invention, technology related to the present invention has: patent CN1287200A introduces a kind of liquid fluorescent whitening agent and synthesis technique thereof of paper industry special use.Its synthesis technique comprises that feed purification is processed, organic reaction is synthetic, the work in-process purification process, refine concentrated four steps of finished product.Be mainly to utilize the vibration mill sieve that raw material is ground to 500 orders, the work in-process purification process is to utilize reverse osmosis unit to be purified to semi-finished product material liquid, purifying products, stable storing.Patent CN1303424A discloses a kind of white dyes of undesired salt and water-soluble title complex of quaternary ammonium compound of being substantially devoid of.Its title complex is to select the white dyes of sulfonation and specific quaternary ammonium compound to carry out complex reaction, removes subsequently the nearly all excessive salt formed in this reaction process, generates a kind of water-soluble complexes.The purification technique adopted has solvent extraction, is separated, high pressure ultrafiltration and other filter methods.Patent CN1411452A discloses a kind of water miscible amphoteric flourescent whitening agents, radical X comprising a whitening agent feature, X comprises at least one anion substituent, and at least one tertiary amine groups Z with at least one color development not, basically be aliphatic polyquaternium-hydroxyl radical Y covalent attachment, Y comprises more than one quaternary amine group, and wherein each hydroxyl radical, optionally disconnected and/or replace by one or more other heteroatomss.Patent CN200510104309.6 discloses a kind of quaternary ammonium salt fluorescent brighteners.Its synthetic method is that cyanuric chloride reacts with Sulphanilic Acid, DSD acid and trolamine or triethylamine successively, synthesizes quaternary amine type triazine radical amido diphenyl ethylene white dyes.
Most triazine-DSD acids white dyes all exists anti-strongly-acid and light fastness all poor, the shortcoming easily precipitated under acidic conditions.
Summary of the invention
In order to solve the shortcoming of above-mentioned background technology, the present invention proposes low water solubility white dyes and synthetic method and application containing the dodecyl dimethyl quaternary ammonium salt group, the present invention relates to a kind of low water solubility white dyes and synthetic method and purposes with germicidal action, it is the low water solubility white dyes of the dodecyl dimethyl quaternary ammonium salt group containing having the sterilization anti-microbial effect, it utilizes the sulfonic acid type white dyes that contains the quaternary amine group is amphoteric substance, have the performance of optical fluorescence whitening agent and positively charged ion auxiliary concurrently, improved its anti-strongly-acid, associativity and fastness to washing with fiber, and there is bactericidal property, for plastics, paint, printing ink, brightening of synthon etc., practicality improves greatly.
For achieving the above object, the present invention adopts following technical proposals:
The present invention has synthesized a series of containing dodecyl dimethyl quaternary ammonium salt group triazine-DSD acids white dyes---have the low water solubility white dyes of germicidal action, its structure is as follows:
Wherein, RH is aminocompound, is diethylamine, m-chloro aniline, 2-amino-4-methylvaleric acid, 2 aminopentanedioic acid, 2,7-diamino enanthic acid, 2-amino-3-(4-hydroxy phenyl) propionic acid.
Above RH can be expressed as respectively:
The invention also discloses the above-mentioned synthetic method with white dyes of germicidal action, comprise the following steps:
(1) make solvent with water, 0～6 ℃, Dodecyl Dimethyl Amine and cyanuric chloride are carried out to the first step condensation reaction;
(2) make solvent with water, 45～50 ℃, the second step condensation reaction is carried out in the first step condensation product and DSD acid;
(3) make solvent with water, 80～85 ℃, the second step condensation product carries out the 3rd step condensation reaction with aminocompound again;
Wherein, described aminocompound is diethylamine, m-chloro aniline, 2-amino-4-methylvaleric acid, 2 aminopentanedioic acid, 2,7-diamino enanthic acid or 2-amino-3-(4-hydroxy phenyl) propionic acid.
Described step (1) is: in reaction vessel, add water as solvent, then add Dodecyl Dimethyl Amine, ice bath, violent stirring, add the cyanuric chloride with the Dodecyl Dimethyl Amine equimolar amount in batches, temperature of reaction maintains 0～6 ℃, reacts 2～3h.
V/v water in above-mentioned steps (1): Dodecyl Dimethyl Amine=200: 1.
Described step (2) is: the DSD acid to being incorporated as Dodecyl Dimethyl Amine 1/2 molar weight in the first step condensation product, with 20% sodium hydroxide solution adjust pH 8～10, be warming up to 40～50 ℃, and react 3～5h.
Described step (3) is: to add the aminocompound of equimolar amount in the second step condensation product; Regulate pH value scope 8～10, reaction 4h; Be cooled to room temperature after having reacted, regulate pH value to 2～4, separate out solid, suction filtration is dry that solid product is the quaternary white dyes;
The invention also discloses the above-mentioned purposes with white dyes of germicidal action is brightening of plastics, paint, printing ink, synthon etc., it is characterized in that: it is 0.05～0.5% that the consumption of its white dyes of application in white plastic is generally the mass percent that accounts for white plastic, and its using method in paint, printing ink is that every 100kg material adds whitening agent 10-100g.
When pH value 3～5, this series white dyes effect is more excellent.
The invention also discloses the above-mentioned another kind application with white dyes of germicidal action, it is to gram positive organism and gram-negative bacteria tool killing action.
Further, it is better to staphylococcus aureus, intestinal bacteria, dysentery bacillus or mould sterilization effect, through the several minutes contact, can kill.
The accompanying drawing explanation
Fig. 1 is the nucleus magnetic hydrogen spectrum of product in embodiment 1;
Fig. 2 is the infrared absorption spectrum of product in embodiment 1;
Fig. 3 is the ultra-violet absorption spectrum of product in embodiment 1.
Embodiment
Below by specific examples, the present invention will be further elaborated, should be noted that following explanation is only in order to explain the present invention, is not limited its content.
Embodiment 1:
In 500mL there-necked flask (ice-water bath), add 260mL water, after add 9.8g cyanuric chloride and 16.14mL Dodecyl Dimethyl Amine, violent stirring is uniformly dispersed, and temperature maintains 0-3 ℃, regulates pH in 2.0 left and right, the reaction 2.5h, after be elevated to 47 ℃, add 9.76g DSD acid, regulate pH value to 4, reaction 2.5h, after be warmed up to 75 ℃, add the 2.1g diethylamine, regulate pH value to 9.0, reaction 3.5h, dry that solid product is the quaternary white dyes, productive rate 88.3%.
The proton magnetic data:
(DMSO)：1125(s，4H，OH)，11.10(s，2H，NH)，7.65(d，2H，CH＝)，7.28～8.05(m，6H，ArH)，3.63(s，2H)2.84(t，16H，CH2CH2)，0.83-1.61(m，25H，C12H25)
Embodiment 2:
In 500mL there-necked flask (ice-water bath), add 260mL water, then add 9.8g cyanuric chloride and 6.14mL Dodecyl Dimethyl Amine, violent stirring is uniformly dispersed, and maintains 0-3 ℃, reaction 2.5h; Raise temperature to 48 ℃, add 9.76g DSD acid, regulate pH value to 5.0, reaction 3h; Temperature reaction mixture to 85 ℃, add the 3.82g m-chloro aniline, regulates pH value to 8, and reaction 3h, be cooled to room temperature, with 4mol/L hydrochloric acid, adjusts pH to 3, decompress filter, the dry solid product that obtains.Be the quaternary white dyes, productive rate 87.2%.
Fusing point:>250 ℃
The proton magnetic data, spectrogram is shown in Fig. 1:
(DMSO)：11.15(s，2H，NH)，7.40(s，2H，NH)，7.65(d，2H，CH＝)，7.28～8.05(m，14H，ArH)，3.61(s，2H)，0.83-1.61(m，25H，C12H25)
Infrared data, spectrogram is shown in Fig. 2: IR (KBr): 3433,3029,2782,1726,1629,1476,1400,1054,775,537
UV: trans (maximum absorption wavelength 337nm), see Fig. 3.
Embodiment 3:
By add the FWA of different amounts in coating, measure the cardboard whiteness after coating, investigate the variation of its whiteness, the mass percent that the whitening agent consumption accounts for coating is respectively 02%, 0.4%, and 0.8%, 1.0%
Experimental result shows, the concentration of product between 0.6～0.8g/L to whitening effect the best of coating.
Embodiment 4:
Get the intestinal bacteria (streptococcus aureus, Pseudomonas aeruginosa) after activation, be inoculated in liquid nutrient media, 37 ℃ of shaking tables are cultivated 16h, and standby some clean tube, inside add sterile purified water 9mL.Get 1ml intestinal bacteria (streptococcus aureus, Pseudomonas aeruginosa) and make some parts of bacterium liquid, be laid in respectively flat board, cultivate 24h under 37 ℃ on solid nutrient medium.Add respectively the intestinal bacteria that the 1mL cell age is 16h (streptococcus aureus, Pseudomonas aeruginosa) suspension in some clean tube, add respectively again the water of same volume, and add the diethylin optical brightener solutions (for the white dyes of embodiment 1 preparation) of different concns.Vibration, 37 ℃ of temperature, pH is 8, is 20min duration of contact.Sterilizing rate=(1-viable count/former bacterium number) * 100%.The relation of its sterilizing rate and product concentration is as shown in the table.
Experimental result shows, VBL mark product (production code member: 153536-893, chemical plant, the Yellow River, Chang'an, Xi'an) concentration be between 0.10～1.10g/L to streptococcus aureus substantially without killing action.The concentration of product all has very strong killing action to intestinal bacteria (streptococcus aureus, Pseudomonas aeruginosa) between 0.10～1.10g/L.Product concentration sterilization effect when 0.70g/L is better, and when concentration is greater than 0.70g/L, sterilization effect does not have considerable change, so selectable sterilization optimum concn should be 0.70g/L.
Claims (1)
1. there is the synthetic method of the low water solubility white dyes of germicidal action, it is characterized in that, comprise the following steps:
The 500mL there-necked flask, in ice-water bath, add 260mL water, after add 9.8g cyanuric chloride and 16.14mL Dodecyl Dimethyl Amine, violent stirring is uniformly dispersed, temperature maintains 0-3 ℃, regulate pH 2.0, reaction 2.5h, after be elevated to 47 ℃, add 9.76g DSD acid, regulate pH value to 4, reaction 2.5h, after be warmed up to 75 ℃, add the 2.1g diethylamine, regulate pH value to 9.0, reaction 3.5h is dry that solid product is the quaternary white dyes.
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| CN102898855B (en) * | 2012-09-29 | 2013-12-11 | 山东大学 | Synthesis and application of cetyl or octadecyl dimethyl tertiary amine quaternary ammonium salt high performance fluorescent whitening agent having amino acid structure |
| CN102850819A (en) * | 2012-09-29 | 2013-01-02 | 山东大学 | Synthesis and application of cetyl and octadecyl dimethyl tertiary amine hyamine type fluorescent whitening agent with hydrophilic amino |
| CN102863813A (en) * | 2012-09-29 | 2013-01-09 | 山东大学 | Synthesis and application of efficient composite type long-chain tertiary amine quatemary ammonium salt fluorescent whitening agents |
| CN103483328B (en) * | 2013-08-30 | 2016-01-06 | 华南理工大学 | A kind of toluylene white dyes and its preparation method and application |
| CN103949185B (en) * | 2014-03-21 | 2015-12-09 | 中北大学 | A kind of anion surfactant possessing bactericidal activity and preparation method thereof |
| CN107446375A (en) * | 2017-07-08 | 2017-12-08 | 广西壮族自治区工程技术研究院 | The synthesis and application of tetrasulfonic acid sodium EMA quaternary ammonium salt fluorescent whitening agent |
Citations (3)
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|---|---|---|---|---|
| CN1251581A (en) * | 1997-03-25 | 2000-04-26 | 西巴特殊化学品控股有限公司 | Fluorescent whitening agents |
| WO2004085594A1 (en) * | 2003-03-24 | 2004-10-07 | Ciba Specialty Chemicals Holding Inc. | Detergent compositions |
| CN101307031A (en) * | 2008-06-27 | 2008-11-19 | 山东大学 | Amino-chloro-benzene-containing quaternary ammonium salt type fluorescent whitener, synthesizing method thereof and applications |
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| JPS6112987A (en) * | 1984-06-28 | 1986-01-21 | 日本化薬株式会社 | Dyeing of cellulose or cellulose-containing material |
| JPS62273266A (en) * | 1986-05-20 | 1987-11-27 | Shin Nisso Kako Co Ltd | Fluorescent brightener composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1251581A (en) * | 1997-03-25 | 2000-04-26 | 西巴特殊化学品控股有限公司 | Fluorescent whitening agents |
| WO2004085594A1 (en) * | 2003-03-24 | 2004-10-07 | Ciba Specialty Chemicals Holding Inc. | Detergent compositions |
| CN101307031A (en) * | 2008-06-27 | 2008-11-19 | 山东大学 | Amino-chloro-benzene-containing quaternary ammonium salt type fluorescent whitener, synthesizing method thereof and applications |
Non-Patent Citations (1)
| Title |
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| 王军 主编.抗菌型表面活性剂的性能.《功能性表面活性剂制备与应用》.2009,(第1版),第208-209页. * |
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