CN102850819A - Synthesis and application of cetyl and octadecyl dimethyl tertiary amine hyamine type fluorescent whitening agent with hydrophilic amino - Google Patents
Synthesis and application of cetyl and octadecyl dimethyl tertiary amine hyamine type fluorescent whitening agent with hydrophilic amino Download PDFInfo
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Abstract
The invention relates to synthesis and application of a series of cetyl and octadecyl dimethyl tertiary amine hyamine type fluorescent whitening agents with hydrophilic amino. The series of whitening agents are mainly applied to papermaking, coating, printing ink and weaving. The synthesis adopts the following synthesis steps that a, cyanuric chloride and N,N-dimethyl cetyl (or octadecyl) alkyl tertiary amine are subjected to reaction for 2.5 hours at 0 to 5 DEG C, the pH(Potential of Hydrogen) value is controlled to be about 3 to 4, and one-step condensation products are synthesized; b, the one-step condensation products and DSD acid are subjected to reaction for 4 hours at 45 DEG C, the pH value is controlled to be 6 to 7, and second-step condensation products are synthesized; and c, the second-step condensation products and series of amino compounds are subjected to reaction for 6 hours at 90 to 95 DEG C, the pH value is controlled to be 8 to 9, and the series of cetyl and octadecyl dimethyl tertiary amine hyamine type fluorescent whitening agents with hydrophilic amino are synthesized.
Description
Technical field
The present invention relates to the fine chemical technology field, a series of synthetic and application with 16 and octadecyl dimethyl tertiary amine quaternary white dyes of hydrophile amino 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, because anionic sulfonic group good water solubility, relatively poor with hydrophobic fabric polyamides fiber, cellulose acetate affinity, dye uptake is not high, whitening effect is general.Conventional fluorescent whitening agent acid resistance is poor simultaneously, easily precipitates under the acidic conditions, and fluorescence property seriously reduces.And the amphoteric flourescent whitening agents with quaternary ammonium salt group have acid resistance preferably, with associativity and the advantages such as high dye uptake, highly whitened of fiber, therefore, the synthetic amphoteric flourescent whitening agents that contains 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.Mainly be 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 that semi-finished product material liquid is purified, 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 amine title complex to carry out complex reaction, removes subsequently the nearly all excessive salt that forms in this reaction process, generates a kind of water-soluble complexes.The purification technique that adopts 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 ammonium salt group, and wherein each hydroxyl radical is optional by one or more other heteroatomss disconnection and/or replacements.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 triazine radical amido diphenyl ethylene white dyes.
Summary of the invention
In order to solve the shortcoming of above-mentioned background technology, the present invention proposes and the hexadecyl and the synthesizing of octadecyl dimethyl tertiary amine group quaternary white dyes that contain amino structure reach application, it utilizes the type white dyes that contains quaternary ammonium salt group is amphoteric substance, it has optical fluorescence concurrently and brightens activity with the positively charged ion auxiliary, improved its anti-strongly-acid, good with associativity, fastness to washing and the whitening effect of fiber, practicality improves greatly.
To achieve these goals, the present invention adopts technical scheme:
Have 16 and octadecyl dimethyl tertiary amine quaternary triazine-DSD acids white dyes of hydrophile amino, its structure is as follows:
Wherein, R
1Lose the group that forms behind the hydrogen atom for amino in the aminocompound, described aminocompound is Sulphanilic Acid, diethanolamine, diethylamine, para-amino benzoic acid, ethanol ammonia, m-chloro aniline, R
2For-(CH
2)
15CH
3(CH
2)
17CH
3
Above-mentioned synthetic method with 16 and octadecyl dimethyl tertiary amine quaternary triazine-DSD acids white dyes of hydrophile amino comprises the following steps:
In the 1000mL there-necked flask, add 500mL water and 36.90g cyanuric chloride, ice bath, temperature maintains 0-5 ℃; Stir and add N with the cyanuric chloride equimolar amount, N-dimethyl 16 or octadecyl tertiary amine, adding 10% NaOH solution, to make pH value of reaction system be 3-4, reaction 2.5h; Then add the DSD acid (4,4`-diaminobenzil-disulfonic acid) with cyanuric chloride 1/2 molar weight, be warming up to 40-50 ℃, and with 10% NaOH solution adjust pH 6-7, react 4h; Add at last and N, the aminocompound of N-methyl hexadecyl tertiary amine equimolar amount is regulated pH value 8-9 with 10% NaOH solution, and reaction 6h is cooled to room temperature, and adding sodium-chlor makes saturated, separates out solid, and suction filtration dryly gets yellow product.
16 and the application of octadecyl dimethyl tertiary amine quaternary triazine DSD acids white dyes aspect pure cotton cloth is brightened with hydrophile amino.
Described application method is: when pure cotton cloth was carried out fluorescent brightening, the whitening agent consumption was that the 0.03-0.35%(of pure cotton cloth weight is dye bath concentration owf), bath raio is 1:40; Be 7-8 with 10% NaOH solution adjust pH, add the crystallization saltcake, 1L solution adds 5g crystallization saltcake; During dyeing, in the solution of the cotton cloth impregnated that cuts out such as above-mentioned different concns, heating, and temperature is risen with 2 ℃/min, heating 15min, temperature rises to 50 ℃ from 20 ℃, and then, temperature keeps 50 ℃, behind the 15min, cotton is shifted out from bath, flushing is dry in cold water.
Described owf is dye bath concentration, i.e. the weight ratio of whitening agent and the cotton that will brighten, and described bath raio is dye liquor volume and cotton weight ratio.
Synthetic and the application of the hexadecyl that contains amino structure that the present invention proposes and octadecyl dimethyl tertiary amine group quaternary white dyes, it utilizes the type white dyes that contains quaternary ammonium salt group is amphoteric substance, it has optical fluorescence concurrently and brightens activity with the positively charged ion auxiliary, improved its anti-strongly-acid, good with associativity, fastness to washing and the whitening effect of fiber, practicality improves greatly.
Description of drawings
Fig. 1 is the nuclear magnetic spectrogram of embodiment 1 preparing product.
Embodiment
Embodiment 1:
In the 1000mL there-necked flask, add 500mL deionized water and 36.90g cyanuric chloride, ice bath, temperature maintains 0-5 ℃; Stir and also to add 53.90g N, N-dimethyl 16 (or 18) alkyl tertiary amine, adding 10% NaOH solution, to make pH value of reaction system be 3-4, reaction 2.5h; Then add 37.04g DSD acid, be warming up to 40-50 ℃, and with 10% NaOH solution adjust pH 6-7, react 4h; Add at last the 34.64g Sulphanilic Acid, regulate pH value 8-9 with 10% NaOH solution, reaction 6h is cooled to room temperature, adds sodium-chlor and makes saturatedly, separates out solid, suction filtration, dry must yellow product
Nuclear magnetic spectrogram: take example 1 as example, product structure is: R
1Be the amino group that forms behind the hydrogen atom, the R of losing in the Sulphanilic Acid
2For-(CH
2)
15CH
3, corresponding nuclear magnetic spectrogram data are
1H-NMR (DMSO-d
6): 10.72 (s, NH, 2H), 9.54 (s, NH, 2H), 8.20 (s, ArH, 2H), 7.88 (s, CH=CH, 2H), 7.59 (d, ArH, 4H), 7.57 (d, ArH, 4H), 0.69-1.54 (m, NC
16H
33(CH
3)
2, 78H).。
Embodiment 2:
In the 1000mL there-necked flask, add 500mL deionized water and 36.90g cyanuric chloride, ice bath, temperature maintains 0-5 ℃; Stir and also to add 53.90g N, N-dimethyl 16 (or 18) alkyl tertiary amine, adding 10% NaOH solution, to make pH value of reaction system be 3-4, reaction 2.5h; Then add 37.04g DSD acid, be warming up to 40-50 ℃, and with 10% NaOH solution adjust pH 6-7, react 4h; Add at last the 21.03g diethanolamine, regulate pH value 8-9 with 10% NaOH solution, reaction 6h is cooled to room temperature, adds sodium-chlor and makes saturatedly, separates out solid, suction filtration, dry must yellow product.
Embodiment 3:
In the 1000mL there-necked flask, add 500mL deionized water and 36.90g cyanuric chloride, ice bath, temperature maintains 0-5 ℃; Stir and also to add 53.90g N, N-dimethyl 16 (or 18) alkyl tertiary amine, adding 10% NaOH solution, to make pH value of reaction system be 3-4, reaction 2.5h; Then add 37.04g DSD acid, be warming up to 40-50 ℃, and with 10% NaOH solution adjust pH 6-7, react 4h; Add at last the 14.63g diethylamine, regulate pH value 8-9 with 10% NaOH solution, reaction 6h is cooled to room temperature, adds sodium-chlor and makes saturatedly, separates out solid, suction filtration, dry must yellow product.
Embodiment 4:
In the 1000mL there-necked flask, add 500mL deionized water and 36.90g cyanuric chloride, ice bath, temperature maintains 0-5 ℃; Stir and also to add 53.90g N, N-dimethyl 16 (or 18) alkyl tertiary amine, adding 10% NaOH solution, to make pH value of reaction system be 3-4, reaction 2.5h; Then add 37.04g DSD acid, be warming up to 40-50 ℃, and with 10% NaOH solution adjust pH 6-7, react 4h; Add at last the 27.43g para-amino benzoic acid, regulate pH value 8-9 with 10% NaOH solution, reaction 6h is cooled to room temperature, adds sodium-chlor and makes saturatedly, separates out solid, suction filtration, dry must yellow product.
Embodiment 5:
In the 1000mL there-necked flask, add 500mL deionized water and 36.90g cyanuric chloride, ice bath, temperature maintains 0-5 ℃; Stir and also to add 53.90g N, N-dimethyl 16 (or 18) alkyl tertiary amine, adding 10% NaOH solution, to make pH value of reaction system be 3-4, reaction 2.5h; Then add 37.04g DSD acid, be warming up to 40-50 ℃, and with 10% NaOH solution adjust pH 6-7, react 4h; Add at last 12.22g ethanol ammonia, regulate pH value 8-9 with 10% NaOH solution, reaction 6h is cooled to room temperature, adds sodium-chlor and makes saturatedly, separates out solid, suction filtration, dry must yellow product.
Embodiment 6:
In the 1000mL there-necked flask, add 500mL deionized water and 36.90g cyanuric chloride, ice bath, temperature maintains 0-5 ℃; Stir and also to add 53.90g N, N-dimethyl 16 (or 18) alkyl tertiary amine, adding 10% NaOH solution, to make pH value of reaction system be 3-4, reaction 2.5h; Then add 37.04g DSD acid, be warming up to 40-50 ℃, and with 10%NaOH solution adjust pH 6-7, react 4h; Add at last the 21.51g m-chloro aniline, regulate pH value 8-9 with 10% NaOH solution, reaction 6h is cooled to room temperature, adds sodium-chlor and makes saturatedly, separates out solid, suction filtration, dry must yellow product.
Embodiment 7
Select its whitening effect to cotton of six kinds of product tests among above 6 embodiment, R in six kinds of products
1Be respectively Sulphanilic Acid, diethanolamine, diethylamine, para-amino benzoic acid, ethanol ammonia, the amino group that forms behind the hydrogen atom that loses in the m-chloro aniline; R
2For-(CH
2)
15CH
3The time, the product note is done product 1 to product 6.Dye liquor is 7-8 with 10% NaOH solution adjust pH, and the whitening agent consumption is that the 0.03-0.35%(of pure cotton cloth weight is dye bath concentration owf), bath raio is 1:40; Add the crystallization saltcake, 1L solution adds 5g crystallization saltcake; During dyeing, in the solution of the cotton cloth impregnated that cuts out such as above-mentioned different concns, heating, and temperature is risen with 2 ℃/min, heating 15min, temperature rises to 50 ℃ from 20 ℃, and then, temperature keeps 50 ℃, behind the 15min, cotton is shifted out from bath, the flushing drying is surveyed whiteness in cold water.
These six kinds of products are to the whitening effect of pure cotton cloth, and are as shown in table 1:
Table 1 has the hexadecyldimethyl benzyl ammonium tertiary amine quaternary ammonium salt high-performance white dyes of amino structure to the whitening effect of pure cotton cloth
Experiment results proved, 16 and octadecyl dimethyl tertiary amine quaternary triazine-DSD acids white dyes with hydrophile amino that the present invention is prepared have good whitening effect to cotton.
Claims (4)
1. have 16 and octadecyl dimethyl tertiary amine quaternary triazine-DSD acids white dyes of hydrophile amino, its structure is as follows:
Wherein, R
1Lose the group that forms behind the hydrogen atom for amino in the aminocompound, described aminocompound is Sulphanilic Acid, diethanolamine, diethylamine, para-amino benzoic acid, ethanol ammonia, m-chloro aniline, R
2For-(CH
2)
15CH
3(CH
2)
17CH
3
2. the synthetic method with 16 and octadecyl dimethyl tertiary amine quaternary triazine-DSD acids white dyes of hydrophile amino claimed in claim 1 is characterized in that, comprises the following steps:
In the 1000mL there-necked flask, add 500mL water and 36.90g cyanuric chloride, ice bath, temperature maintains 0-5 ℃; Stir and add N with the cyanuric chloride equimolar amount, N-methyl 16 or octadecyl tertiary amine, adding 10% NaOH, to make pH value of reaction system be 3-4, reaction 2.5h; Then add the DSD acid with cyanuric chloride 1/2 molar weight, be warming up to 40-50 ℃, and with 10% NaOH adjust pH 6-7, react 4h; Add at last and N, the aminocompound of N-dimethyl hexadecyl tertiary amine equimolar amount is regulated pH value 8-9 with 10% NaOH, and reaction 6h is cooled to room temperature, and adding sodium-chlor makes saturated, separates out solid, and suction filtration dryly gets yellow product.
3. 16 and octadecyl dimethyl tertiary amine quaternary triazine with hydrophile amino claimed in claim 1-application of DSD acids white dyes aspect pure cotton cloth is brightened.
4. 16 and octadecyl dimethyl tertiary amine quaternary triazine with hydrophile amino as claimed in claim 3-application of DSD acids white dyes aspect pure cotton cloth is brightened, it is characterized in that: when pure cotton cloth is carried out fluorescent brightening, the whitening agent consumption is the 0.03-0.35% of pure cotton cloth weight, and bath raio is 1:40; Regulating Value in Dyeing Process with 10%NaOH is 7-8, adds the crystallization saltcake, and 1L solution adds 5g crystallization saltcake; During dyeing, in the solution of the cotton cloth impregnated that cuts out such as above-mentioned different concns, heating, and temperature is risen with 2 ℃/min, heating 15min, temperature rises to 50 ℃ from 20 ℃, and then, temperature keeps 50 ℃, behind the 15min, cotton is shifted out from bath, dry after the flushing in cold water.
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Cited By (7)
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| CN106588801A (en) * | 2016-12-20 | 2017-04-26 | 贺州学院 | Dicarboxylic acid heavy calcium carbonate powder fluorescent whitening agent as well as preparation method and application thereof |
| CN106632116A (en) * | 2016-12-20 | 2017-05-10 | 贺州学院 | Water-soluble fluorescent whitening agent for coarse whiting powder as well as preparation method and application thereof |
| CN107321264A (en) * | 2017-06-16 | 2017-11-07 | 广西碳酸钙产业化工程院有限公司 | A kind of Shuangzi fluorescent brightening surfactant and preparation method and application |
| CN107739347A (en) * | 2017-10-12 | 2018-02-27 | 贺州学院 | 3 methylaniline diphenyl ethylene derivatives and its production and use |
| CN109504369A (en) * | 2018-11-28 | 2019-03-22 | 贺州学院 | A kind of sulfoamido stilbene disulfonic acid class color difference modifying agent |
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| CN102504570A (en) * | 2011-09-26 | 2012-06-20 | 山东大学 | Fluorescent whitening agent with di-ethers quaternary ammonium salt and synthesis and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106588801A (en) * | 2016-12-20 | 2017-04-26 | 贺州学院 | Dicarboxylic acid heavy calcium carbonate powder fluorescent whitening agent as well as preparation method and application thereof |
| CN106632116A (en) * | 2016-12-20 | 2017-05-10 | 贺州学院 | Water-soluble fluorescent whitening agent for coarse whiting powder as well as preparation method and application thereof |
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| CN107321264A (en) * | 2017-06-16 | 2017-11-07 | 广西碳酸钙产业化工程院有限公司 | A kind of Shuangzi fluorescent brightening surfactant and preparation method and application |
| CN107739347A (en) * | 2017-10-12 | 2018-02-27 | 贺州学院 | 3 methylaniline diphenyl ethylene derivatives and its production and use |
| CN109504369A (en) * | 2018-11-28 | 2019-03-22 | 贺州学院 | A kind of sulfoamido stilbene disulfonic acid class color difference modifying agent |
| CN109627221A (en) * | 2018-11-28 | 2019-04-16 | 贺州学院 | A kind of novel amino urea-talan color difference modifying agent |
| CN109942569A (en) * | 2018-11-28 | 2019-06-28 | 贺州学院 | A kind of thiazolyl talan quaternary ammonium salt color difference modifying agent |
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