CN102863813A - Synthesis and application of efficient composite type long-chain tertiary amine quatemary ammonium salt fluorescent whitening agents - Google Patents
Synthesis and application of efficient composite type long-chain tertiary amine quatemary ammonium salt fluorescent whitening agents Download PDFInfo
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- CN102863813A CN102863813A CN2012103810815A CN201210381081A CN102863813A CN 102863813 A CN102863813 A CN 102863813A CN 2012103810815 A CN2012103810815 A CN 2012103810815A CN 201210381081 A CN201210381081 A CN 201210381081A CN 102863813 A CN102863813 A CN 102863813A
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Abstract
The invention relates to a synthesis and an application of efficient composite type long-chain tertiary amine quatemary ammonium salt fluorescent whitening agents and particularly relates to a synthesis and an application of a series of dimethyl tertiary amine quatemary ammonium salt DSD acid-triazine composite type fluorescent whitening agents containing dodecyl/tetradecyl and hexadecyl/octadearyl. The series of whitening agents are mainly applied to paper making, coating, oil ink and spinning. The synthesis steps include a, subjecting cyanuric chloride and DSD acid to reaction to synthesize a one-step condensation product at the temperature below 0 DEG C; b, subjecting the one-step condensation product and a dodecyl/tetradecyl or hexadecyl/octadearyl dimethyl tertiary amine mixture to reaction to synthesize a two-step condensation product; and c, subjecting the two-step condensation product and a series of amino compounds to reaction to synthesize the series of efficient composite type long-chain tertiary amine quatemary ammonium salt fluorescent whitening agents. According to performance test and application results, the whitening agents are cheap in synthesis raw material, high in productivity, high in fluorescent emission performance, capable of obviously whitening cotton cloths under the alkaline condition and exerting an action of synergistic unite and suitable for mass industrialization production.
Description
Technical field
The present invention relates to the fine chemical technology field, the synthetic and application of a series of efficient compound long chain tertiary amine quaternary ammonium salt white dyess is 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 mostly is the single type white dyes, and not only cost of material is high, fluorescent emission a little less than, and whitening effect is relatively poor.Fewer by the compound white dyes report that two or more components form.Two components or multi-component white dyes do not interfere with each other Optical Absorption and radiation, the radiation wavelength scope broadens, apparent fluorescence intensity is strengthened, produced the whitening effect stronger than single component, played the effect of synergy, the this patent introduction contain 12/tetradecyl, 16/octadecyl dimethyl tertiary amine quaternary ammonium salt DSD acid-not only cost of material is cheap for triazine efficient compound long chain tertiary amine quaternary ammonium salt white dyes, productive rate is higher, and its fluorescent emission performance is stronger, pass through composite synergistic, filter paper and cotton there are obvious whitening effect, are fit to large-scale industrial production and application.Therefore, syntheticly contain 12/tetradecyl, 16/octadecyl dimethyl tertiary amine quaternary ammonium group DSD acid-triazine efficient compound long chain tertiary amine quaternary ammonium salt white dyes 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.
Most triazine-DSD acids white dyes all exists cost of material higher, and productive rate is lower, the single type poor-performing, fluorescent emission a little less than, the shortcoming such as acid resistance is relatively poor, and whiteness value is lower.
Summary of the invention
In order to solve the shortcoming of above-mentioned background technology, the present invention proposes the synthetic and application of efficient compound long chain tertiary amine quaternary ammonium salt white dyes, it utilizes the compound white dyes that contains quaternary ammonium salt group is amphoteric substance, it has the activity of optical fluorescence whitening agent and positively charged ion auxiliary concurrently, improved its anti-strongly-acid, with associativity and the fastness to washing of fiber, practicality improves greatly.
In order to address the above problem, the present invention by the following technical solutions:
Efficient compound long chain tertiary amine quaternary ammonium salt white dyes, its structure is as follows:
Wherein, R
1For the amino on the aminocompound loses formed compound group behind the hydrogen atom, described aminocompound is respectively ethanol ammonia, diethanolamine, diethylamine, para-amino benzoic acid, iminodiethanoic acid, m-chloro aniline, Sulphanilic Acid, L-glutamic acid, TYR, any in the leucine; R
2For-(CH
2)
15CH
3, R
3For-(CH
2)
17CH
3Or R
2For-(CH
2)
11CH
3, R
3For-(CH
2)
13CH
3
The synthesis step of above-mentioned compound long chain tertiary amine quaternary ammonium salt white dyes is as follows:
At first in the 1000mL there-necked flask, add 500mL deionized water and 0.1mol DSD acid (4,4`-diaminobenzil-disulfonic acid), ice bath, temperature maintains 0 ~ 5 ℃, and violent stirring adds the 0.2mol cyanuric chloride in batches, drip 10% NaOH solution, make pH be controlled at 4, reaction 3h; Then add 0.2mol 12/tetradecyl dimethyl tertiary amine or 16/octadecyl dimethyl tertiary amine, NaOH solution with 10% is regulated pH to 8, be warming up to 45 ℃, reaction 4h, add at last the above-mentioned aminocompound of 0.2mol, the NaOH solution with 10% is regulated, and makes pH remain on 10, be warming up to 90 ℃, reaction 6h; Be cooled to room temperature after reaction is finished, liquid rotating in the reactor is moved on in the large beaker, add the 500mL deionized water, the hydrochloric acid soln with 10% is regulated pH to 3, separates out solid, and the suction filtration drying obtains efficient compound long chain tertiary amine quaternary ammonium salt white dyes.
Efficient compound long chain tertiary amine quaternary ammonium salt white dyes carries out the application of fluorescent brightening to cotton.
Described application method the steps include: cotton is carried out fluorescent brightening, is 0%, 0.02% according to owf in beaker, 0.05%, 0.08%, 0.15%, 0.2%, 0.3%, bath raio 1:40 carries out dye bath, it is 11 that NaOH solution with 10% is transferred pH, with the cotton 30min that dyes at ambient temperature, take out in room temperature or 60 ℃ lower dryly, survey the whiteness performance.
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.
The present invention synthesizes a series of long chain tertiary amine quaternary triazines-compound white dyes of DSD acid, and not only cost of material is cheap for this compound whitening agent, and productive rate is higher, and its fluorescent emission performance is stronger.Because the existence of cationic season-ammonium salt group, this type of fluorescence increases the activity that has the positively charged ion auxiliary from agent, its dye uptake is compared non-quaternary ammonium salt white dyes with degree of fixation better, associativity and fastness to washing with fiber have obviously been improved, this whitening agent is compound whitening agent, by composite synergistic, cotton there is obvious whitening effect, be fit to large-scale industrial production and application.
Embodiment
Embodiment 1:
Be equipped with to 1000mL in the there-necked flask of agitator and thermometer, add successively the 500mL deionized water, 37.04g DSD acid, temperature is controlled at 0 ℃, and dispersed with stirring is even, then adds the 36.90g cyanuric chloride, and the NaOH solution with 10% is regulated pH to 4, behind the reaction 3h; Continue temperature reaction mixture to 45 ℃, add 48.29g 12/tetradecyl dimethyl tertiary amine, regulate pH value to 8 with 10%NaOH solution, react 4h.Add at last the 26.62g iminodiethanoic acid, regulate pH to 10 with 10%NaOH solution, be warming up to 90 ℃, reaction 6h is cooled to room temperature, liquid rotating in the reactor is moved on in the large beaker, add the 500mL deionized water, the hydrochloric acid soln with 10% is regulated pH to 3, separates out solid, filtration, drying get target compound.
Embodiment 2:
Be equipped with to 1000mL in the there-necked flask of agitator and thermometer, add successively the 500mL deionized water, 37.04g DSD acid, temperature is controlled at 0 ℃, and dispersed with stirring is even, then adds the 36.90g cyanuric chloride, and the NaOH solution with 10% is regulated pH to 4, behind the reaction 3h; Continue temperature reaction mixture to 45 ℃, add 48.29g 12/tetradecyl dimethyl tertiary amine, regulate pH value to 8 with 10%NaOH solution, react 4h.Add at last the 15.01g glycine, regulate pH to 10 with 10%NaOH solution, be warming up to 90 ℃, reaction 6h is cooled to room temperature, liquid rotating in the reactor is moved on in the large beaker, add the 500mL deionized water, the hydrochloric acid soln with 10% is regulated pH to 3, separates out solid, filtration, drying get target compound.
Embodiment 3:
Be equipped with to 1000mL in the there-necked flask of agitator and thermometer, add successively the 500mL deionized water, 37.04g DSD acid, temperature is controlled at 0 ℃, and dispersed with stirring is even, then adds the 36.90g cyanuric chloride, and the NaOH solution with 10% is regulated pH to 4, behind the reaction 3h; Continue temperature reaction mixture to 45 ℃, add 48.29g 12/tetradecyl dimethyl tertiary amine, regulate pH value to 8 with 10%NaOH solution, react 4h.Add at last the 26.24g leucine, regulate pH to 10 with 10%NaOH solution, be warming up to 90 ℃, reaction 6h is cooled to room temperature, liquid rotating in the reactor is moved on in the large beaker, add the 500mL deionized water, the hydrochloric acid soln with 10% is regulated pH to 3, separates out solid, filtration, drying get target compound.
Embodiment 4:
Be equipped with to 1000mL in the there-necked flask of agitator and thermometer, add successively the 500mL deionized water, 37.04g DSD acid, temperature is controlled at 0 ℃, and dispersed with stirring is even, then adds the 36.90g cyanuric chloride, and the NaOH solution with 10% is regulated pH to 4, behind the reaction 3h; Continue temperature reaction mixture to 45 ℃, add 59.51g 16/octadecyl dimethyl tertiary amine, regulate pH value to 8 with 10%NaOH solution, react 4h.Add at last 12.22g ethanol ammonia, regulate pH with 10%NaOH solution and transfer to 10, be warming up to 90 ℃, reaction 6h is cooled to room temperature, liquid rotating in the reactor is moved on in the large beaker, add the 500mL deionized water, the hydrochloric acid soln with 10% is regulated pH to 3, separates out solid, filtration, drying get target compound.
Embodiment 5:
Be equipped with to 1000mL in the there-necked flask of agitator and thermometer, add successively the 500mL deionized water, 37.04g DSD acid, temperature is controlled at 0 ℃, and dispersed with stirring is even, then adds the 36.90g cyanuric chloride, and the NaOH solution with 10% is regulated pH to 4, behind the reaction 3h; Continue temperature reaction mixture to 45 ℃, add 59.51g 16/octadecyl dimethyl tertiary amine, regulate pH value to 8 with 10%NaOH solution, react 4h.Add at last the 27.43g para-amino benzoic acid, regulate pH with 10%NaOH solution and transfer to 10, be warming up to 90 ℃, reaction 6h is cooled to room temperature, liquid rotating in the reactor is moved on in the large beaker, add the 500mL deionized water, the hydrochloric acid soln with 10% is regulated pH to 3, separates out solid, filtration, drying get target compound.
Embodiment 6:
Be equipped with to 1000mL in the there-necked flask of agitator and thermometer, add successively the 500mL deionized water, 37.04g DSD acid, temperature is controlled at 0 ℃, and dispersed with stirring is even, then adds the 36.90g cyanuric chloride, and the NaOH solution with 10% is regulated pH to 4, behind the reaction 3h; Continue temperature reaction mixture to 45 ℃, add 59.51g 16/octadecyl dimethyl tertiary amine, regulate pH value to 8 with 10%NaOH solution, react 4h.Add at last the 21.51g m-chloro aniline, regulate pH with 10%NaOH solution and transfer to 10, be warming up to 90 ℃, reaction 6h is cooled to room temperature, liquid rotating in the reactor is moved on in the large beaker, add the 500mL deionized water, the hydrochloric acid soln with 10% is regulated pH to 3, separates out solid, filtration, drying get target compound.
Embodiment 7:
Cotton is boiled 30min in water, take out, too much moisture is extruded in the water flushing gently, in the 200mL beaker, be 0%, 0.02%, 0.05% with synthetic white dyes W1-W11 according to owf, 0.08%, 0.15%, 0.2%, 0.3% dye bath, bath raio 1:40, it is 11 that the NaOH solution with 10% is regulated pH, the cotton of processing is entered to dye by the dye vat number order, and constantly stir, room temperature dyeing 30min, wash, dry or in oven dry below 60 ℃, survey whiteness.
R among the W1-W11
1Be respectively ethanol ammonia, diethanolamine, diethylamine, para-amino benzoic acid, iminodiethanoic acid, m-chloro aniline, Sulphanilic Acid, L-glutamic acid, TYR, the amino group that forms behind the hydrogen atom, the R of losing in the leucine
2For-(CH
2)
15CH
3, R
3For-(CH
2)
17CH
3, brighten the result as described in Table 1:
Table 1 efficient compound long chain tertiary amine quaternary ammonium salt white dyes is to the whitening effect of cotton
In the table: owf is dye bath concentration, and FBs is production code member.
The result proves, not only cost of material is cheap for this compound whitening agent, and productive rate is higher, and its fluorescent emission performance is stronger, by compound synergic, cotton is had obvious whitening effect, is fit to large-scale industrial production and application.
Claims (4)
1. efficient compound long chain tertiary amine quaternary ammonium salt white dyes, its structure is as follows:
Wherein, R
1For the amino on the aminocompound loses a formed group of hydrogen atom, described aminocompound is respectively ethanol ammonia, diethanolamine, diethylamine, para-amino benzoic acid, iminodiethanoic acid, m-chloro aniline, Sulphanilic Acid, L-glutamic acid, TYR, any in the leucine; R
2For-(CH
2)
15CH
3, R
3For-(CH
2)
17CH
3Or R
2For-(CH
2)
11CH
3, R
3For-(CH
2)
13CH
3
2. such as the synthetic method of the described efficient compound long chain tertiary amine of claim l quaternary ammonium salt white dyes, it is characterized in that, step is as follows: at first in the 1000mL there-necked flask, add 500mL deionized water and 0.1mol DSD acid (4,4`-diaminobenzil-disulfonic acid), ice bath, temperature maintain 0 ~ 5 ℃, violent stirring, add in batches the 0.2mol cyanuric chloride, drip 10% NaOH solution, make pH be controlled at 4, reaction 3h; Then add 0.2mol 12/tetradecyl dimethyl tertiary amine or 16/octadecyl dimethyl tertiary amine, NaOH solution with 10% is regulated pH to 8, be warming up to 45 ℃, reaction 4h, add at last the above-mentioned aminocompound of 0.2mol, the NaOH solution with 10% is regulated, and makes pH remain on 10, be warming up to 90 ℃, reaction 6h; Be cooled to room temperature after reaction is finished, liquid rotating in the reactor is moved on in the large beaker, add the 500mL deionized water, the hydrochloric acid soln with 10% is regulated pH to 3, separates out solid, and the suction filtration drying obtains efficient compound long chain tertiary amine quaternary ammonium salt white dyes.
3. efficient compound long chain tertiary amine quaternary ammonium salt white dyes claimed in claim 1 carries out the application of fluorescent brightening to cotton.
4. cotton is carried out the application of fluorescent brightening aspect according to claims 3 described efficient compound long chain tertiary amine quaternary ammonium salt white dyess, it is characterized in that, cotton is boiled 30min in water, take out, the water flushing, extrude gently too much moisture, in beaker, be 0%, 0.02%, 0.05% with synthetic white dyes according to dye bath concentration owf, 0.08%, 0.15%, 0.2%, 0.3%; bath raio 1:40; carry out dye bath, regulate pH 11 with 10% NaOH solution, with the cotton 30min that dyes at ambient temperature; take out in room temperature or 60 ℃ lower dryly, survey the whiteness performance.
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| CN103910755A (en) * | 2014-01-16 | 2014-07-09 | 上海工程技术大学 | Cyanuric chloride-based quaternary ammonium salt compound and preparation method thereof |
| CN106049025A (en) * | 2016-07-15 | 2016-10-26 | 东华大学 | Polycarboxylic acid formaldehyde-free non-ironing fabric whitening liquid and application thereof |
| 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 |
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| CN103910755B (en) * | 2014-01-16 | 2016-08-24 | 上海工程技术大学 | A kind of quarternary ammonium salt compound based on Cyanuric Chloride and preparation method thereof |
| CN103910755A (en) * | 2014-01-16 | 2014-07-09 | 上海工程技术大学 | Cyanuric chloride-based quaternary ammonium salt compound and preparation method thereof |
| CN106049025A (en) * | 2016-07-15 | 2016-10-26 | 东华大学 | Polycarboxylic acid formaldehyde-free non-ironing fabric whitening liquid and application thereof |
| CN106588800B (en) * | 2016-12-20 | 2019-08-13 | 贺州学院 | Tetrabasic carboxylic acid heavy calcium carbonate powder fluorescent whitening agent and its preparation method and application |
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| CN106588800A (en) * | 2016-12-20 | 2017-04-26 | 贺州学院 | Tetracarboxylic acid heavy calcium carbonate powder fluorescent whitening agent and 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 |
| CN106632116B (en) * | 2016-12-20 | 2019-08-13 | 贺州学院 | A kind of water solubility heavy calcium carbonate powder fluorescent whitening agent and its preparation method and application |
| CN107188863A (en) * | 2017-06-16 | 2017-09-22 | 贺州学院 | A kind of EMA quaternary ammonium salt fluorescent whitening agent and preparation method and application |
| CN107188862A (en) * | 2017-06-16 | 2017-09-22 | 贺州学院 | A kind of morpholinyl multipurpose fluorescence brightening agent and preparation method and application |
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| CN107188863B (en) * | 2017-06-16 | 2021-04-20 | 贺州学院 | Ethyl methacrylate quaternary ammonium salt fluorescent whitening agent and preparation method and application thereof |
| CN107311952A (en) * | 2017-07-06 | 2017-11-03 | 广西碳酸钙产业化工程院有限公司 | A kind of preparation method and applications of calcium carbonate powder brightening agent and surfactant |
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| CN109627221A (en) * | 2018-11-28 | 2019-04-16 | 贺州学院 | A kind of novel amino urea-talan color difference modifying agent |
| 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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Application publication date: 20130109 |