CN102504568B - Fluorescent bleaching agent containing tetrathionate as well as preparation method and application - Google Patents
Fluorescent bleaching agent containing tetrathionate as well as preparation method and application Download PDFInfo
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Abstract
The invention discloses a fluorescent bleaching agent containing tetrathionate. The fluorescent bleaching agent has a structure shown as the accompanying drawing, wherein R2 is any one material in -NHCH(COOH)CH2CH2COOH, -NHCH2COOH, -NHCH(COOH)CH2CH2(CH3)2, -NHCH2CH2CH2CH2CH(NH2)COOH and -NHCH(COOH)CH2PhOH(P). The fluorescent bleaching agent containing tetrathionate has the following purposes of: (1) carrying out fluorescent bleaching on paper pulp in the paper making process; (2) being used as a washing agent to be applied or being used as accessories to be matched with conventional washing agents to be used; (3) carrying out fluorescent bleaching in the coating process; and (4) being used as toxic substances to be applied to cell toxicity tests and methyl thiazolyl tetrazolium (MTT) colorimetric tests.
Description
Technical field
The present invention relates to the fine chemical technology field, provide a series of containing tetrasulfonic acid there is low toxicity efficient and environment-friendly type white dyes, and preparation method thereof with application.
Background technology
At present, triazine-DSD acids white dyes, be triazinylaminodiphenethylenes ethylenes fluorescence brightener, because its higher cost performance is widely used in the industries such as papermaking, weaving, coating, washing composition, become domestic and international research and produce maximum a kind of white dyess.But traditional triazine-DSD acids white dyes, because aromatic amine groups has toxicity, cause being restricted in a lot of fields; And most of triazines-DSD acids white dyes exists anti-strongly-acid and light fastness all poor, the shortcoming easily precipitated under acidic conditions.And the white dyes with amino acid group has the characteristic of low toxic and environment-friendly, therefore, the synthetic low toxic and environment-friendly type white dyes containing amino acid group has a wide range of applications field, has important practical significance.
Before the present invention, technology related to the present invention has: Chinese patent CN1287200A has introduced 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 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.Chinese 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 mixture to carry out complex reaction, remove subsequently the nearly all excessive salt formed in this reaction process, generate a kind of water-soluble complexes, the purification technique of employing has solvent extraction, is separated, high pressure ultrafiltration and other filter methods.Chinese 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.Chinese patent CN1803796A discloses a kind of quaternary ammonium salt fluorescent brighteners, and 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.
Summary of the invention
For above-mentioned prior art, the invention provides and a kind ofly containing tetrasulfonic acid, there is the efficient environment-friendly type white dyes of low toxicity, it is the white dyes that contains nontoxic amino acid group, the performance that not only there is optical fluorescence whitening agent and negatively charged ion, and toxicity reduces greatly, be applicable to the every field such as biological medicine, practicality is high; The present invention also provides the preparation method and application of this white dyes.
For achieving the above object, the present invention adopts following technical proposals:
A kind of white dyes containing tetrasulfonic acid, its structure is as follows:
Wherein, R
2for-NHCH (COOH) CH
2cH
2cOOH ,-NHCH
2cOOH ,-NHCH (COOH) CH
2cH
2(CH3)
2,-NHCH
2cH
2cH
2cH
2cH (NH
2) COOH ,-any in NHCH (COOH) CH2PhOH (P).
The preparation method of the above-mentioned white dyes containing tetrasulfonic acid, step is:
(1) cyanuric chloride and DSD acid are made solvent with water and are carried out the first step condensation reaction;
(2) after above-mentioned reaction finishes, rising temperature to 45～50 ℃, then add Sulphanilic Acid, carries out the second step condensation reaction;
(3) after above-mentioned reaction finishes, rising temperature to 80～85 ℃, add amino acid, carries out the 3rd step condensation reaction, obtains the white dyes containing tetrasulfonic acid.
Described step (1) is specially: in reaction vessel, add distilled water as solvent, then add DSD acid, violent stirring under condition of ice bath, then add cyanuric chloride, reacted, wherein, DSD acid is 1: 2 with the mol ratio of cyanuric chloride, and temperature of reaction maintains below 8 ℃, reaction times 2～3h.
Described step (2) is specially: add the Sulphanilic Acid with the cyanuric chloride equimolar amount, adjust pH to 8～10, be warming up to 45～50 ℃, reaction times 3～5h.
Described step (3) is specially: add the amino acid with the cyanuric chloride equimolar amount; Regulate pH value to 8～10, reaction times 3-6h, preferably 4h; After having reacted, be cooled to room temperature, regulate pH value to 2～4, separate out solid, the suction filtration drying, obtain solid product, is the white dyes containing tetrasulfonic acid.
In described step (3), amino acid is any in L-glutamic acid, glycine, leucine, Methionin, tyrosine.
White dyes containing tetrasulfonic acid of the present invention has following purposes:
(1) in paper-making process, paper pulp is carried out to fluorescent brightening, while specifically applying, keep the pH value 2～9,0.03～1.2% of the weight that consumption is paper pulp.
(2) as washing composition application or as batching and conventional washing composition compatibility application, while specifically applying, in the clothes washings such as white health clothing, its consumption is clothing 0.02～0.4%, and the pH value is 4～10.
(3) carry out fluorescent brightening in coating process, while specifically applying, can the solution form allocate in any stage for preparing coating, conventional amount used be over dry pigment heavy 0.10～0.75%.
(4) as toxicant application in cell toxicity test, the experiment of MTT colorimetric, known according to RGR, in use range, the toxicity rank is 0 grade.
The accompanying drawing explanation
Fig. 1 is the nucleus magnetic hydrogen spectrum of product in embodiment 1;
Fig. 2 is the ultra-violet absorption spectrum of product in embodiment 1;
Fig. 3 is cytotoxicity chart in embodiment 6.
Embodiment
Below by specific examples, the present invention is further elaborated, should be noted that following explanation is only in order to explain the present invention, is not the restriction to its protection domain.
Embodiment 1: preparation is containing the white dyes of tetrasulfonic acid
In 500mL there-necked flask (ice-water bath), add 250mL water, then add 9.8g cyanuric chloride and 9.82gDSD acid, violent stirring is uniformly dispersed, and maintains 0-3 ℃, reaction 2.5h; Raise temperature to 50 ℃, add the 9.18g Sulphanilic Acid, regulate pH value to 5.0, reaction 3h; Temperature reaction mixture to 85 ℃, add the 1.83g leucine, regulates pH value to 8, and reaction 3h, be cooled to room temperature, with 4mol/L hydrochloric acid, adjusts pH to 3, decompress filter, and the dry solid product that obtains, be product, productive rate 85.6%.
Its fusing point is:>250 ℃.
The proton magnetic data, spectrogram is shown in Fig. 1:
(300MHz；DMSO-d6，δ)：0.88-1.87(m，18H，CH
2CH(CH
3)
2)，3.44(t，2H，CH)，4.58(s，2H，NH)，7.58-7.51(d，8H，ArH)，7.56(d，2H，CH＝CH)，8.03-7.79(d，4H，ArH)，8.33(d，2H，ArH)，10.74(s，2H，NH)，11.17(s，2H，NH)，11.72(s，4H，OH).
UV: trans (maximum absorption wavelength 332nm), see Fig. 2.
Can draw thus, its structural formula is:
Embodiment 2: preparation is containing the white dyes of tetrasulfonic acid
In 500mL there-necked flask (ice-water bath), add 250mL water, after add 9.8g cyanuric chloride and 9.82gDSD acid, violent stirring is uniformly dispersed, and temperature maintains 0-4 ℃, regulates pH in 2.5 left and right, the reaction 2.5h, after be elevated to 45 ℃, add the 9.18g Sulphanilic Acid, regulate pH value to 4.5, reaction 2.5h, after be warmed up to 85 ℃, add 4.47g Methionin, regulate pH value to 8.5, reaction 3.0h, dry that solid product is product, productive rate 87.2%.
The proton magnetic data:
(300MHz；DMSO-d6，δ)：1.41-2.74(m，2OH，[CH
2]
5)，3.88(s，4H，NH
2)，7.72(d，2H，CH＝CH)，7.57(m，8H，ArH)，8.03(d，4H，ArH)，8.33(s，2H，ArH)，9.33(s，6H，NH)，10.15-11.75(s，6H，OH).
Embodiment 3: preparation is containing the white dyes of tetrasulfonic acid
In 500mL there-necked flask (ice-water bath), add 250mL water, after add 9.8g cyanuric chloride and 9.82gDSD acid, 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 45 ℃, add the 9.18g Sulphanilic Acid, regulate pH value to 4.2, reaction 2.5h, after be warmed up to 80 ℃, add the 4.6g glycine, regulate pH value to 8.0, reaction 3.0h, dry that solid product is product, productive rate 85.8%.
The proton magnetic data:
(300MHz；DMSO-d6，δ)：3.68-4.02(s，4H，CH
2)，7.84(d，2H，CH＝CH)，7.62-7.55(m，8H，ArH)，8.31(d，4H，ArH)，9.26(s，2H，ArH)，9.65(s，6H，NH)，11.15-11.76(s，6H，OH).
Embodiment 4: preparation is containing the white dyes of tetrasulfonic acid
In 500mL there-necked flask (ice-water bath), add 250mL water, after add 9.8g cyanuric chloride and 9.82gDSD acid, 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 45 ℃, add the 9.18g Sulphanilic Acid, regulate pH value to 4.2, reaction 2.5h, after be warmed up to 80 ℃, add 2.4g tyrosine, regulate pH value to 8.0, reaction 4.0h, dry that solid product is product, productive rate 80.8%.
The proton magnetic data:
(300MHz；DMSO-d6，δ)：2.09(d，4H，CH
2)，3.06(t，2H，CH)，7.21(d，2H，CH＝CH)，6.69-8.40(m，22H，ArH)，9.16-9.34(s，6H，NH)，9.66-11.66(s，8H，OH).
Embodiment 5: contain the application of the white dyes of tetrasulfonic acid
Accurately take each 0.400g of white dyes of embodiment 1～4 preparation, be mixed with the different concns solution of 0.05～1.20g/L, carry out Coloration experiment: dyeing is used
the qualitative quick filter paper of 7cm, bath raio 1: 150, pH value scope control is 7～8.Dyeing 30min, dye completely, and in dry below 80 ℃, result is as shown in table 1.
The whiteness of white dyes under different concns that table 1 embodiment 1～4 is prepared
Experimental result shows, the whitening effect of product effect in the lower concentration situation is better, and along with the continuous increase whitening effect of concentration reduces.Product is applicable to use under low consistency conditions.
Embodiment 6: contain the application of the white dyes of tetrasulfonic acid
Cytotoxic detection: 4 * 104/mL cell suspension inoculation that will prepare, in 96 well culture plates, is established negative control, positive control and is supplied examination material group, and each specimen is carried out 6 groups of parallel laboratory tests, and 100 mountain cell suspensions are inoculated in every hole.After putting 37 ℃ of cultivation 24h of 5%CO2 incubator, discard original fluid.The blank group adds fresh cell culture fluid, positive controls adds lower concentration DMSO solution, do not add test sample solution (50%, 25%, 20%, 15%10%5% concentration) for the examination material component, every hole 100 μ L, put the CO2 incubator and continue to cultivate.After 48h, every hole adds the MTT solution that the 20mL mass concentration is 5g/L, after continuing to cultivate 4h, discards liquid in hole, adds 150 μ L DMSO, puts on vibrator the 10min that vibrates, and under microplate reader 570nm and 630nm wavelength, measures absorbancy.All specimen and articles for use all pass through autoclaving.
Calculate relative appreciation rate (RGR) by following formula:
RGR=(trial-product group absorbancy/blank group absorbancy) * 100%.
According to RGR, that toxicity grading is as follows: 0 grade: RGR >=100%; 1 grade: 80%～99%; 2 grades: 50%～79%; 3 grades: 30%～49%; 4 grades: 0%～29%.Cytotoxicity analysis knows that compound is safe, all nontoxic in the concentration range of experimental study.(annotate: the positive control group of Y)
Result as shown in Figure 3.These several compounds are safe as seen in Figure 3, under lower concentration, are 0 grade, under high density, are 1 grade.
Claims (2)
1. the white dyes containing tetrasulfonic acid, its structure is as follows:
Wherein, R
2for:
-NHCH
2cOOH ,-NHCH (COOH) CH
2cH (CH
3)
2,-NHCH
2cH
2cH
2cH
2cH (NH
2) COOH ,-NHCH (COOH) CH
2any in PhOH.
2. the preparation method of the described white dyes containing tetrasulfonic acid of claim l, is characterized in that,
Work as R
2for-NHCH (COOH) CH
2cH (CH
3)
2the time, step is: in the 500mL there-necked flask, add 250mL water, then add 9.8g cyanuric chloride and 9.82g DSD acid, violent stirring is uniformly dispersed, and maintains 0-3 ℃, reaction 2.5h; Raise temperature to 50 ℃, add the 9.18g Sulphanilic Acid, regulate pH value to 5.0, reaction 3h; Temperature reaction mixture to 85 ℃, add the 1.83g leucine, regulates pH value to 8, and reaction 3h, be cooled to room temperature, with 4mol/L hydrochloric acid, adjusts pH to 3, decompress filter, and the dry solid product that obtains, be product;
Work as R
2for-NHCH
2cH
2cH
2cH
2cH (NH
2) during COOH, step is: in the 500mL there-necked flask, add 250mL water, after add 9.8g cyanuric chloride and 9.82g DSD acid, violent stirring is uniformly dispersed, temperature maintains 0-4 ℃, regulate pH in 2.5 left and right, reaction 2.5h, after be elevated to 45 ℃, add the 9.18g Sulphanilic Acid, regulate pH value to 4.5, reaction 2.5h, after be warmed up to 85 ℃, add 4.47g Methionin, regulate pH value to 8.5, reaction 3.0h is dry that solid product is product;
Work as R
2for-NHCH
2during COOH, step is: in the 500mL there-necked flask, add 250mL water, after add 9.8g cyanuric chloride and 9.82g DSD acid, violent stirring is uniformly dispersed, temperature maintains 0-3 ℃, regulate pH in 2.0 left and right, reaction 2.5h, after be elevated to 45 ℃, add the 9.18g Sulphanilic Acid, regulate pH value to 4.2, reaction 2.5h, after be warmed up to 80 ℃, add the 4.6g glycine, regulate pH value to 8.0, reaction 3.0h is dry that solid product is product;
Work as R
2for-NHCH (COOH) CH
2during PhOH, step is: in the 500mL there-necked flask, add 250mL water, after add 9.8g cyanuric chloride and 9.82g DSD acid, violent stirring is uniformly dispersed, temperature maintains 0-3 ℃, regulate pH in 2.0 left and right, reaction 2.5h, after be elevated to 45 ℃, add the 9.18g Sulphanilic Acid, regulate pH value to 4.2, reaction 2.5h, after be warmed up to 80 ℃, add 2.4g tyrosine, regulate pH value to 8.0, reaction 4.0h is dry that solid product is product.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803796A (en) * | 2005-10-17 | 2006-07-19 | 山东大学 | Highly effective environment friendly triazine amino stilbene fluorescent bleachng agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803796A (en) * | 2005-10-17 | 2006-07-19 | 山东大学 | Highly effective environment friendly triazine amino stilbene fluorescent bleachng agent |
Non-Patent Citations (4)
| Title |
|---|
| 双三嗪氨基二苯乙烯类荧光增白剂;孙保国等;《纸和造纸》;20030930(第5期);42-44 * |
| 孙保国等.双三嗪氨基二苯乙烯类荧光增白剂.《纸和造纸》.2003,(第5期),42-44. |
| 王永运.荧光增白剂VBL系列产品的生产及应用概况.《精细与专用化学品》.1998,(第8期),2-6. |
| 荧光增白剂VBL系列产品的生产及应用概况;王永运;《精细与专用化学品》;19980423(第8期);2-6 * |
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