CN110079119B - Bisazo type sun-proof acid dye containing H acid structure and preparation method thereof - Google Patents
Bisazo type sun-proof acid dye containing H acid structure and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B43/00—Preparation of azo dyes from other azo compounds
- C09B43/11—Preparation of azo dyes from other azo compounds by introducing hydrocarbon radicals or substituted hydrocarbon radicals on primary or secondary amino groups
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B43/00—Preparation of azo dyes from other azo compounds
- C09B43/28—Preparation of azo dyes from other azo compounds by etherification of hydroxyl groups
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/39—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using acid dyes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/653—Nitrogen-free carboxylic acids or their salts
- D06P1/6533—Aliphatic, araliphatic or cycloaliphatic
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/673—Inorganic compounds
- D06P1/67333—Salts or hydroxides
- D06P1/6735—Salts or hydroxides of alkaline or alkaline-earth metals with anions different from those provided for in D06P1/67341
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/14—Wool
- D06P3/16—Wool using acid dyes
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Abstract
The invention belongs to the field of chemical industry, and particularly relates to a disazo type sun-proof acid dye containing an H acid structure and a preparation method thereof. The preparation method comprises the following steps: step 1), chlorination reaction of pentamethylpiperidinol, thereby preparing and obtaining a chlorinated intermediate product HALS-Cl; and 2) condensing HALS-Cl and the disazo type acid dye containing the H acid structure to finally obtain the disazo type sun-proof acid dye containing the H acid structure as a product. Aiming at the problem that the light fastness of the disazo acid dye containing the H acid structure is low, two hindered amine light stable fragments are simultaneously introduced at the ortho-position of an azo bond in the dye structure, and hydroxyl and amino are respectively converted into ether bond (-O-) and imino (-NH-), so that the amino (-NH-) is effectively avoided2) Or hydroxyl (-OH), and simultaneously realizes the close range protection of the double azo bond, thereby developing a series of disazo type acid dyes with excellent light fastness.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a disazo type sun-proof acid dye containing an H acid structure and a preparation method thereof.
Background
H acid (1-amino-8-naphthol-3, 6-disulfonic acid) is an important intermediate for preparing active, acidic and direct dyes, and can be used for producing more than 130 dye varieties, wherein more than 90 dye varieties are hot-market varieties. The global demand of H acid is over 15 million tons every year, and the output value is over 70 million yuan.
The acid dye is a dye type which contains acid groups in the dye molecule and can be combined with amino groups in protein fiber molecules in an ionic bond. The acid dye has the characteristics of bright color, good level dyeing property, simple and convenient dyeing method, complete chromatogram, lower cost and the like, and is mainly applied to dyeing and printing of silk, wool, chinlon and other fibers and blended fabrics thereof.
The azo-type acid dye accounts for a large proportion of the acid dyes. Among them, disazo type acid dyes containing H acid structure generally have poor light fastness (for example, the light fastness of c.i. acid green 19 is only 3 grade, the light fastness of c.i. acid blue 87 is 3-4 grade, and the light fastness of c.i. acid black 1 is 5 grade), and have a larger difference with yellow pyrazolone type acid dyes, anthraquinone dyes (generally having light fastness of more than 5 grade), and the disazo type acid dyes containing H acid structure are easy to be discolored and discolored due to photofading after long-term light exposure in combination use.
The disazo type acid dye containing the H acid structure is easy to fade after being illuminated, and the generation of high-concentration singlet oxygen under the illumination condition is the main reason of dye fading. The fading phenomenon of the dye is caused by amino (-NH) with higher electron cloud density in an H acid structure2) Hydroxyl (-OH) and azo (-N-) are susceptible to singlet oxygen oxidation resulting in a change in the conjugated system of the dye.
The hindered amine light stabilizer is an organic amine compound with steric hindrance, has the effects of quenching singlet oxygen and eliminating active free radicals, has a good inhibition effect on the photo-oxidative degradation reaction of the organic compound, and is a light stabilizer with excellent performance.
Disclosure of Invention
Aiming at the problem of low light fastness of the disazo acid dye with the H acid structure, two hindered amine light stabilizing segments are introduced at the same time at the ortho position of an azo bond in the dye structure, and a hydroxyl group and an amino group are respectively converted into an ether bond (-O-) and an imino group (-NH-), so that the amino group (-NH-) is effectively avoided2) Or hydroxyl (-OH), and simultaneously realizes the close range protection of the double azo bond, thereby developing a series of disazo type acidic acid with excellent light fastnessA dye.
In order to solve the technical problems, the invention provides a disazo type sun-proof acid dye containing an H acid structure, which has a structural general formula as follows:
in the formula: r1H, Cl; r2H, Cl; r3Is H, NO2；R4H, Cl; r4The aromatic ring is benzene ring or naphthalene ring.
When R is4When the aromatic ring is a benzene ring, R4Is Cl; when R is4When the aromatic ring is naphthalene ring, R4Is H.
The structural formula of the improved disazo type sun-proof acid dye containing the H acid structure is any one of the following structures:
the invention also provides a preparation method of the disazo type sun-proof acid dye containing the H acid structure, which comprises the chlorination reaction of pentamethylpiperidinol in the step 1), so as to prepare and obtain a chlorinated intermediate product HALS-Cl; further comprising the following step 2):
2) HALS-Cl is condensed with disazo type acid dyes containing H acid structure:
weighing NaOH and dissolving in deionized water, adding a disazo type acid dye containing an H acid structure, stirring until the disazo type acid dye is completely dissolved, heating to 46-50 ℃, reacting for 1.5-2H, then adding HALS-Cl obtained in the step 1), continuously heating to 91-95 ℃, and carrying out heat preservation reaction for 7-8H; the HALS-Cl: disazo acid dyes containing an H acid structure: the molar ratio of NaOH is 2:1: 2;
and after the reaction is finished, adding sodium chloride into the obtained reaction product solution until the sodium chloride is saturated (namely, adding excessive sodium chloride), separating out a salt-containing product, filtering, removing salt in the salt-containing product by adopting a DMF-ether method, and drying to obtain the disazo type sun-proof acid dye containing the H acid structure as the product.
As an improvement of the preparation method of the invention: the disazo acid dye containing the H acid structure is C.I. acid blue 87, C.I. acid green 19 or C.I. acid black 1; the correspondingly obtained disazo type sun-proof acid dyes containing the H acid structure are AD-1, AD-2 and AD-3.
The reaction formula is as follows:
in the condensation reaction, 30 +/-5 mL of deionized water is used for every 0.015mol of NaOH.
The step 1) of the invention is a chlorination reaction of pentamethylpiperidinol, which comprises the following steps:
adding 1,2,2,6, 6-pentamethylpiperidinol into thionyl chloride, heating to 60-80 ℃, and continuously stirring for reacting for 1.5-2.5 h, wherein the weight ratio of the thionyl chloride: the molar ratio of the 1,2,2,6, 6-pentamethylpiperidinol is 3.5-4.5: 1 (preferably 4: 1);
adding absolute ethyl alcohol into the obtained reaction product, uniformly stirring, then dropwise adding triethylamine until the pH value is adjusted to 7 +/-1, then adding diethyl ether, and uniformly stirring until no new precipitate is generated; filtering to obtain filtrate and filter cake (i.e. precipitate); washing the filter cake with diethyl ether, combining the obtained washing liquid with the filtrate, and then carrying out reduced pressure distillation to obtain a chlorinated intermediate product HALS-Cl;
the reaction formula is as follows:
in the step 1), the volume ratio of the absolute ethyl alcohol to the diethyl ether is 1: 1; 80-120 mL of absolute ethyl alcohol is used for every 0.06mol of 1,2,2,6, 6-pentamethylpiperidinol.
The sun-proof acidic dye simultaneously takes ether bond (-O-) and imino (-NH-) as bridging groups in a molecular structure, and two ends of the molecular structure are respectively connected with a dye chromogen containing an H acid structure and a hindered amine light stabilizer segment.
On the basis of the disazo type acid dye containing an H acid structure, the disazo type acid dye and two hindered amine light stable segments react and are connected to the same molecule to prepare the novel sun-proof acid dye, the two azo groups are protected in a short distance, and finally the high sun-proof performance of the dye is realized.
According to the invention, the hindered amine light stable segment is introduced into the structure of the bisazo acid dye, so that the dye photodegradation reaction can be effectively inhibited, and the light fastness of the dye is improved.
The disazo type sun-proof acid dye containing the H acid structure has the following advantages:
compared with the existing commercialized acid dye with similar structure, the light-fast acid dye can capture free radicals through hindered amine, inhibit dye photooxidation degradation, play a role in light stabilization on the dye, and greatly improve the light resistance of the dye. In conclusion, the disazo type acid dye containing the H acid structure and two hindered amine light stabilizing segments are introduced into the same molecule, so that the sun-proof acid dye with excellent performance is developed, and the application prospect is good.
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The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a curve of a wool fabric dyeing process.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
example 1, a method for preparing a disazo type light-fast acid dye (black dye) containing an H acid structure, sequentially carrying out the following steps:
1) and chlorination reaction of pentamethylpiperidinol:
17.4mL (0.24mol) of thionyl chloride was added to a 100mL three-necked flask, 10.3g (0.06mol) of 1,2,2,6, 6-pentamethylpiperidinol was added to the three-necked flask in portions with stirring (in order to control the temperature not to exceed 60 ℃ C.), and the reaction was continued with stirring at 80 ℃ for 1.5 hours. After the reaction is finished, transferring the reaction solution into a 250mL beaker, adding 100mL of absolute ethyl alcohol into the beaker, fully stirring, slowly dropwise adding triethylamine into the beaker under the ice bath condition until the pH value of the solution is adjusted to be neutral, adding 100mL of diethyl ether into the beaker, enabling white precipitate to appear in the solution, and uniformly stirring until no new precipitate is generated; filtering and washing the filter cake twice with diethyl ether (the dosage of each diethyl ether is 50ml), combining the filtrate and the washing liquid, distilling at 90 ℃ under normal pressure, evaporating the solvents of absolute ethyl alcohol and diethyl ether, and obtaining 11.3g of chlorinated intermediate product HALS-Cl as residual liquid in a three-neck flask.
2) And condensation reaction:
weighing 0.02mol (about 0.8g) of NaOH, dissolving in 30mL of deionized water, transferring to a three-neck flask, adding 0.01mol of C.I. acid black 1, stirring until the solution is completely dissolved, heating to 46-50 ℃, reacting for 2h, dropwise adding 0.02mol of HALS-Cl (obtained in the step 1) into the solution, heating to 91-95 ℃ after dropwise adding (the dropwise adding time is about 1h), and keeping stirring and continuing to react for 8 h.
After the reaction is finished, adding sodium chloride solid into the obtained reaction product solution until sodium chloride is saturated, salting out a dye product, and filtering to obtain a salt-containing dye (salt-containing product);
removing salt in the salt-containing dye by adopting a DMF-ether method, collecting and drying, and specifically comprising the following steps: DMF-Ether method: dissolving 2g of salt-containing dye in 15mL of DMF (dye dissolved and salt insoluble), filtering to remove salt, adding 100mL of anhydrous ether into the filtrate to separate out the dye, filtering, collecting a filter cake, and drying at room temperature to constant weight; obtaining the black lightfast acid dye AD-1.
The structural formula of the black sun-proof acid dye AD-1 is as follows:
1H NMR(400MHz,DMSO-d6)：8.39(d,2H),8.19(d,2H),8.12(s,1H),8.04(s,1H),7.93 (d,2H),7.46(m,3H),2.63(m,1H),2.27(m,6H),1.74(d,4H),1.49(d,24H),1.15(s,24H)；ESI MS(m/z,％):438.2([M-2Na]/2-,100)。
example 2, a method for preparing a disazo type light-fast acid dye (blue dye) containing an H acid structure, sequentially carrying out the following steps:
1) and chlorination reaction of pentamethylpiperidinol: same as in step 1 of example 1).
2) And condensation reaction:
weighing 0.02mol of NaOH, dissolving in 30mL of deionized water, transferring to a three-neck flask, adding 0.01mol of C.I. acid blue 87, stirring until the solution is completely dissolved, heating to 46-50 ℃, reacting for 2h, dropwise adding 0.02mol of HALS-Cl (obtained in the step 1) into the solution, heating to 91-95 ℃ after dropwise adding, and keeping stirring and continuing to react for 8 h.
After the reaction is finished, adding sodium chloride solid into the reaction product solution until the sodium chloride is saturated, salting out a dye product, and filtering to obtain a salt-containing dye; removing salt in the salt-containing dye by adopting a DMF-ether method, collecting and drying to obtain the blue light-fast acid dye AD-2.
The structural formula of the blue light-fast acid dye AD-2 is as follows:
1H NMR(400MHz,DMSO-d6)：8.12(s,1H),8.04(s,1H),7.87(d,2H),7.47(d,2H),7.40 (t,2H),7.34(t,2H),2.64(m,1H),2.27(m,6H),1.74(d,4H),1.49(d,4H),1.15(s,24H)；ESI MS(m/z,％):449.6([M-2Na]/2-,100)。
example 3, a method for preparing a disazo type light-fast acid dye (green dye) containing an H acid structure, sequentially carrying out the following steps:
1) and chlorination reaction of pentamethylpiperidinol: same as in step 1 of example 1).
2) And condensation reaction:
weighing 0.02mol of NaOH, dissolving in 30mL of deionized water, transferring to a three-neck flask, adding 0.01mol of C.I. acid green 19, stirring until the solution is completely dissolved, heating to 46-50 ℃, reacting for 2h, dropwise adding 0.02mol of HALS-Cl (obtained in the step 1) into the solution, heating to 91-95 ℃ after dropwise adding, and keeping stirring and continuing to react for 8 h.
After the reaction is finished, adding sodium chloride into the reaction product solution until the sodium chloride is saturated, salting out a dye product, and filtering to obtain a salt-containing dye; and removing salt in the salt-containing dye by adopting a DMF-ether method, collecting and drying to obtain the green sun-proof acid dye AD-3.
The structural formula of the green sun-proof acid dye AD-3 is as follows:
1H NMR(400MHz,DMSO-d6)：8.12(s,1H),8.04(s,1H),7.99(d,1H),7.87(m,2H),7.67 (m,2H),7.52(t,1H),7.41(m,2H),7.32(m,2H),2.62(m,1H),2.27(m,6H),1.74(d,4H),1.49(d, 4H),1.15(s,24H)；ESI MS(m/z,％):474.6([M-2Na]/2-,100)。
the application of the disazo type lightfast acid dye containing H acid structure in the dyeing of wool fabric is illustrated by experiments.
Experiment 1, taking 1kg of wool fabric, adjusting the pH value to 4.5-5.0 according to 2% owf of acid dye and 5% owf of anhydrous sodium sulphate and acetic acid, wherein the bath ratio is 1:20, and the dyeing process curve is shown in figure 1;
after dyeing is finished, taking out a dyed cloth sample, washing, combining dyeing residual liquid and washing liquid, fixing the absorbance of a volume measuring device, and solving the dye uptake of the dye by utilizing the Lambert-beer law; and measuring the water fastness, the dry rubbing fastness, the wet rubbing fastness and the light fastness of the dyed cloth sample. The results are shown in Table 1.
TABLE 1 dyeing performance and fastness data of acid dyes for wool fabrics
Comparative example 1, the black acid dye in experiment 1 was changed to the following dyes, respectively: c.i. acid black 1, black modified dye 2, the remainder being identical to experiment 1.
The results obtained are shown in table 2 below in comparison with example 1.
TABLE 2 comparison of the properties of the black dyes
| Dye uptake (%) | Wavelength of maximum absorption (nm) | Light fastness (grade) | |
| Example 1 | 99.4 | 605 | 8 |
| C.I. acid Black 1 | 95.6 | 605 | 5 |
| Black modified dye 1 | 96.1 | 605 | 6 |
| Black modified dye 2 | 95.8 | 605 | 5-6 |
The improvement of the light fastness of the embodiment 1 is obvious and reaches 8 grades. Note: the light fastness level 8 belongs to the highest level (the light fastness level is 8, the level 1 is the worst, and the level 8 is the highest). Compared with the C.I. acid black 1, the light fastness of the black modified dye 1 and the black modified dye 2 is not obviously improved, and is only improved by 0.5-1 grade.
Comparative example 2, the blue acid dye in experiment 1 was changed to the following dyes, respectively: c.i. acid blue 87, blue modified dye 1, blue modified dye 2, the remainder being identical to experiment 1.
The results obtained are shown in table 3 below in comparison with example 2.
TABLE 3 comparison of the properties of blue dyes
The light fastness of the embodiment 2 is obviously improved and reaches 7-8 grades. Compared with the C.I. acid blue 87, the improvement of the light fastness of the blue modified dye 1 and the blue modified dye 2 is not obvious and is only improved by 0.5 grade.
Comparative example 3, the green acid dye in experiment 3 was changed to c.i. acid green 19, green modified dye 1, green modified dye 2, and the remainder was identical to experiment 1.
The results obtained are shown in table 4 below in comparison with example 3.
TABLE 4 comparison of the Properties of the Green dyes
| Dye uptake (%) | Wavelength of maximum absorption (nm) | Light fastness (grade) | |
| Example 3 | 99.5 | 608 | 7-8 |
| C.i. acid green 19 | 93.5 | 607 | 3 |
| Green modified dye 1 | 93.6 | 607 | 4 |
| Green modified dye 2 | 93.9 | 608 | 4 |
The light fastness of the embodiment 3 is obviously improved and reaches 7-8 grades. Compared with the C.I. acid green 19, the green modified dye 1 and the green modified dye 2 have unobvious improvement on the light fastness and only improve the level 1.
To sum up, in the disazo type acid dye containing the H acid structure, because the disazo structure exists in the structure, the simultaneous protection of two azo bonds is difficult to realize by only introducing one hindered amine segment, and the amino (-NH) group2) Or the residue of hydroxyl (-OH) group does not improve the light fastness of the dye completely. Therefore, two hindered amine light-stabilizing segments must be simultaneously introduced in the adjacent positions of azo bonds in the dye structure to effectively improve the light fastness of the dye.
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (3)
1. The disazo type sun-proof acid dye containing the H acid structure is characterized in that the structural formula is any one of the following:
2. the process for the preparation of the disazo type sunscreen acid dyes containing H acid structure as claimed in claim 1, comprising the chlorination of pentamethylpiperidinol in step 1) to obtain the chlorinated intermediate product HALS-Cl; the method is characterized by further comprising the following step 2):
2) HALS-Cl is condensed with disazo type acid dyes containing H acid structure:
weighing NaOH and dissolving in deionized water, adding a disazo type acid dye containing an H acid structure, stirring until the disazo type acid dye is completely dissolved, heating to 46-50 ℃, reacting for 1.5-2H, then adding HALS-Cl obtained in the step 1), continuously heating to 91-95 ℃, and carrying out heat preservation reaction for 7-8H; the HALS-Cl: disazo acid dyes containing an H acid structure: the molar ratio of NaOH is 2:1: 2;
and after the reaction is finished, adding sodium chloride into the obtained reaction product solution until the sodium chloride is saturated, separating out a salt-containing product, filtering, removing salt in the salt-containing product by adopting a DMF-ether method, and drying to obtain the disazo type sun-proof acid dye containing the H acid structure as the product.
3. The process for preparing disazo type lightfast acid dyes containing H acid structure as claimed in claim 2, wherein:
the disazo acid dyes containing the H acid structure are C.I. acid black 1, C.I. acid blue 87 and C.I. acid green 19; the correspondingly obtained disazo type sun-proof acid dyes containing the H acid structure are AD-1, AD-2 and AD-3.
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