CN113930085B - Sun-proof anthraquinone disperse dye and preparation method thereof - Google Patents
Sun-proof anthraquinone disperse dye and preparation method thereof Download PDFInfo
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- CN113930085B CN113930085B CN202111316457.XA CN202111316457A CN113930085B CN 113930085 B CN113930085 B CN 113930085B CN 202111316457 A CN202111316457 A CN 202111316457A CN 113930085 B CN113930085 B CN 113930085B
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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
- C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
- C09B5/24—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings the heterocyclic rings being only condensed with an anthraquinone nucleus in 1-2 or 2-3 position
- C09B5/2409—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings the heterocyclic rings being only condensed with an anthraquinone nucleus in 1-2 or 2-3 position not provided for in one of the sub groups C09B5/26 - C09B5/62
- C09B5/2436—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings the heterocyclic rings being only condensed with an anthraquinone nucleus in 1-2 or 2-3 position not provided for in one of the sub groups C09B5/26 - C09B5/62 only nitrogen-containing hetero rings
- C09B5/2445—Phtaloyl isoindoles
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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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/008—Preparations of disperse dyes or solvent dyes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses aA sun-proof anthraquinone disperse dye has a structural general formula:wherein: r is H or CH 3 . The preparation method of the sun-proof anthraquinone disperse dye comprises the following steps: adding 1, 4-diaminoanthraquinone-2, 3-dicarboxylic anhydride into polymethylpiperidine amine, and reacting after heating; adding ethanol into the obtained target disperse dye solution for segregation, cooling, carrying out suction filtration, washing a filter cake with ethanol, washing with hot water, and drying to obtain the sun-proof anthraquinone disperse dye. The dye has wide application prospect in the field with strict requirements on light fastness.
Description
Technical Field
The invention relates to a sun-proof anthraquinone disperse dye and a preparation method thereof.
Technical Field
The production of the disperse dye in China reaches 37.1 ten thousand tons in 2020, and the annual output of the disperse dye in China accounts for 48.2% of the total annual output of the disperse dye in China. Disperse dyes can be classified into azo type and anthraquinone type according to the structure of a chromophore, and anthraquinone type disperse dyes have higher light fastness than azo dyes due to the characteristic of low electron cloud density on an aromatic ring in the structure. However, in recent years, new anthraquinone dyes with new structures are reported, and the problem of dye light fastness is increasingly outstanding in the case that the existing anthraquinone disperse dyes are old in variety and the dye light fastness cannot reach the application standard under special environments, especially in the fields of tropical and mountain areas, outdoors, in vehicles, offshore, deserts and aerospace. With the development of science and technology and society, the requirement of people on the light fastness of textiles is continuously improved in recent years, and the traditional anthraquinone type commercial dye has difficulty in meeting the strict requirement on the light fastness of special textiles.
There are two types of anthraquinone dye fading mechanisms, namely a photo-oxidation fading mechanism and a photo-reduction fading mechanism. Both fade mechanisms are intimately related to the molecular structure of the dye, the light fastness of which is related to the structure of the chromophore of the dye and to the substituents in the dye molecule. It is generally considered that an electron donating group such as a hydroxyl group or an amine group accelerates the discoloration, and an electron withdrawing group such as a chlorine atom or a bromine atom retards the discoloration. Therefore, the conventional method is to introduce electron withdrawing groups on amino groups of anthraquinone disperse dye, reduce electron cloud density of dye color bodies and amino groups, and improve the light fastness of the dye.
The invention 201010142513.8, namely a preparation method of disperse blue 60 and homologs thereof, provides anthraquinone disperse dye C.I. disperse blue 60 with better light fastness, and can meet the application requirements of conventional textiles on light fastness. However, c.i. disperse blue 60 does not meet the light fastness requirements of textiles in special environments and therefore improvements are needed.
The invention 200910049519.8, namely a sun-proof water-soluble dye, a preparation method and application thereof, introduces group hindered amine 4-Z-2, 6-tetramethyl piperidine amine and water-soluble group sulfonic acid groups into general water-insoluble dye.
The invention of 201810793731.4, namely red sun-proof K-type reactive dye and a preparation method thereof, is that 1,2, 6-pentamethylpiperidinol or 2, 6-tetramethylpiperidine amine is introduced into X-type reactive dye;
the structural formula of the 1,2, 6-pentamethylpiperidinol is as follows:the structural formula of the 2, 6-tetramethyl piperidine amine is as follows: />
The invention of 201911041570.4, namely a water-soluble cross-linking color fixing agent with a light stabilization function and a preparation method thereof, discloses 4 water-soluble cross-linking color fixing agents with a light stabilization function, wherein cyanuric chloride serving as a component A is firstly mixed with ice water and then pulped, and then a component B is added to perform a first condensation reaction at a temperature of between 0 and 5 ℃ and a pH value of between 5 and 6; the component B is pentamethylpiperidinol or tetramethylpiperidine amine; adding a C component into a product obtained by the first condensation reaction, and performing a second condensation reaction at the temperature of 40-45 ℃ and the pH value of 6-7, wherein the C component is para-ester or meta-ester; the obtained product is filtered, and the obtained filter cake is a water-soluble crosslinking color fixing agent with a light stabilization function. The scheme can simultaneously improve the wet processing fastness and the like of the nylon dyeing product.
The dye structures or light stabilizer structures protected in the last 3 patents contain water-soluble groups such as sulfonic acid groups.
Disclosure of Invention
The invention solves the technical problem of providing a sun-proof anthraquinone disperse dye and a preparation method thereof, wherein the disperse dye has the characteristic of higher light fastness.
In order to solve the technical problems, the invention provides a sun-proof anthraquinone disperse dye, the molecular structure of which contains hindered amine light stabilizing fragments, and the general formula of the dye is as follows:
wherein: r is H or CH 3 。
As a further improvement of the sun-proof anthraquinone disperse dye, the structural formula of the disperse dye is any one of the following:
the invention also provides a preparation method of the sun-proof anthraquinone disperse dye, which comprises the following steps:
1) Placing the polymethylpiperidine amine into a container, adding the dried 1, 4-diaminoanthraquinone-2, 3-dicarboxylic anhydride under stirring, heating to 105-110 ℃ for reaction for 3-5 hours, and obtaining a target disperse dye solution;
polymethylpiperidinamine: 1, 4-diaminoanthraquinone-2, 3-dicarboxylic anhydride = 5:1 molar ratio;
2) Adding ethanol into the target disperse dye solution obtained in the step 1) for segregation, cooling to 25+/-5 ℃, performing suction filtration, washing a filter cake with ethanol, washing with hot water (about 60-70 ℃) and drying (drying to constant weight at 80 ℃) to obtain the finished product, namely the sun-proof anthraquinone disperse dye.
As an improvement of the preparation method of the sun-proof anthraquinone disperse dye:
when the polymethylpiperidine amine is tetramethylpiperidine amine, the sunfast anthraquinone disperse dye is A1;
when the polymethylpiperidine amine is pentamethylpiperidine, the sunfast anthraquinone disperse dye is A2.
The reaction formula of the invention is as follows:
r is H or CH 3 。
The preparation method of the sun-proof anthraquinone disperse dye selects 1, 4-diamino anthraquinone-2, 3-dicarboxylic anhydride and polymethyl piperidine amine as raw materials, and introduces hindered amine light stabilization fragments on the basis of 1, 4-diamino anthraquinone color bodies, thereby effectively improving the light fastness of the dye.
The sun-proof anthraquinone disperse dye is used for dyeing hydrophobic Polyester (PET) fibers, and the dyeing process comprises the following steps: adding 0.25-0.5g of anthraquinone dye, 0.5-1g of dispersant NNO, 10-40g of zirconium beads (with the diameter of 1-2 mm) and 20-60mL of water into a sand mill, sanding for 4-8 hours, filtering through a fine nylon filter cloth after sanding, collecting dye dispersion liquid, and fixing the volume of the dye dispersion liquid in a 500mL volumetric flask (namely, fixing the volume to 500 mL) by deionized water to obtain dye color paste; transferring the disperse dye color paste according to the chromaticity requirement of 1-2% owf, and according to the bath ratio of 1:30-50, adding water, transferring to a dyeing cup, adding PET fabric, placing into a high temperature and high pressure dyeing instrument, heating to 90deg.C at a heating rate of 2deg.C/min, slowly heating to 130deg.C at 1deg.C/min, maintaining for 1 hr, cooling to room temperature, taking out dyed cloth sample, washing, respectively absorbing dye solutions before and after dyeing, and measuring the maximum absorption wavelength (lambda) with ultraviolet-visible spectrophotometer max ) Absorbance was measured and dye uptake was calculated using lambert-beer law.
The lightproof anthraquinone disperse dye is improved on the basis of a1, 4-diaminoanthraquinone chromophore structure, and a hindered amine light stabilization segment (namely tetramethyl piperidine amine or pentamethyl piperidine amine group) with the functions of eliminating free radicals and quenching singlet oxygen is introduced, so that the singlet oxygen and the quenching free radicals can be effectively eliminated under the condition of illumination, the photochemical reaction of the dye is inhibited, and the lightproof fastness of the dye is improved. The dye has wide application prospect in the field with strict requirements on light fastness.
In conclusion, the lightfast anthraquinone disperse dye overcomes the disadvantage that the traditional commercial anthraquinone disperse dye is not suitable for special environments with high requirements on light fastness, and simultaneously has excellent light fastness and enriches the varieties of high light fastness disperse dyes as a novel anthraquinone disperse dye structure.
It is emphasized that: the present invention is a hydrophobic disperse dye, and the dye structure or the light stabilizer structure protected by 200910049519.8, 201810793731.4 and 201911041570.4 contains water-soluble groups such as sulfonic acid groups, and exists in the form of aggregates when dyed and dyed into fibers, which is different from the state of the structure in the hydrophilic fibers.
Detailed Description
The invention will be further described with reference to the following specific examples, but the scope of the invention is not limited thereto:
1, 4-diaminoanthraquinone-2, 3-dicarboxylic anhydride, tetramethylpiperidinamine and pentamethylpiperidininamine are all known compounds.
Example 1, a sun-proof anthraquinone disperse dye and a preparation method thereof are carried out according to the following steps:
0.1mol (about 15.8 g) of tetramethyl piperidine amine is taken as a raw material, the raw material is mixed with 0.02mol of 1, 4-diamino anthraquinone-2, 3-dicarboxylic anhydride, the mixture is placed in a three-neck flask to react for 5 hours at 105 ℃ to the end point of the reaction, then a proper amount (about 30 ml) of ethanol is added for separation, the temperature is reduced to normal temperature (25+/-5 ℃), suction filtration is carried out, a filter cake is washed by ethanol (about 30 ml), then the filter cake is washed by hot water (about 100ml of hot water at 60 ℃), the filter cake is dried to constant weight at 80 ℃ in an oven, the dried finished product is 8.16g, and the yield is 91.4%, thus obtaining the target product A1.
1 H NMR(400MHz,DMSO-d6)：δ8.29(t,2H),7.83(d,2H),4.80(s,4H),3.60(m,1H),2.12(s,1H),1.79(d,2H),1.54(d,2H),1.22(s,12H)；ESI MS(m/z,％):447.2([M+H] + ,100)。
EXAMPLE 2,
Taking 0.1mL (about 17.2 g) of pentamethylpiperidine as a raw material, mixing the pentamethylpiperidine with 0.02mL of 1, 4-diaminoanthraquinone-2, 3-dicarboxylic anhydride, placing the mixture in a three-neck flask for reaction at 110 ℃ for 3 hours to a reaction end point, adding a proper amount of ethanol (about 30 mL) for separation, cooling to normal temperature, carrying out suction filtration, washing a filter cake with ethanol, washing with hot water, drying in an oven at 80 ℃ to constant weight, and obtaining a finished product of 9.03g in a yield of 92.3%, thereby obtaining the sun-proof anthraquinone disperse dye A2 with the following structure:
1 H NMR(400MHz,DMSO-d6)：δ8.29(t,2H),7.85(d,2H),4.83(s,4H),3.60(m,1H),2.26(s,3H),1.79(d,2H),1.54(d,2H),1.23(s,12H)；ESI MS(m/z,％):461.2([M+H] + ,100)。
experiment 1,
Taking 0.25g of dye (A1/A2), 0.5g of dispersant NNO, 12g of zirconium beads (1 mm) and 20mL of water, sanding for 8 hours in a sand mill, filtering with fine nylon cloth after sanding, and fixing the volume of the collected dispersion liquid to 500mL (in a 500mL volumetric flask) with deionized water to prepare dye color paste; transferring disperse dye color paste according to the chromaticity requirement of 2% owf, and according to the bath ratio of 1:50 adding deionized water, then transferring the solution to a dyeing cup, adding PET fabric to be dyed, placing the dyeing cup in a high-temperature high-pressure dyeing instrument, and setting a dyeing program as follows: heating to 90deg.C at 2deg.C/min, heating to 130deg.C at 1deg.C/min, maintaining the temperature for 1 hr, cooling to room temperature at 2deg.C/min, taking out dyed cloth sample, respectively sucking 1mL of the liquid before and after dyeing into 10mL volumetric flask, metering with acetone to scale, and measuring the maximum absorption wavelength of dye with ultraviolet-visible spectrophotometer (lambda) max ) Absorbance was measured and dye uptake was calculated using lambert-beer law.
The dye uptake of A1 was 95.8% and the dye uptake of A2 was 97.4%.
The dyed cloth sample is subjected to reduction cleaning (the reduction cleaning process is that 2g/L sodium hydrosulfite and 1g/L NaOH are adopted, the bath ratio is 1:50, the temperature is 70 ℃ for 15 min) according to the requirements of a national standard of a method for measuring dyeing color and intensity of disperse dyes (GB/T2394-1980), and the test result shows that:
the light fastness of the dyed cloth samples of the dyes A1 and A2 is 8 grade.
Comparative experiment 1,
C.i. disperse blue 60 dye was substituted for the dye of the present invention and tested as described in experiment 1 above: the dye-uptake was 92.5% and the light fastness was 7.
The specific performance comparisons are shown in table 1 below.
TABLE 1
| Dye | Dye uptake/% | Fastness to light |
| C.i. disperse blue 60 | 92.5 | 7 |
| A1 | 95.8 | 8 |
| A2 | 97.4 | 8 |
According to the results in Table 1, it can be seen that the light fastness of A1 and A2 is better than that of C.I. disperse blue 60 with the same color matrix structure, and the light stability segment is introduced based on the 1, 4-diaminoanthraquinone structure, so that the light fastness can be further improved, and the dyeing rates of A1 and A2 are higher than that of C.I. disperse blue 60, so that the dye-uptake performance is good.
Comparative example 1 the tetramethylpiperidine amine of example 1 was changed to 1,2, 6-pentamethylpiperidine alcohol (abbreviated as pentamethylpiperidine alcohol), and the remainder was identical to example 1.
The obtained product is:
the dye uptake was 90.5% by detection as described in experiment 1 above; the light fastness was grade 7. The comparison with A1 performance is shown in Table 2 below.
TABLE 2
| Dye | Dye uptake/% | Fastness to light |
| A1 | 95.8 | 8 |
| Comparative example 1 | 90.5 | 7 |
The results show that the dye-uptake and the light fastness of the disperse dye obtained in the comparative example 1 are not as good as those of the A1 and A2 light-fast anthraquinone disperse dye.
Finally, it should also be noted that the above list is merely a few specific embodiments of the present invention. Obviously, the invention is not limited to the above embodiments, but many variations are possible. All modifications directly derived or suggested to one skilled in the art from the present disclosure should be considered as being within the scope of the present invention.
Claims (2)
1. The sun-proof anthraquinone disperse dye is characterized by having a structural general formula:
wherein: r is H or CH 3 。
2. The method for preparing the sun-proof anthraquinone disperse dye according to claim 1, which is characterized by comprising the following steps:
1) Adding 1, 4-diaminoanthraquinone-2, 3-dicarboxylic anhydride into polymethylpiperidine amine, heating to 105-110 ℃ for reaction for 3-5 hours to obtain a target disperse dye solution;
polymethylpiperidinamine: 1, 4-diaminoanthraquinone-2, 3-dicarboxylic anhydride = 5:1 molar ratio;
the polymethyl piperidine amine is tetramethyl piperidine amine and pentamethyl piperidine amine;
2) Adding ethanol into the target disperse dye solution obtained in the step 1) for segregation, cooling to 25+/-5 ℃, performing suction filtration, washing a filter cake with ethanol, washing with hot water, and drying to obtain the sun-proof anthraquinone disperse dye.
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| CN101817989A (en) * | 2010-04-08 | 2010-09-01 | 浙江长征化工有限公司 | Method for preparing disperse blue 60 and homologues thereof |
| CN101864188A (en) * | 2009-04-17 | 2010-10-20 | 上海汇友精密化学品有限公司 | Sunproof water-soluble dye, method for preparing same and application thereof |
| CN103305023A (en) * | 2012-03-16 | 2013-09-18 | 上海汇友精密化学品有限公司 | Triazine type azo dye and preparation method thereof |
| CN108912735A (en) * | 2018-07-19 | 2018-11-30 | 浙江理工大学上虞工业技术研究院有限公司 | Red sun-proof K-type reactive dye and preparation method thereof |
| CN110776493A (en) * | 2019-10-30 | 2020-02-11 | 金华双宏化工有限公司 | Water-soluble cross-linking color fixing agent with light stabilization function and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864188A (en) * | 2009-04-17 | 2010-10-20 | 上海汇友精密化学品有限公司 | Sunproof water-soluble dye, method for preparing same and application thereof |
| CN101817989A (en) * | 2010-04-08 | 2010-09-01 | 浙江长征化工有限公司 | Method for preparing disperse blue 60 and homologues thereof |
| CN103305023A (en) * | 2012-03-16 | 2013-09-18 | 上海汇友精密化学品有限公司 | Triazine type azo dye and preparation method thereof |
| CN108912735A (en) * | 2018-07-19 | 2018-11-30 | 浙江理工大学上虞工业技术研究院有限公司 | Red sun-proof K-type reactive dye and preparation method thereof |
| CN110776493A (en) * | 2019-10-30 | 2020-02-11 | 金华双宏化工有限公司 | Water-soluble cross-linking color fixing agent with light stabilization function and preparation method thereof |
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