CN107827872B - Sun-proof emerald green pyridone reactive dye compound and preparation method and application thereof - Google Patents
Sun-proof emerald green pyridone reactive dye compound and preparation method and application thereof Download PDFInfo
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- CN107827872B CN107827872B CN201711137934.XA CN201711137934A CN107827872B CN 107827872 B CN107827872 B CN 107827872B CN 201711137934 A CN201711137934 A CN 201711137934A CN 107827872 B CN107827872 B CN 107827872B
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
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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
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
- C09B47/24—Obtaining compounds having —COOH or —SO3H radicals, or derivatives thereof, directly bound to the phthalocyanine radical
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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
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
- C09B62/507—Azo dyes
- C09B62/513—Disazo or polyazo 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
- D06P1/38—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 reactive dyes
- D06P1/384—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 reactive dyes reactive group not directly attached to heterocyclic group
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- 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
- 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
- D06P1/67358—Halides or oxyhalides
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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
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/66—Natural or regenerated cellulose using reactive dyes
- D06P3/666—Natural or regenerated cellulose using reactive dyes reactive group not directly attached to heterocyclic group
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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
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/02—After-treatment
- D06P5/10—After-treatment with compounds containing metal
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Abstract
The invention discloses a sunproof emerald green pyridone reactive dye compound, a preparation method and application thereof, wherein the dye compound has the following structural formula (I), a + b + c is 3.5, and CuPc, M, n, X and R are1、R2、R3And R4The definition is as described in the specification. The invention also provides a preparation method of the reactive dye compound. The light-fast emerald pyridone reactive dye compound prepared by the method contains yellow and blue double color bodies in molecules, can directly realize intramolecular color matching, and thoroughly solves a series of problems encountered by dye compounding; and the color fastness to sunlight is excellent, the application effect is good, and the development prospect is good.
Description
Technical Field
The invention belongs to the technical field of dyes and preparation thereof, and particularly relates to an intramolecular matching light-fast turquoise green pyridone active dye compound containing yellow and blue double-color bodies, and a preparation method and application thereof.
Background
The reactive dye has the characteristics of bright color, complete chromatogram, excellent wet treatment fastness and the like, and is widely applied to the dyeing and printing of cellulose fibers and protein fibers. With the improvement of living standard of people, the requirements on styles and colors of textiles are higher and higher. At present, the green dye is mostly prepared by compounding two or three dyes, but due to the difference of the solubility of the compounded dye, the directness of the fiber during dyeing, the reactivity of fixation with alkali and the like, the stability during dyeing is poor, the flower is easy to dye, and the head-tail difference is large. For example, a phthalocyanine-structured dye of the reactive blue system, whose molecule is composed of four isoindolines bonded together and forms a complex with copper, has good coplanarity, but has a large molecular weight and therefore has poor diffusion properties in fibers, and often has a problem of poor compatibility when it is matched with a yellow dye (refer to compatibility of reactive turquoise blue with reactive yellow dye [ J ] dye printing, 2007,33(14): 18-21.). Therefore, a more effective method is urgently needed to be found.
Disclosure of Invention
The invention provides a sunproof emerald pyridone reactive dye compound, a preparation method and application thereof, aiming at solving the problems in the prior art.
The light-fast emerald pyridone reactive dye compound provided by the invention can directly realize intramolecular color matching through a yellow color body and a blue color body contained in the molecule, and thoroughly solves a series of problems caused by dye compounding. Meanwhile, as pyridone with high light fastness is introduced into molecules, the light fastness of the dye can be effectively improved, and the dye has good development potential in clothes and/or other textiles, particularly in curtains and automotive interior materials.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a sunproof emerald green pyridone reactive dye compound, which has the following structural general formula (I):
wherein:
the structure represented by CuPc is shown as formula (II);
a+b+c＝3.5；
m is selected from H, Na and K;
n is an integer selected from 1 and 2;
R1selected from-H, -OCH3and-SO2Y；R2Is selected from-SO2Y and-H; wherein Y is selected from-CH2CH2OSO3M、-CH＝CH2and-CH2CH2OH；
R3Selected from-H, -SO3M、-OCH3-COOM and-OH;
x is selected from-Cl and-F;
R4is selected from-CH3and-CH2CH3。
The second aspect of the invention provides a preparation method of the sunfast emerald green pyridone reactive dye compound, which specifically comprises the following steps:
(a) chlorosulfonation reaction
Slowly (within half an hour) adding copper phthalocyanine powder into chlorosulfonic acid at 40 ℃, stirring for 30min, heating to 135-140 ℃, and maintaining the reaction for 3 h; cooling to 80 ℃, dropwise adding thionyl chloride within 2h, heating to 90 ℃, and preserving heat for 2 h; after the reaction is finished, cooling to room temperature, pouring into ice water while stirring, and separating out a precipitate; standing, filtering, and washing the filter cake to be neutral by using ice water to obtain a copper phthalocyanine sulfonyl chloride filter cake for later use;
(b) first condensation reaction
Dissolving the diaminobenzene sulfonic acid derivative in water, adjusting the pH value to 6, carrying out primary condensation reaction with the s-triazine derivative, controlling the temperature and the pH value, and obtaining a condensate solution after the reaction is finished;
(c) diazotization reaction
Maintaining the temperature of the condensate solution in the step (b) at 0-5 ℃, adding concentrated hydrochloric acid, and then dropwise adding a sodium nitrite aqueous solution to perform diazotization reaction; after the reaction is finished, sulfamic acid is added to obtain a diazonium salt solution;
(d) coupling reaction
Dissolving a pyridone derivative in water, adjusting the pH value to 6-7, dropwise adding the diazonium salt solution obtained in the step (c) into the dissolved pyridone derivative, keeping the pH value at 6-7, controlling the temperature at 5-10 ℃, and reacting for 1-2 hours to obtain a coupling solution;
(e) secondary condensation reaction
Adding water to p-phenylenediamine for dissolving, adjusting the pH value to 6-7, then dropwise adding the coupling solution obtained in the step (d) into the solution, keeping the pH value at 6-7, reacting at the temperature of 45-50 ℃ for 3-4 hours, and obtaining a secondary condensate solution;
(f) three times of condensation reaction
Adding water into the copper phthalocyanine sulfonyl chloride filter cake obtained in the step (a) for pulping, adjusting the pH value to 6-7, adding a beta-sulfate ethyl sulfone derivative and the polycondensate solution obtained in the step (e) into the mixture, reacting at the temperature of 45-50 ℃ and keeping the pH value at 6-7, and reacting for 7-8 hours; after the reaction is finished, salting out, suction filtering and drying of a filter cake are carried out, and finally the light-fast emerald pyridone reactive dye compound containing copper phthalocyanine and pyridone double chromogens is obtained.
Further, the diaminobenzene sulfonic acid derivative in the step (b) is selected from one of 2, 4-diaminobenzene sulfonic acid, m-phenylenediamine-4, 6-disulfonic acid and 2, 5-diaminobenzene sulfonic acid.
Further, the s-triazine derivative in the step (b) is selected from one of cyanuric chloride and cyanuric fluoride.
Further preferably, when the s-triazine derivative in step (b) is cyanuric chloride, step (b) is specifically: pulping cyanuric chloride and crushed ice at 0 ℃; dissolving the diaminobenzene sulfonic acid derivative in water, adjusting the pH value to 6, cooling to 0-5 ℃, adding the solution into cyanuric chloride, keeping the pH value at 4-5, and reacting for 2-3 hours to obtain the dichloro-s-triazine type mono-condensate solution.
Further preferably, when the s-triazine derivative in step (b) is melamine, step (b) is specifically: dissolving the diaminobenzene sulfonic acid derivative in water, adjusting the pH value to 6, cooling to-5-0 ℃, dropwise adding the melamine, keeping the pH value at 4-5, and reacting for 30min to obtain the difluoro-s-triazine type first condensate solution.
Further, the pyridone derivative in the step (d) is one selected from the group consisting of N-methyl-3-carboxamido-4-methyl-6-hydroxy-2-pyridone and N-ethyl-3-carboxamido-4-methyl-6-hydroxy-2-pyridone.
Further, the β -sulfate ester ethyl sulfone derivative in the step (f) is selected from a group consisting of 4- (. beta. -sulfate ester ethyl sulfone) aniline, 4- (. beta. -sulfate ester ethyl sulfone) aniline-2-sulfonic acid, 2-methoxy-4- (. beta. -sulfate ester ethyl sulfone) aniline, 2, 5-dimethoxy-4- (. beta. -sulfate ester ethyl sulfone) aniline, 2-amino-5- (. beta. -sulfate ester ethyl sulfone) benzoic acid, 3- (. beta. -sulfate ester ethyl sulfone) aniline-6-sulfonic acid, 2-methoxy-5- (. beta. -sulfate ester ethyl sulfone) aniline, and 2-hydroxy-5- (. beta. -sulfate ester ethyl sulfone) aniline And (4) seed preparation.
The third aspect of the invention provides an application of the sunproof emerald green pyridone reactive dye compound in the processing treatment of textiles.
Further, the sunproof emerald pyridone reactive dye compound realizes the processing treatment of textiles through technical means such as dyeing, printing and the like.
By adopting the technical scheme, compared with the prior art, the invention has the following technical effects:
the sun-proof emerald green pyridone reactive dye compound can directly realize intramolecular color matching through a yellow color body and a blue color body contained in a molecule, and thoroughly solves a series of problems encountered by dye compounding; meanwhile, as pyridone with high light fastness is introduced into molecules, the color fastness to sunlight is excellent, the application effect is good, and the color fastness to sunlight is good, so that the color fastness to sunlight has a good development prospect in clothes and/or other textiles, particularly in curtains and automotive interior materials.
Drawings
FIG. 1 is a Fourier transform infrared spectrum of a light fast emerald green pyridone reactive dye compound (I-6B) prepared in example 33 of the present invention;
FIG. 2 is a UV-VIS absorption spectrum of a light-fast emerald green pyridone reactive dye compound (I-6B) prepared in example 33 of the present invention.
Detailed Description
The present invention will be described in detail and specifically with reference to the following examples to facilitate better understanding of the present invention, but the following examples do not limit the scope of the present invention. For a better understanding of the invention, the dye structures in the examples are shown in the form of the free acid, but their actual form may be an alkali metal salt, e.g. sodium, potassium; the sulfone moiety is described as β -ethyl sulfone sulfate, but it may also exist as β -vinyl sulfone or β -hydroxyethyl sulfone.
Example 1
The embodiment discloses a sunproof emerald green pyridone reactive dye compound and a preparation method thereof, and the preparation method comprises the following specific steps:
(a) chlorosulfonation reaction: slowly (within half an hour) adding 0.100mol of copper phthalocyanine powder into 220mL of chlorosulfonic acid at 40 ℃, stirring for 30min, heating to 135-140 ℃, and maintaining the reaction for 3 h; cooling to 80 ℃, dropwise adding 0.504mol of thionyl chloride within 2h, heating to 90 ℃, and preserving heat for 2 h; after the reaction is finished, cooling to room temperature, pouring into ice water while stirring, and separating out a precipitate; standing, filtering, and washing the filter cake to be neutral by using ice water to obtain a copper phthalocyanine sulfonyl chloride filter cake for later use;
(b) primary condensation reaction: 0.101mol of cyanuric chloride and 60g of crushed ice are pulped for 30min at the temperature of 0 ℃; 0.100mol of 2, 4-diaminobenzene sulfonic acid is dissolved in 160mL of water, the pH value of the solution is adjusted to 6 by using 10% diluted hydrochloric acid, then the solution is added into cyanuric chloride, the pH value is kept to be 4-5, and the reaction is carried out for 2-3 h, so as to obtain dichloro s-triazine type first condensate solution;
(c) diazotization reaction: maintaining the temperature of the first condensate solution in the step (b) at 0-5 ℃, and adding 13mL of concentrated hydrochloric acid; 0.106mol of sodium nitrite is prepared into 40 percent aqueous solution, the aqueous solution is slowly added into the condensate, and the mixture is detected by Congo red test paper and starch potassium iodide test paper and is instantly changed into blue. After reacting for 1.5h, adding sulfamic acid to decompose excessive nitrous acid to obtain a diazonium salt solution;
(d) coupling reaction: dissolving 0.100mol of N-methyl-3-formamido-4-methyl-6-hydroxy-2-pyridone in 60mL of water, and adjusting the pH value to 6-7 by using a 20% sodium carbonate solution; dropwise adding the diazonium salt solution obtained in the step (c) into dissolved pyridone, keeping the pH value at 6-7, controlling the temperature at 5-10 ℃, and reacting for 1-2 hours to obtain a coupling solution;
(e) secondary condensation reaction: taking 0.100mol of p-phenylenediamine, adding 150mL of water for dissolving, and adjusting the pH value to 6-7 by using 10% dilute hydrochloric acid; dropwise adding the coupling solution obtained in the step (d) into the solution, keeping the pH value at 6-7, and reacting at the temperature of 45-50 ℃ for 3-4 h to obtain a secondary condensate solution;
(f) and (3) tertiary condensation reaction: adding 200mL of water into the copper phthalocyanine sulfonyl chloride filter cake in the step (a), pulping for 30min, adjusting the pH value to 6-7 by using a 20% sodium carbonate solution, adding 0.100mol of 4- (beta-sulfate ester ethyl sulfonyl) aniline and the polycondensate solution in the step (e), reacting at the temperature of 45-50 ℃, maintaining the pH value at 6-7, and reacting for 7-8 h; after the reaction is finished, salting out, suction filtration and filter cake drying are carried out, and finally the light-fast emerald pyridone reactive dye compound containing copper phthalocyanine and pyridone double chromogens is obtained, and the structure is shown as the formula (I-1A) in the table 1.
Examples 2 to 9
The embodiment discloses a sunproof emerald green pyridone reactive dye compound and a preparation method thereof, and the specific steps are similar to those in the embodiment 1. The difference lies in that: the 4- (beta-sulfate ethyl sulfone) aniline in the step (f) is changed into 4- (beta-sulfate ethyl sulfone) aniline-2-sulfonic acid, 2-methoxy-4- (beta-sulfate ethyl sulfone) aniline, 2, 5-dimethoxy-4- (beta-sulfate ethyl sulfone) aniline, 2-amino-5- (beta-sulfate ethyl sulfone) benzoic acid, 3- (beta-sulfate ethyl sulfone) aniline-6-sulfonic acid, 2-methoxy-5- (beta-sulfate ethyl sulfone) aniline and 2-hydroxy-5- (beta-sulfate ethyl sulfone) aniline, the dosage is 0.100 mol; and (f) finally obtaining the emerald pyridone reactive dye compound containing the copper phthalocyanine and the pyridone double color body, wherein the structures of the emerald pyridone reactive dye compound are shown as formulas (I-2A) to (I-9A) in the table 1.
Examples 10 to 18
The embodiment discloses a sunproof emerald green pyridone reactive dye compound and a preparation method thereof, and the specific steps are similar to those of embodiment 1 to embodiment 9. The difference lies in that: changing the 2, 4-diaminobenzene sulfonic acid in the step (b) into m-phenylenediamine-4, 6-disulfonic acid, wherein the using amount of the 2, 4-diaminobenzene sulfonic acid is 0.100 mol; and (f) finally obtaining the emerald pyridone reactive dye compound containing the copper phthalocyanine and the pyridone double color bodies, wherein the structures of the emerald pyridone reactive dye compound are shown as formulas (I-10A) to (I-18A) in the table 1.
Examples 19 to 27
The embodiment discloses a sunproof emerald green pyridone reactive dye compound and a preparation method thereof, and the specific steps are similar to those of embodiment 1 to embodiment 9. The difference lies in that: changing 2, 4-diaminobenzene sulfonic acid in the step (b) into m-2, 5-diaminobenzene sulfonic acid, wherein the using amount is 0.100 mol; and (f) finally obtaining the emerald pyridone reactive dye compound containing the copper phthalocyanine and the pyridone double color body, wherein the structures of the emerald pyridone reactive dye compound are shown as formulas (I-19A) to (I-27A) in the table 1.
Examples 28 to 54
The embodiment discloses a sunproof emerald green pyridone reactive dye compound and a preparation method thereof, and the specific steps are similar to those of embodiment 1 to embodiment 27. The difference lies in that: changing N-methyl-3-formamido-4-methyl-6-hydroxy-2-pyridone in the step (d) into N-ethyl-3-formamido-4-methyl-6-hydroxy-2-pyridone, wherein the using amount is 0.100 mol; and (f) finally obtaining the emerald pyridone reactive dye compound containing the copper phthalocyanine and the pyridone double color body, wherein the structures of the emerald pyridone reactive dye compound are shown as formulas (I-1B) to (I-27B) in the table 1.
The light-fast emerald pyridone reactive dye compound (I-6B) obtained in example 33 was subjected to a spectrum test using a fourier infrared spectrometer and an ultraviolet-visible absorption spectrometer, and the results are shown in fig. 1 and 2, respectively.
Examples 55 to 108
The embodiment discloses a sunproof emerald green pyridone reactive dye compound and a preparation method thereof, and the specific steps are similar to those of embodiment 1 to embodiment 54. With the difference that step (b) is: dissolving the diaminobenzene sulfonic acid derivative in 160mL of water, adjusting the pH value to 6, cooling to-5-0 ℃, dropwise adding 0.103mol of melamine, keeping the pH value within the range of 4-5, and reacting for 30min to obtain a difluoro-s-triazine type first condensate solution; the reaction temperature of the step (d) is 0-5 ℃; the reaction temperature of the step (e) is 15-20 ℃; and (f) finally obtaining the emerald pyridone reactive dye compound containing the copper phthalocyanine and the pyridone double color bodies, wherein the structures of the emerald pyridone reactive dye compound are shown as formulas (I-1C) to (I-27C) and formulas (I-1D) to (I-27D) in the table 1.
TABLE 1
Application example
The emerald green pyridone reactive dye compounds prepared in examples 1, 5, 9, 29, 33, 37, 57, 61, 73, 85 and 89 are applied to dyeing of cotton fabrics as application examples 1, 5, 9, 29, 33, 37, 57, 61, 73, 85 and 89, and the formula and dyeing process of the dye solution are as follows: 2.5g of fabric, 2 percent (o.m.f) of dye, 60g/L of sodium chloride, 15g/L of soda ash and 1: 20 of bath ratio; during dyeing, the fabric is dyed at room temperature, the temperature is raised to 60 ℃ within 20min, sodium carbonate is added for fixation after dyeing for 20min, and the temperature is kept for 40 min; after dyeing is finished, the fabric is taken out and washed by cold water, then soaped (soaping agent is 2g/L, bath ratio is 1: 20, 98 ℃ is multiplied by 10min), washed by cold water and dried, and finally the emerald green dyed fabric is obtained.
The dyed fabrics were tested for crocking fastness (ISO105-X12), washing fastness (ISO105-C06(C1S)) and light fastness (ISO105-B02(Method2)) respectively, and the results of each fastness are shown in Table 2.
Comparative example
Reactive turquoise blue G (RemazolTurquaiseBlueG) and RemazolBrilliant yellow4GL (RemazolBrilliant yellow4GL) are blended at a mass ratio of 10: 3 and then applied to dyeing of cotton fabrics, the specific formula, process and color fastness test are the same as those of the application examples, and the results of the color fastness of the color-blended dyed fabrics are shown in Table 2.
TABLE 2
As can be seen from the color fastness test results in the table 2, the light-fast emerald green pyridone reactive dye compound disclosed by the invention has excellent rubbing color fastness and washing fastness, is equivalent to or superior to a comparative example, has obviously superior light-fast fastness performance to the comparative example, has high color yield, saves cost, has good application effect, and has a good development prospect in clothes and/or other textiles, especially in curtains and automotive interior materials.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.
Claims (4)
1. A sunproof emerald green pyridone reactive dye compound has a structural formula (A)
）：
Formula (A), (B) and
) Formula (II)
Wherein:
the structure represented by CuPc is shown as formula (II);
a + b + c =3.5, and a > 0, b > 0, c > 0;
m is H;
n is an integer selected from 1 and 2;
R1selected from-H, -OCH3and-SO2CH2CH2OSO3H；R2Is selected from-SO2CH2CH2OSO3H and-H; and R is1And R2Not simultaneously being the same group, and R1And R2One of them is-SO2CH2CH2OSO3H；
R3Selected from-H, -SO3H、-OCH3-COOH and-OH;
x is selected from-Cl and-F;
R4is selected from-CH3and-CH2CH3；
The preparation method of the sunproof emerald green pyridone reactive dye compound comprises the following steps:
(a) chlorosulfonation reaction
Slowly adding copper phthalocyanine powder into chlorosulfonic acid at 40 ℃, stirring for 30min, heating to 135-140 ℃, and maintaining the reaction for 3 h; cooling to 80 ℃, dropwise adding thionyl chloride within 2h, heating to 90 ℃, and preserving heat for 2 h; after the reaction is finished, cooling to room temperature, pouring into ice water while stirring, and separating out a precipitate; standing, filtering, and washing the filter cake to be neutral by using ice water to obtain a copper phthalocyanine sulfonyl chloride filter cake for later use;
(b) first condensation reaction
Dissolving the diaminobenzene sulfonic acid derivative in water, adjusting the pH value to 6, carrying out primary condensation reaction with the s-triazine derivative, controlling the temperature and the pH value, and obtaining a condensate solution after the reaction is finished;
(c) diazotization reaction
Maintaining the temperature of the condensate solution in the step (b) at 0-5 ℃, adding concentrated hydrochloric acid, and then dropwise adding a sodium nitrite aqueous solution to perform diazotization reaction; after the reaction is finished, sulfamic acid is added to obtain a diazonium salt solution;
(d) coupling reaction
Dissolving a pyridone derivative in water, adjusting the pH value to 6-7, dropwise adding the diazonium salt solution obtained in the step (c) into the dissolved pyridone derivative, keeping the pH value at 6-7, controlling the temperature at 5-10 ℃, and reacting for 1-2 hours to obtain a coupling solution;
(e) secondary condensation reaction
Adding water to p-phenylenediamine for dissolving, adjusting the pH value to 6-7, then dropwise adding the coupling solution obtained in the step (d) into the solution, keeping the pH value at 6-7, reacting at the temperature of 45-50 ℃ for 3-4 hours, and obtaining a secondary condensate solution;
(f) three times of condensation reaction
Adding water into the copper phthalocyanine sulfonyl chloride filter cake obtained in the step (a) for pulping, adjusting the pH value to 6-7, adding a beta-sulfate ethyl sulfone derivative and the polycondensate solution obtained in the step (e) into the mixture, reacting at the temperature of 45-50 ℃ and keeping the pH value at 6-7, and reacting for 7-8 hours; after the reaction is finished, salting out, suction filtering and drying a filter cake to finally obtain a light-fast emerald pyridone reactive dye compound containing copper phthalocyanine and pyridone double chromogens;
the diaminobenzene sulfonic acid derivative in the step (b) is selected from one of 2, 4-diaminobenzene sulfonic acid, m-phenylenediamine-4, 6-disulfonic acid and 2, 5-diaminobenzene sulfonic acid;
the s-triazine derivative in the step (b) is selected from one of cyanuric chloride and cyanuric fluoride;
the pyridone derivative in the step (d) is selected from one of N-methyl-3-formamido-4-methyl-6-hydroxy-2-pyridone and N-ethyl-3-formamido-4-methyl-6-hydroxy-2-pyridone;
the beta-sulfate ethyl sulfone derivative in the step (f) is selected from 4- (beta-sulfate ethyl sulfone) aniline, 4- (beta-sulfate ethyl sulfone) aniline-2-sulfonic acid, 2-methoxy-4- (beta-sulfate ethyl sulfone) aniline, 2, 5-dimethoxy-4- (beta-sulfate ethyl sulfone) aniline, 2-amino-5- (beta-sulfate ethyl sulfonyl) benzoic acid, 3- (beta-sulfate ethyl sulfonyl) aniline-6-sulfonic acid, 2-methoxy-5- (beta-sulfate ethyl sulfonyl) aniline and 2-hydroxy-5- (beta-sulfate ethyl sulfonyl) aniline.
2. The sunfast emerald pyridone reactive dye compound of claim 1, wherein when the s-triazine derivative in step (b) is cyanuric chloride, step (b) is specifically: pulping cyanuric chloride and crushed ice at 0 ℃; dissolving the diaminobenzene sulfonic acid derivative in water, adjusting the pH value to 6, cooling to 0-5 ℃, adding the solution into cyanuric chloride, keeping the pH value at 4-5, and reacting for 2-3 hours to obtain the dichloro-s-triazine type mono-condensate solution.
3. The sunfast emerald pyridone reactive dye compound of claim 1, wherein when the s-triazine derivative of step (b) is melamine, step (b) is specifically: dissolving the diaminobenzene sulfonic acid derivative in water, adjusting the pH value to 6, cooling to-5-0 ℃, dropwise adding the melamine, keeping the pH value at 4-5, and reacting for 30min to obtain the difluoro-s-triazine type first condensate solution.
4. Use of the sunfast emerald pyridone reactive dye compound of claim 1 in the treatment of textiles.
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|---|---|---|---|---|
| JPS5465729A (en) * | 1977-10-18 | 1979-05-26 | Cassella Farbwerke Mainkur Ag | Water soluble fiber reactive green phthalocyanineeazo dye |
| JPS6187759A (en) * | 1984-09-06 | 1986-05-06 | Nippon Kayaku Co Ltd | Water-soluble phthalocyanine compound and method for coloring surface film of substrate by using the same |
| JPH0219803A (en) * | 1988-07-08 | 1990-01-23 | Nippon Kayaku Co Ltd | Color filter |
| CN1052494A (en) * | 1988-09-23 | 1991-06-26 | 山道士有限公司 | Phthalocyanine fibre-reactive dyes |
| CN101580646A (en) * | 2008-05-13 | 2009-11-18 | 珠海纳思达企业管理有限公司 | Weather-proof dye and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5465729A (en) * | 1977-10-18 | 1979-05-26 | Cassella Farbwerke Mainkur Ag | Water soluble fiber reactive green phthalocyanineeazo dye |
| JPS6187759A (en) * | 1984-09-06 | 1986-05-06 | Nippon Kayaku Co Ltd | Water-soluble phthalocyanine compound and method for coloring surface film of substrate by using the same |
| JPH0219803A (en) * | 1988-07-08 | 1990-01-23 | Nippon Kayaku Co Ltd | Color filter |
| CN1052494A (en) * | 1988-09-23 | 1991-06-26 | 山道士有限公司 | Phthalocyanine fibre-reactive dyes |
| CN101580646A (en) * | 2008-05-13 | 2009-11-18 | 珠海纳思达企业管理有限公司 | Weather-proof dye and application thereof |
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