CN114989088A - Meta-aramid fiber color development method and used treating agent - Google Patents
Meta-aramid fiber color development method and used treating agent Download PDFInfo
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- CN114989088A CN114989088A CN202210682637.8A CN202210682637A CN114989088A CN 114989088 A CN114989088 A CN 114989088A CN 202210682637 A CN202210682637 A CN 202210682637A CN 114989088 A CN114989088 A CN 114989088A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D229/00—Heterocyclic compounds containing rings of less than five members having two nitrogen atoms as the only ring hetero atoms
- C07D229/02—Heterocyclic compounds containing rings of less than five members having two nitrogen atoms as the only ring hetero atoms containing three-membered rings
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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
- D06P1/02—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 azo dyes
- D06P1/04—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 azo dyes not containing metal
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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
- D06P3/24—Polyamides; Polyurethanes
- D06P3/28—Preparing azo dyes on the material
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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
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention discloses a treating agent for a meta-aramid color development method, which has a structural general formula as follows:
the invention also discloses a color development method for the meta-aramid fiber by using the treating agent, which comprises the steps of swelling the aramid fiber at a certain temperature by using dimethyl sulfoxide and the like, soaking the aramid fiber in a specific treating agent solution to enable a large amount of the treating agent to be adsorbed on the aramid fiber, firmly bonding the treating agent on the fiber through chemical reaction at a high temperature, and finally developing the treated aramid fiber by using a diazonium salt solution. The method is simple to operate, and the colored aramid fiber fabric has the advantages of rich color spectrum, convenient color depth adjustment, high color fixation rate and excellent color fastness.
Description
Technical Field
The invention relates to the technical field of coloring of high polymer materials, in particular to a coloring technology of synthetic fibers, and particularly relates to a color development method for aramid fabrics.
Background
The main chain of the macromolecule of the meta-aramid fiber, namely the poly (m-phenyleneisophthalamide) fiber, is formed by alternately connecting amido bonds and aromatic rings and is arranged in a zigzag manner, a large number of hydrogen bonds exist among molecules, and strong van der Waals force exists among fiber molecules. Therefore, the meta-aramid fiber has the characteristics of regular and compact structure, high crystallinity, high glass transition temperature and the like. Therefore, m-aramid has a problem of difficult dyeing (modern textile technology, 2022,30(2), 9-17).
The literature (Dyes and Pigments,2021,194,109555) reports Dyes containing a bis-aziridine structure as follows:
the dye is dissolved in methanol, placed into a fabric, heated to 70 ℃ to enable the dye to be adsorbed on aramid fiber, and then the dye and the aramid fiber are subjected to chemical reaction at a high temperature of 150 ℃, so that the dye is firmly combined on the aramid fiber. The problems are that the dyed aramid fiber fabric has dark color and low reaction rate. In the document, the aramid fiber fabric can be dyed repeatedly for multiple times to obtain higher color depth and color fixing rate. The dyeing method of the document is not flexible, and in order to obtain a color, a dye with a corresponding color needs to be synthesized.
Diazo-coupled color development techniques can be analogized to traditional insoluble azo dye dyeing techniques. The insoluble azo dye dyeing technology is that fabric is first primed with coupling component solution and then treated with ice cooled diazo component solution to produce color and produce fixed water insoluble azo dye. The insoluble azo dye dyeing technology is mainly applied to cotton fabrics, and the azo dye formed on the cotton fabrics is a water-insoluble substance, so that the dyed cotton fabrics have good color fastness such as washing resistance, but the bonding force between the dye and the cotton fibers is only weak acting force such as hydrogen bonds, van der waals force and the like.
Diazo-coupling color development technology is also applied to the field of dyeing of silk fabrics (such as: CN 101781855A). The side group of the silk fibroin fiber macromolecule chain has a phenol hydroxyl group of tyrosine, and the group has the capability of performing coupling reaction with diazonium salt under an alkaline condition, so that an azo color body is formed, and the color of silk fabric is developed. However, the color reaction condition needs to be carried out under an alkaline condition, and the silk fiber is damaged to a certain extent.
The application report of the diazo-coupling color development technology on synthetic fibers, particularly aramid fibers, is not seen yet.
Disclosure of Invention
The invention aims to provide a color development method aiming at meta-aramid and a treating agent used by the method.
In order to solve the technical problems, the invention provides a treating agent for a meta-aramid color development method, which has a structural general formula as follows:
R 1 is a hydrogen atom, R 2 Optionally selected from hydrogen atom or cyano group.
As an improvement of the treating agent, the treating agent is as follows:
the invention also provides a developing method for the meta-aramid fiber by using the treating agent, which comprises the following steps:
(1) first pretreatment:
soaking the meta-aramid fabric in an organic solvent I, taking out, cleaning and drying;
(2) second pretreatment:
soaking the fabric obtained by the treatment in the step (1) in an organic solvent II containing a treating agent, taking out and airing the fabric, and baking the fabric;
(3) color development:
and (3) placing the fabric obtained by the treatment in the step (2) in an organic solvent III, adding a diazonium salt aqueous solution for color development, taking out, cleaning and drying.
As an improvement of the color development method for m-aramid of the present invention, in the step (1):
the organic solvent I is N, N-dimethylformamide or dimethyl sulfoxide (preferably dimethyl sulfoxide);
the soaking temperature is 20-80 ℃ (the preferred temperature is 55 ℃), and the soaking time is 0.5-6 h (the preferred soaking time is 3 h);
the cleaning method comprises washing with clear water at room temperature (until the eluate does not contain organic solvent I), and oven drying at 60 + -5 deg.C to constant weight.
As a further improvement of the color development method for m-aramid of the present invention, in the step (2):
the organic solvent II is: methanol, acetone, dichloromethane, tetrahydrofuran; the concentration of the treating agent in the organic solvent II containing the treating agent is 0.05-5 g/L;
the soaking temperature is 25 +/-5 ℃, and the soaking time is 1 +/-0.2 h;
the baking temperature is 150-200 ℃ (preferably 180 ℃); the baking time is 0.5-2 h (preferably 1 h).
As a further improvement of the color development method aiming at the meta-aramid fiber of the invention: the diazonium salt in the step (3) is a product generated by diazotization of aromatic compounds containing primary amino groups.
As a further improvement of the color development method aiming at the meta-aramid fiber of the invention:
the aromatic compound containing primary amino group is aniline, p-toluidine, p-anisidine, p-chloroaniline, p-nitroaniline, o-chloro-p-nitroaniline, 2, 6-dibromo-4-nitroaniline, p-cyanoaniline, 1-naphthylamine, 2-nitro-5-aminothiazole, 2-aminobenzothiazole and 3-amino-5-nitrobenzo [ d ] isothiazole.
As a further improvement of the color development method for m-aramid of the present invention, in the step (3):
the organic solvent III is methanol and N, N-dimethylformamide, and the dosage of the organic solvent III is to completely immerse the fabric;
0.01-1 mmol of diazonium salt is used for every gram of fabric;
the color development temperature is 0-5 ℃; the color development time is 0.5 +/-0.1 h;
the cleaning method comprises the following steps: washing with water (normal temperature tap water washing till no obvious color falls), then soaping (soap formula: soap flakes 1g/L, sodium carbonate 1 g/L; process: bath ratio 1:50, 80 deg.C, 10min), and finally washing with water (normal temperature tap water washing till no obvious color falls); the drying is carried out at 60 +/-5 ℃ until the weight is constant.
As a further improvement of the color development method aiming at the meta-aramid fiber of the invention: the following treatment process is added between the step (2) and the step (3):
cleaning the fabric obtained by the treatment in the step (2) (i.e. the fabric baked in the step (2)) by using N, N-dimethylformamide (bath ratio is 1:50, temperature is 60 ℃, time is 10min), and then washing (normal-temperature tap water washing is carried out for 5 min); drying (drying at 60 +/-5 ℃ to constant weight);
and (4) carrying out step (3) on the dried fabric.
In the present invention:
the preparation method of the diazonium salt aqueous solution is the conventional method, and the specific method can refer to the open literature (silk, 2019,56(6), 1-5). The aqueous diazonium salt solution is prepared by the following general method: diazotizing an aromatic compound containing primary amino group, acid and sodium nitrite in water to generate a diazonium salt aqueous solution; the using amount of the sodium nitrite is 1-1.2 times of the mole number of the aromatic compound containing primary amino group; the reaction temperature is 0-5 ℃; the reaction time was about 0.5 h.
The inventor finds in practice that the m-aramid treated by dimethyl sulfoxide can be developed by using weak alkaline arylamine diazonium salt in a methanol system and the like, and the basic principle is that the weak alkaline arylamine and m-phenylenediamine units in the m-aramid macromolecules are subjected to coupling reaction to form azo color bodies. The main problems of the color development method include: (1) because the amido group has weak power supply, the m-phenylenediamine unit is difficult to generate the coupling reaction, and the coupling reaction can be generated only by using weak alkaline arylamine diazonium salt; (2) the color of the color-developing aramid fiber is mainly brown color, and the color type is single.
In order to solve the problems, the aramid fiber is grafted with the treating agent, so that the method can use the alkalescent arylamine diazonium salt for coupling reaction and also can use the strongly alkaline arylamine diazonium salt for coupling reaction; thus overcoming the disadvantage of having to use weakly basic diazonium salts of aromatic amines for the coupling reaction to take place. And, the present invention enriches the structure types, so the achievable color variety also increases.
The invention provides a whole set of scheme for aramid color development, and solves the problem that the diazo-coupling technology cannot be well applied to aramid color development. In the present invention:
(1) the aramid fiber fabric is pretreated by using optimized organic solvents such as dimethyl sulfoxide and the like, so that the aramid fiber is swelled, the effect of adsorbing more coupling components is achieved, and a foundation is laid for achieving deep color subsequently;
(2) the aramid fiber fabric is treated by using a special treating agent as a coupling component, the treating agent is promoted to react on the aramid fiber in a baking mode, and the coupling component is combined on the aramid fiber in a covalent bond mode, so that a foundation is laid for the firm combination of an azo color body formed subsequently on the aramid fiber;
(3) according to the invention, aniline substances (treating agents) are used as coupling components, so that the coupling reaction condition is an acidic condition, and the diazonium salt solution system is acidic, so that pH value adjustment is not required during color development;
(4) according to the invention, after the aramid fabric is treated by the treating agent, the color fixing rate of the final color body and the aramid fabric can be further improved by a cleaning mode of an organic solvent.
The scheme provided by the invention has strict sequence requirements, each step provided by the scheme cannot be omitted, the sequence cannot be disordered, or the effect of enabling the aramid fiber to be firm and deep in color cannot be achieved.
In summary, compared with the prior art, the invention has the following advantages:
the method comprises the steps of swelling the aramid fiber at a certain temperature by using dimethyl sulfoxide and the like, soaking the aramid fiber in a specific treating agent solution to enable a large amount of treating agents to be adsorbed on the aramid fiber, firmly bonding the treating agents on the fiber through chemical reaction at a high temperature, and finally developing the treated aramid fiber by using a diazonium salt solution.
The treatment of dimethyl sulfoxide to aramid fiber obviously increases the adsorption capacity of aramid fiber to the treating agent.
The treating agent can chemically react with the aramid fiber, so that a reaction site is provided for the subsequent diazo salt color development reaction on one hand, and the formed color body can be firmly combined on the aramid fiber on the other hand.
The invention has the technical advantage that the aramid fabric can be pretreated according to the steps (1) and (2) of the method of the invention and then only needs to be developed by using corresponding diazonium salt according to the required color. Compared with the traditional method of dyeing by adopting dye, the method has more flexibility.
The method is simple to operate, and the colored aramid fiber fabric has the advantages of rich color spectrum, convenient color depth adjustment, high color fixation rate and excellent color fastness.
Compared with the method for directly dyeing by adopting the dye, the method has the advantage that the obtained color-developing aramid fiber can obtain extra special colored light which is different from the dye-dyed fabric.
In conclusion, the treatment agent which cannot react with the aramid fiber can be cleaned by cleaning the cured aramid fiber with the organic solvent, so that the combination degree of the treatment agent on the aramid fiber and the aramid fiber is improved, the combination degree of the color body on the finally developed aramid fiber and the aramid fiber can be further improved, and the color fixation rate of the developed aramid fiber is greatly improved.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a drawing of Compound 3 1 H NMR spectrum.
FIG. 2 shows a scheme for preparing a compound 3 13 C NMR spectrum.
FIG. 3 is a drawing of Compound 5 1 H NMR spectrum.
FIG. 4 is a drawing of Compound 5 13 C NMR spectrum.
FIG. 5 is a flow chart of the color rendering operation.
FIG. 6 is a color rendering schematic diagram of aramid fiber.
FIG. 7 is a K/S value curve of an o-chloro-p-nitroaniline diazonium salt chromogenic aramid fabric.
FIG. 8 is a K/S value curve of 2-nitro-5-aminothiazole diazonium salt chromogenic aramid fabric.
FIG. 9 is a K/S value curve of p-chloroaniline diazonium salt chromogenic aramid fabric.
FIG. 10 is a K/S value curve of the aramid fabric obtained by using the compound 8.
Detailed Description
The invention and the manner of carrying out the invention are further illustrated in the following examples and figures. These examples are intended only to illustrate the invention further and are not intended to limit the scope of the invention thereto. The starting materials or reagents described in the present invention are commercially available unless otherwise specified. Among them, compound 1 is commercially available from Hill chemical industry development Co., Ltd or is synthesized by itself using a literature method (Dyes and Pigments,2021,194,109555). The preparation method of the diazonium salt aqueous solution is the conventional method, and the specific method can refer to the open literature (silk, 2019,56(6), 1-5). Compound 8 was also synthesized by literature methods (Dyes and Pigments,2021,194,109555). The specification of the meta-aramid fabric in the examples described below is: twill, 160g/cm 2 . Before the fabric is used, impurities such as oil solution and the like are ensured to be avoided.
Preparing raw materials:
synthesis of Compound 3
Under the protection of nitrogen, compound 1(2mmol, 460mg), compound 2(2mmol, 330mg), 4-dimethylaminopyridine (DMAP, 0.2mmol, 25mg), dicyclohexylcarbodiimide (DCC, 2mmol, 412mg) and dichloromethane (20ml) are added in sequence into a three-neck reaction flask with magnetons, and then stirred at room temperature (20-25 ℃) for 12 hours. After the raw materials are completely reacted by thin-layer chromatography analysis, removing dichloromethane by using a rotary evaporator, and carrying out column chromatography separation on residues by using silica gel (200-300 meshes), wherein an eluent: v Petroleum ether /V Ethyl acetate (iii) 5/1 at a flow rate of 2 to 3mL/min, and collecting the eluate containing fractions having a specific shift value (Rf value) of 0.3 to 0.4 to give compound 3 as a colorless liquid, 611mg, in 81% yield. 1 H NMR(CDCl 3 ,400MHz)δ8.02(d,J＝8.8Hz,2H),7.25-7.22(m,4H),6.78(d,J＝8.4Hz,2H),6.71(dd,J 1 ＝J 2 ＝7.2Hz,1H),4.49(t,J 1 ＝6.4Hz,J 2 ＝6.0Hz,2H),3.70(t,J 1 ＝6.0Hz,J 2 ＝6.4Hz,2H),3.45(q,J 1 ＝6.8Hz,J 2 ＝7.2Hz,2H),1.20(t,J 1 ＝6.8Hz,J 2 ＝7.2Hz,3H). 13 C NMR(CDCl 3 ,100MHz)δ165.70,147.78,134.02,131.28,130.14,129.58,126.53,122.07(q,J＝273Hz),116.58,112.31,62.99,48.96,45.43,28.60(q,J＝41Hz),12.48.MS(ESI+):378.1[M+H].
Synthesis of Compound 5
Substitution of compound 2(2mmol, 330mg) for compound 4(2mmol, 380mg), the other synthetic steps were as described for "synthesis of compound 3" to give compound 5 as a colorless liquid, 684mg, in 85% yield. 1 H NMR(CDCl 3 ,400MHz)δ8.06(d,J＝8.4Hz,2H),7.34(dd,J 1 ＝8.4Hz,J 2 ＝7.6Hz,2H),7.30(d,J＝8.0Hz,2H),6.89-6.85(m,3H),4.57(t,J＝6.0Hz,2H),3.88(t,J＝6.0Hz,2H),3.83(t,J＝6.8Hz,2H),2.68(t,J＝6.8Hz,2H). 13 C NMR(CDCl 3 ,100MHz)δ165.46,146.14,133.99,130.94,129.99,129.82,126.47,121.96(q,J＝273Hz),118.40,117.86,112.97,62.62,50.07,47.47,28.50(q,J＝41Hz),16.01.MS(ESI+):403.1[M+H].
Preparation of diazonium salts
Preparation example 1: preparation of aniline diazonium salts
Aniline (5mmol, 465mg) is accurately weighed, added into a reaction bottle filled with 2mL concentrated hydrochloric acid water solution (50mL), placed in an ice-water bath, and stirred for reaction at the temperature of 0-5 ℃. Subsequently, an aqueous solution (10mL) containing sodium nitrite (5mmol, 345mg) was slowly added over 10min, and the reaction was continued for 30 min. The obtained diazonium salt solution was made up to 1L (diazonium salt concentration 5mmol/L) using deionized water and stored in an ice-water bath. The aqueous aniline diazonium salt solution is obtained.
Preparation example 2: preparation of p-toluidine diazonium salt
The aniline (5mmol) was replaced with p-toluidine (5mmol), otherwise see preparation example 1. This was an aqueous solution of p-toluidine diazonium salt.
Preparation example 3: preparation of p-methoxyaniline diazonium salt
Aniline (5mmol) was replaced with p-anisidine (5mmol), otherwise see preparation example 1. The aqueous solution of p-methoxyaniline diazonium salt is obtained.
Preparation example 4: preparation of 1-naphthylamine diazonium salt
Aniline (5mmol) was replaced with 1-naphthylamine (5mmol), otherwise see preparation example 1. The obtained 1-naphthylamine diazonium salt aqueous solution.
Preparation example 5: preparation of p-chloroaniline diazonium salts
Parachloroaniline (5mmol, 638mg) was weighed accurately into a reaction flask, concentrated hydrochloric acid (2mL) was added slowly while deionized water (50mL) was added, and the solid was dissolved completely by heating to 70 ℃. Then the reaction flask is placed in an ice bath to be cooled to 0-5 ℃, sodium nitrite (5mmol, 345mg) is added into the reaction flask in 3 batches within 5min, and the reaction is continued for 30 min. The obtained diazonium salt solution was made up to 1L (diazonium salt concentration 5mmol/L) using deionized water and stored in an ice-water bath. The aqueous solution of p-chloroaniline diazonium salt is obtained.
Preparation example 6: preparation of para-cyanoaniline diazonium salt
P-chloroaniline (5mmol) was replaced with p-cyanoaniline (5mmol), otherwise see preparation example 5. The aqueous solution of the diazonium salt of the paracyano aniline is obtained.
Preparation example 7: preparation of p-nitroaniline diazonium salt
P-chloroaniline (5mmol) was replaced with p-nitroaniline (5mmol), otherwise see preparation example 5. The obtained product is p-nitroaniline diazonium salt aqueous solution.
Preparation example 8: preparation of o-chloro-p-nitroaniline diazonium salt
Sodium nitrite (5mmol, 345mg) is slowly added into 2.5mL of concentrated sulfuric acid at 0 ℃ (ice water bath), and stirred to completely dissolve the sodium nitrite (if the dissolution rate is slow when the sodium nitrite is in block form, the reaction bottle can be transferred into an oil bath kettle, slightly heated to 30 ℃, and cooled to 0 ℃ after the sodium nitrite is completely dissolved). 6mL of a mixed acid (V) of propionic acid and glacial acetic acid is added dropwise within 10min Propionic acid ∶V Glacial acetic acid 1: 5), stirring is continued for 0.5h after the end of the dropping, during which the temperature is kept at 0 ℃. Subsequently, 6mL of a mixed acid of propionic acid and glacial acetic acid (V) containing o-chloro-p-nitroaniline (5mmol, 863mg) was slowly added dropwise over 10min Propionic acid ∶V Glacial acetic acid 1: 5), and stirring for 4 hours after the dripping is finished to prepare the o-chloro-p-nitroaniline diazonium salt. The solution was made up to 1L (diazonium salt concentration 5mmol/L) using deionized water and stored at 0 ℃ until use. The obtained product is the o-chloro-p-nitroaniline diazonium salt aqueous solution.
Preparation example 9: preparation of 2, 6-dibromo-4-nitroaniline diazonium salt
The o-chloro-p-nitroaniline (5mmol) was replaced with 2, 6-dibromo-4-nitroaniline (5mmol), otherwise see preparation example 8. To obtain the 2, 6-dibromo-4-nitroaniline diazonium salt aqueous solution.
Preparation example 10: preparation of 2-nitro-5-aminothiazole diazonium salt
The o-chloro-p-nitroaniline (5mmol) was replaced with 2-nitro-5-aminothiazole (5mmol), otherwise see preparation 8. The obtained 2-nitro-5-aminothiazole diazonium salt solution.
Preparation example 11: preparation of 2-aminobenzothiazole diazonium salt
O-chloro-p-nitroaniline (5mmol) was replaced with 2-aminobenzothiazole (5mmol), otherwise see preparation 8. The obtained 2-aminobenzothiazole diazonium salt aqueous solution.
Preparation example 12: preparation of 3-amino-5-nitrobenzo [ d ] isothiazoldiazonium salt
O-chloro-p-nitroaniline (5mmol) was replaced with 3-amino-5-nitrophenyl [ d ] oisothiazole (5mmol), otherwise see preparation 8. The obtained 3-amino-5-nitrobenzene [ d ] isothiazole diazonium salt solution.
Example 1: the meta-aramid color development method comprises the following steps of:
(1) first pretreatment:
soaking 1g of meta-aramid fabric in a 100mL single-neck flask containing 20mL of dimethyl sulfoxide, placing the single-neck flask in an oil bath kettle at 55 ℃, keeping for 3 hours, taking out, washing with tap water at room temperature (until eluent is in a colorless state), and drying at 60 ℃ to constant weight;
(2) second pretreatment:
soaking the aramid fiber fabric obtained by the treatment in the step (1) in a methanol (20mL) solution containing a compound 3(40mg), taking out after soaking for 1h at 25 ℃, airing until the weight basically does not change any more, and then placing the fabric in an oven at 180 ℃ for baking for 1 h;
(3) color development:
immersing the aramid fiber fabric treated in the step (2) in a 100mL flat-bottom three-neck flask filled with 5mL of methanol, placing the three-neck flask in an ice water bath, keeping the ambient temperature in the flask at 0-5 ℃, adding 10mL of the o-chloro-p-nitroaniline diazonium salt aqueous solution with the concentration of 5mmol/L obtained in the preparation example 8 (namely 0.05mmol of the o-chloro-p-nitroaniline diazonium salt), shaking the flask by hand to quickly and uniformly mix the solution, immediately showing the red color of the visible fabric, continuously waiting for 30min until the color of the fabric is not obviously deepened, taking out the fabric, washing the fabric with tap water at normal temperature (washing the water with tap water till the washing liquid has no obvious color and drops), and then washing with soap, wherein the formula of the soap washing liquid is as follows: 1g/L of soap chips, 1g/L of sodium carbonate and the balance of water; the soaping process comprises the following steps: the bath ratio is 1:50, 80 ℃,10 min, finally washing with water at normal temperature (washing with tap water until no obvious color drops in the washing liquid), and finally drying the fabric in an oven at 60 ℃ to constant weight.
Example 2: compound 3(40mg) in step (2) of example 1 was replaced with compound 5(40mg), and the other procedures were as described in example 1.
Example 3: the methanol (20mL) in step (2) of example 1 was replaced with acetone (20mL) and the other working up steps were as described in example 1.
Example 4: the methanol (20mL) in step (2) of example 1 was replaced with dichloromethane (20mL) and the other working up steps were as described in example 1.
Example 5: the methanol (20mL) in step (2) of example 1 was replaced with tetrahydrofuran (20mL) and the other working up steps were as described in example 1.
Example 6: compound 3(40mg) was replaced with compound 3(100mg) in step (2) of example 1, and the other operating procedures were as described in example 1.
Example 7: compound 3(40mg) was replaced with compound 3(20mg) in step (2) of example 1, and the other procedures were as described in example 1.
Example 8: compound 3(40mg) was replaced with compound 3(10mg) in step (2) of example 1, and the other procedures were as described in example 1.
Example 9: compound 3(40mg) was replaced with compound 3(1mg) in step (2) of example 1, and the other procedures were as described in example 1.
Example 10: the o-chloro-p-nitroaniline diazonium salt (0.05mmol) in step (3) of example 1 was replaced with aniline diazonium salt (0.05mmol), and the other procedures were as described in example 1.
Example 11: the o-chloro-p-nitroaniline diazonium salt (0.05mmol) in step (3) of example 1 was replaced with p-toluidine diazonium salt (0.05mmol), that is, the aqueous p-toluidine diazonium salt solution obtained in preparation example 2 was used, and the other procedures were as described in example 1.
Example 12: the o-chloro-p-nitroaniline diazonium salt (0.05mmol) in step (3) of example 1 was replaced with p-methoxyaniline diazonium salt (0.05mmol), and the other procedures were as described in example 1.
Example 13: the o-chloro-p-nitroaniline diazonium salt (0.05mmol) in step (3) of example 1 was replaced with p-chloroaniline diazonium salt (0.05mmol), and the other procedures were as described in example 1.
Example 14: the o-chloro-p-nitroaniline diazonium salt (0.05mmol) in step (3) of example 1 was replaced with p-nitroaniline diazonium salt (0.05mmol) and the other operating steps were as described in example 1.
Example 15: the o-chloro-p-nitroaniline diazonium salt (0.05mmol) in step (3) of example 1 was replaced with 2, 6-dibromo-4-nitroaniline diazonium salt (0.05mmol), and the other procedures were as described in example 1.
Example 16: the o-chloro-p-nitroaniline diazonium salt (0.05mmol) in step (3) of example 1 was replaced with p-cyanoaniline diazonium salt (0.05mmol), and the other procedures were as described in example 1.
Example 17: the o-chloro-p-nitroaniline diazonium salt (0.05mmol) in step (3) of example 1 was replaced with 1-naphthylamine diazonium salt (0.05mmol), and the other procedures were as described in example 1.
Example 18: the o-chloro-p-nitroaniline diazonium salt (0.05mmol) in step (3) of example 1 was replaced with 2-nitro-5-aminothiazole diazonium salt (0.05mmol), and the other procedures were as described in example 1.
Example 19: the o-chloro-p-nitroaniline diazonium salt (0.05mmol) in step (3) of example 1 was replaced with 2-aminobenzothiazole diazonium salt (0.05mmol), and the other procedures were as described in example 1.
Example 20: the o-chloro-p-nitroaniline diazonium salt (0.05mmol) in step (3) of example 1 was replaced with 3-amino-5-nitrophenyl [ d ] isothiazolium diazonium salt (0.05mmol), and the other procedures were as described in example 1.
Example 21: 5mL of methanol was replaced with 5mL of N, N-dimethylformamide in step (3) of example 1, and the other operating steps were as described in example 1.
And (3) effect testing:
a method for judging fabric color comprises the following steps: and observing with naked eyes.
Secondly, a method for testing the color depth (K/S) value of the fabric comprises the following steps: and testing by adopting a Datacolor 600 computer color measuring and matching instrument under the conditions of a D65 light source and a 10-degree visual angle, wherein the K/S value is a color depth value corresponding to the highest peak on a K/S curve of the measured fabric, a plurality of different sites of the measured fabric are selected for testing during testing, and the obtained data are averaged.
Thirdly, a method for testing the color fixing rate of the fabric: placing the fabric in a single-neck flask containing N, N-Dimethylformamide (DMF) (100ml), heating to 120 deg.C, maintaining for 10min, replacing with new DMF, repeating the above operation until no more obvious color is present in the solvent, taking out the fabric, cooling, washing with clear water, and air drying.
The K/S values before and after the above operation were measured in this way and are respectively designated as K 1 And K 2 。
The fixation rate f is calculated according to the following formula:
fourthly, a color fastness test method:
the soaping color fastness of the fabric is tested by a test method B (2) in GB/T3921-; the color fastness to rubbing of the fabric is tested by GB/T3920-2008; the sublimation color fastness is tested according to the national standard GB/T6152-1997.
The effects of the embodiment are as follows:
first, the fabric colors, color depth values and fixation ratios obtained in examples 1 to 21 are shown in table 1 below.
TABLE 1
Description of the drawings: the "purple light" is judged by naked eyes.
The results of the above examples show that: the method provided by the invention can ensure that the aramid fiber can obtain firm dark and thick color; within the scope of the method provided by the invention, excellent coloring effect can be achieved by using a specified treating agent; the use of acetone, dichloromethane and tetrahydrofuran in step (2) of the present invention all had substantially equivalent effects to those when methanol was used; in the step (2), the concentration of the treating agent in the solvent is 0.05-5 g/L, the aramid fibers are developed, and the color depth of the colored aramid fibers is obviously increased along with the increase of the concentration of the treating agent; the method provided by the invention can ensure that the aramid fiber can obtain wide color chromatogram and has better color fixation rate; the use of N, N-dimethylformamide in step (3) of the present invention also has an effect comparable to that when methanol is used.
Second, the color fastness data of the fabrics obtained in examples 1 to 21 are shown in table 2 below.
TABLE 2
The color fastness test results of the examples 1 to 21 show that the soaping color fastness, the friction color fastness and the sublimation color fastness of the colored aramid fibers obtained by the method are all 4 grades or above.
Example 22, compared with example 1, the following treatment process is added between the step (2) and the step (3):
and (3) after the step (2), cleaning the baked fabric by using N, N-dimethylformamide (bath ratio is 1:50, temperature is 60 ℃, time is 10min), then washing by water (normal-temperature tap water washing is 5min), and then drying to constant weight at 60 ℃.
And (4) carrying out the subsequent step (3) on the dried fabric.
The other operating steps are as described in example 1.
Effect of example 22
The color of the colored aramid fiber is purple red, the color depth (K/S value) is 22, and the fixation rate is 98%. The soaping color fastness (discoloration) of the colored aramid fiber is grade 5, the dry friction color fastness is grade 5, the wet friction color fastness is grade 4-5, and the sublimation color fastness (discoloration) is grade 4-5. Compared with the result of the example 1, it can be known that if the baked aramid fiber fabric in the step (2) of the method is washed by the organic solvent, the color fixing rate of the colored aramid fiber fabric can be effectively improved on the premise that the color light of the fabric is kept unchanged and the color depth value is not obviously reduced. Meanwhile, various color fastness performances of the colored fabric are excellent.
Comparative example 1:
the aramid fabric is developed by directly adopting the color development of the step (3) of the example 1 without a pretreatment process.
Comparative example 2:
the aramid fabric was subjected to color development by the second pretreatment of step (2) and the color development of step (3) of example 1 without the first pretreatment.
Comparative example 3:
the aramid fabric was subjected to color development using the first pretreatment of step (1) and the color development of step (3) of example 1 without performing the second pretreatment.
Comparative example 4:
the aramid fabric was subjected to color development by the first pretreatment of step (1) and the color development of step (3) of example 1 without performing the second pretreatment, and the o-chloro-p-nitroaniline diazonium salt (0.05mmol) in step (3) of example 1 was replaced with aniline diazonium salt (0.05mmol), and the other procedures were as described in example 1.
Comparative example 5:
the steps (1) and (2) in the example 1 are exchanged, namely, the aramid fiber fabric is soaked in the methanol solution of the compound 3 for treatment, and then the treated fabric is soaked in dimethyl sulfoxide for treatment, and the rest is the same as the example 1.
Comparative example 6: 20mL of dimethyl sulfoxide in step (1) of example 1 was replaced with 20mL of N, N-dimethylformamide as in example 1.
Comparative example 7: the oil bath pan at 55 ℃ in step (1) of example 1 was replaced with an oil bath pan at 20 ℃ as in example 1.
Comparative example 8: the 55 ℃ oil bath pan in step (1) of example 1 was replaced with an 80 ℃ oil bath pan, otherwise as in example 1.
Comparative example 9: the soaking in the step (1) of example 1 was replaced by soaking for 3 hours and 0.5 hour, and the rest was the same as in example 1.
Comparative example 10: the soaking in the step (1) of the example 1 is replaced by soaking for 3 hours for 6 hours, and the rest is the same as the example 1.
Comparative example 11: compound 3(40mg) in step (2) of example 1 was replaced with compound 2(40mg), otherwise as in example 1.
Comparative example 12: example 1 was repeated except that compound 3(40mg) in step (2) of example 1 was replaced with compound 6(40mg), wherein compound 6 had the following structural formula:
the synthesis procedure of compound 6 was as follows:
replacement of compound 1(2mmol, 460mg) with compound 7(2mmol, 436mg, which compound 7 is self-synthesized by literature methods (Bioorganic & Medicinal Chemistry,2012,20(21),6523 and 6532)) and other synthetic steps as described in example 1 gave compound 6 as a colorless liquid, 417mg, yield 57%. MS (ESI +):366.1[ M + H ].
Comparative example 13: the oven at 180 ℃ in step (2) of example 1 was replaced with an oven at 150 ℃ and the other operating steps were as described in example 1.
Comparative example 14: the oven at 180 ℃ in step (2) of example 1 was replaced with an oven at 200 ℃ and the other operating steps were as described in example 1.
Comparative example 15: the baking time of 1h in the step (2) of the example 1 is replaced by baking time of 0.5h, and other operation steps are as described in the example 1.
Comparative example 16: the baking 1h in the step (2) of the example 1 is replaced by baking 2h, and other operation steps are as described in the example 1.
The comparative examples above have the following effects in table 3:
TABLE 3
Comparing the above respective proportions with example 1, it can be seen that:
the results of comparative example 1 show that the color development of aramid fabric can not be realized by directly using diazonium salt without pretreatment.
The results of comparative example 2 show that only a very light color can be obtained when the treatment agent is directly used without dimethyl sulfoxide treatment and then the color is developed with the diazonium salt. This is because if the aramid fiber is not sufficiently swollen without the treatment with dimethyl sulfoxide, the treatment agent hardly enters the fiber, that is, the treated aramid fiber contains a small amount of the treatment agent, and the color development is light.
Comparative example 3 the results show that in the process of the invention, the color development of aramid fibers is possible with o-chloro-p-nitroaniline diazonium salt in the absence of a treatment step with a treating agent, but the color obtained is different from that of example 1.
Comparative example 4 the results show that in the process of the present invention, the use of aniline diazonium salt (i.e., a non-weakly basic primary arylamine diazonium salt) does not allow for color development of aramid fibers in the absence of a treating agent treatment step. This is because there is no treatment agent on the treated aramid fiber, and the non-weakly basic primary arylamine diazonium salt does not have a coupling reaction site for reaction, thereby making color development impossible.
Comparative example 5 the results show that the specific order of the steps of the process of the present invention cannot be reversed, and that the color development is very slight if the steps (1) and (2) are reversed. This is because, after the steps are exchanged, the treating agent hardly enters the interior of the aramid fiber, and even if the dimethyl sulfoxide treatment is further performed, the content of the treating agent in the aramid fiber cannot be increased.
Comparative example 6 the results show that the organic solvent in step (1) of the process of the present invention also allows for the development of color in the aramid, but the color depth of the colored aramid is far less than that of dimethyl sulfoxide.
The results of comparative example 7 show that when the temperature of dimethyl sulfoxide treatment of aramid fiber in step (1) of the process of the present invention is as low as 20 ℃, the color development effect is poor because dimethyl sulfoxide does not swell aramid fiber well at low temperature, resulting in failure to obtain enough treating agent on aramid fiber in step (2) and resulting in light color development.
Comparative example 8 the results show that when the temperature of the dimethyl sulfoxide treated aramid fiber in step (1) of the method of the present invention is as high as 80 ℃, the color development effect equivalent to that of example 1 can be obtained. But in order to save energy and reduce emission, the treatment temperature is preferably 55 ℃.
The results of comparative example 9 show that when the dimethyl sulfoxide treatment time of the aramid fiber in step (1) of the method of the present invention is as short as 0.5h, the color development effect is poor because, when the time is not enough, the dimethyl sulfoxide cannot fully swell the aramid fiber, so that sufficient treatment agent cannot be obtained on the aramid fiber in step (2), and the color development is light.
Comparative example 10 the results show that when the dimethyl sulfoxide treatment time of the aramid fiber in step (1) of the method of the present invention is extended to 6 hours, the color development effect equivalent to that of example 1 can be obtained. However, in order to save energy and reduce emission, the preferred soaking time of the invention is 3 h.
The results of comparative examples 11 and 12 show that when the treating agent structure in step (2) of the present invention does not contain a bisaziridine structure, although the aramid fabric can also obtain a certain color, the color floats on the surface of the fabric, and completely falls off under the treatment of N, N-dimethylformamide, and the colored fabric is also not resistant to soaping, rubbing, sublimation, and has extremely low various color fastness.
The results of comparative example 13 show that when the baking temperature in step (2) of the present invention is 150 ℃, the aramid fiber has lighter color yield and more floating color, the fixation rate is significantly reduced, and the color fastness is also significantly lower, because when the temperature is insufficient, the treating agent does not completely react with the fiber, resulting in more final floating color.
Comparative example 14 the results show that when the baking temperature in step (2) of the present invention is increased to 220 c, a color developing effect comparable to that of example 1 can be obtained. But in order to save energy and reduce emission, the baking temperature is preferably 180 ℃.
The results of comparative example 15 show that when the baking time in step (2) of the present invention is shortened to 0.5h, the aramid fiber has lighter color and more floating color, the fixation rate is significantly reduced, and the color fastness is also significantly lower, because the treating agent does not completely react with the fiber when the baking time is insufficient, resulting in more final floating color.
Comparative example 16 the results show that when the baking time in step (2) of the present invention is extended to 2 hours, the color developing effect comparable to that of example 1 can be obtained. But in order to save energy and reduce emission, the preferred baking time of the invention is 1 h.
Comparative example 17: example 1, step (2), wherein compound 3(40mg) was replaced with compound 8(40mg) and no procedure in step (3) was performed, was otherwise as in example 1, wherein compound 8 has the structure:
comparative example 17 effect: since the compound 8 is red, red aramid fiber can be obtained, and a K/S value curve of the red aramid fiber is shown in FIG. 10. Fig. 10 is significantly different from fig. 7 (i.e., the aramid K/S value curve obtained in example 1). The main performance is as follows: fig. 7 shows a high absorption value near 400nm, while the absorption value at the corresponding position in fig. 10 is very low, i.e. the aramid fibers obtained by the method of the invention have obviously different colors.
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 (9)
1. The treating agent used in the meta-aramid color development method is characterized in that the structural general formula of the treating agent is as follows:
R 1 is a hydrogen atom, R 2 Optionally selected from hydrogen atom or cyano group.
2. The treating agent according to claim 1, characterized in that the treating agent is:
3. a method for developing a color of a meta-aramid fiber using the treating agent according to claim 1 or 2, comprising the steps of:
(1) first pretreatment:
soaking the meta-aramid fabric in an organic solvent I, taking out, cleaning and drying;
(2) second pretreatment:
soaking the fabric obtained by the treatment in the step (1) in an organic solvent II containing a treating agent, taking out and airing the fabric, and baking the fabric;
(3) color development:
and (3) placing the fabric obtained by the treatment in the step (2) in an organic solvent III, adding a diazonium salt aqueous solution for color development, taking out, cleaning and drying.
4. The color development method for m-aramid as claimed in claim 3, characterized in that in the step (1):
the organic solvent I is N, N-dimethylformamide or dimethyl sulfoxide;
the soaking temperature is 20-80 ℃, and the soaking time is 0.5-6 h;
the cleaning method comprises washing with clear water at room temperature, and oven drying at 60 + -5 deg.C to constant weight.
5. The color development method for m-aramid as claimed in claim 4, characterized in that in the step (2):
the organic solvent II is: methanol, acetone, dichloromethane, tetrahydrofuran; the concentration of the treating agent in the organic solvent II containing the treating agent is 0.05-5 g/L;
the soaking temperature is 25 +/-5 ℃, and the soaking time is 1 +/-0.2 h;
the baking temperature is 150-200 ℃; the baking time is 0.5-2 h.
6. The color development method for m-aramid fiber according to any one of claims 3 to 5, characterized in that the diazonium salt in the step (3) is a product generated by diazotizing an aromatic compound containing primary amino group.
7. The color development method for m-aramid as claimed in claim 6, characterized in that:
the aromatic compound containing primary amino group is aniline, p-toluidine, p-anisidine, p-chloroaniline, p-nitroaniline, o-chloro-p-nitroaniline, 2, 6-dibromo-4-nitroaniline, p-cyanoaniline, 1-naphthylamine, 2-nitro-5-aminothiazole, 2-aminobenzothiazole and 3-amino-5-nitrobenzo [ d ] isothiazole.
8. The color development method for m-aramid as claimed in claim 7, characterized in that in the step (3):
the organic solvent III is methanol and N, N-dimethylformamide, and the dosage of the organic solvent III is to completely immerse the fabric;
0.01-1 mmol of diazonium salt is used for every gram of fabric;
the color development temperature is 0-5 ℃; the color development time is 0.5 plus or minus 0.1 h;
the cleaning method comprises the following steps: washing with water, then soaping and finally washing with water; the drying is carried out at 60 +/-5 ℃ until the weight is constant.
9. The color development method for m-aramid fiber according to any one of claims 3 to 7, characterized in that: the following treatment process is added between the step (2) and the step (3):
cleaning the fabric obtained by the treatment in the step (2) by using N, N-dimethylformamide, and then washing with water; drying;
and (4) carrying out the subsequent step (3) on the dried fabric.
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| CN116876243A (en) * | 2023-07-09 | 2023-10-13 | 浙江理工大学 | Modified dyeing method of cotton fabric and modifier used in same |
| CN117402507A (en) * | 2023-09-22 | 2024-01-16 | 浙江理工大学 | Dyeing method for terylene and reactive dye containing two diazo groups |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115976677A (en) * | 2022-12-07 | 2023-04-18 | 浙江桐昆新材料研究院有限公司 | Method for preparing colored meta-aramid by adopting reactive stock solution coloring technology |
| CN115976677B (en) * | 2022-12-07 | 2023-12-22 | 浙江桐昆新材料研究院有限公司 | Method for preparing colored meta-aramid fiber by adopting reactive stock solution coloring technology |
| CN116876243A (en) * | 2023-07-09 | 2023-10-13 | 浙江理工大学 | Modified dyeing method of cotton fabric and modifier used in same |
| CN117402507A (en) * | 2023-09-22 | 2024-01-16 | 浙江理工大学 | Dyeing method for terylene and reactive dye containing two diazo groups |
| CN117402507B (en) * | 2023-09-22 | 2024-03-26 | 浙江理工大学 | Dyeing method for terylene and reactive dye containing two diazo groups |
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