CN111019386B - Anthraquinone structure carboxylic acid type dye for dyeing alginate fibers, and preparation method and dyeing process thereof - Google Patents

Anthraquinone structure carboxylic acid type dye for dyeing alginate fibers, and preparation method and dyeing process thereof Download PDF

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CN111019386B
CN111019386B CN201911305518.5A CN201911305518A CN111019386B CN 111019386 B CN111019386 B CN 111019386B CN 201911305518 A CN201911305518 A CN 201911305518A CN 111019386 B CN111019386 B CN 111019386B
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dyeing
dye
carboxylic acid
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alginate
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CN111019386A (en
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黄昊飞
李赵义
张琪
孟华杰
姜兆辉
秦浩然
肖鹏业
李玉超
左村村
傅忠君
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Shandong University of Technology
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/39—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using acid dyes
    • D06P1/40—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using acid dyes using acid dyes without azo groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/02—Formation of carboxyl groups in compounds containing amino groups, e.g. by oxidation of amino alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
    • C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
    • C07C227/20—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters by hydrolysis of N-acylated amino-acids or derivatives thereof, e.g. hydrolysis of carbamates
    • 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
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/16—Amino-anthraquinones
    • C09B1/20—Preparation from starting materials already containing the anthracene nucleus
    • C09B1/26—Dyes with amino groups substituted by hydrocarbon radicals
    • 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

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Abstract

The invention relates to the technical field of carboxylic acid type dyes, in particular to an anthraquinone structure carboxylic acid type dye for dyeing alginate fibers, and a preparation method and a dyeing process thereof. The anthraquinone structure carboxylic acid type dye passes through Ca in alginate fiber2+Forming complex bond with fiber to realize the aim of dyeing alginate fiber with carboxylic acid dye. The anthraquinone structure carboxylic acid type dye has no macromolecular skeleton, small molecular weight and simple structure, and is easier to permeate into fibers; in addition, other metal ions for enhancing complex bonds are not required to be additionally added in the dyeing process, so that the loss of the strength of the alginate fibers can be avoided. The fiber dyed by the invention has uniform color and bright color, and can completely meet the requirements of dyeing and processing of the alginate fiber. In addition, the dyeing process is simple and convenient, the conditions are mild, the traditional dyeing equipment is adopted, and the industrial prospect is wide.

Description

Anthraquinone structure carboxylic acid type dye for dyeing alginate fibers, and preparation method and dyeing process thereof
Technical Field
The invention relates to the technical field of carboxylic acid type dyes, in particular to an anthraquinone structure carboxylic acid type dye for dyeing alginate fibers, and a preparation method and a dyeing process thereof.
Background
The alginate fiber is a novel biomass fiber, and the raw material is from brown algae. It is prepared by extracting sodium alginate from natural seaweed and then carrying out wet spinning technology. The fiber not only has the characteristics of moisture absorption, heat preservation, softness, biocompatibility and the like of natural fiber, but also has excellent flame retardant, antibacterial and electromagnetic shielding properties, so the fiber has a great application prospect in the field of clothing textile.
Since the invention of 1944, the alginate fiber is mainly applied to the medical fields of medical dressings, band-aids, bandages, masks and the like. Because the seaweed fiber can not be deeply dyed, the seaweed fiber is not applied to the field of clothing textile on a large scale. The calcium alginate fiber has ion exchange performance, so that the calcium alginate fiber cannot be dyed in a solution containing inorganic salt such as sodium salt, or Ca in the fiber2+Is easy to be covered by Na+Instead, a hydrogel state is formed. In the using process of the traditional dye, a large amount of inorganic salt is generally required to be added for accelerating dyeing, so that the traditional dye is difficult to dye fibers. Because the alginate fiber has great application potential in the field of clothing textile, the problem of dyeing is solved, and the alginate fiber is the key for developing the clothing market of alginate fiber.
The existing dyeing methods for alginate fibers can be basically divided into five types, namely stock solution coloring, fiber modification, direct dyeing by adopting the existing reactive dyes, dyeing by adopting dyes containing polyamine type skeleton structures and dyeing by adopting macromolecular dyes containing carboxyl groups.
The first type is a method of coloring with a dope. Chinese patent CN104264280A discloses a method for coloring alginate fiber stock solution by adopting lake dye, which comprises the steps of adding sodium alginate into deionized water, stirring to fully dissolve the sodium alginate, preparing alginate fiber spinning stock solution, then adding lake dye into the alginate fiber spinning stock solution, stirring and mixing uniformly, filtering and defoaming to prepare the lake dye coloring alginate fiber spinning solution, and further preparing the alginate fiber colored by the lake dye. Wangping et al (Wangping, Zhangiping, Tiananli, et al. influence of fluorescent pigment on alginate fiber spinning solution and its film properties [ J ] textile science 2015,36(5):48-53.) alginate fiber stock solution was colored with fluorescent pigment, and its film forming properties were studied.
The second is a method of fiber modification. Chinese patent CN101736440A discloses a method for manufacturing dyeable alginate fiber, which comprises the steps of adding a water-soluble dendritic macromolecular compound into alginate fiber spinning solution, adopting wet spinning equipment and process, and carrying out solidification, drafting, washing and post-treatment to obtain the alginate fiber with good dyeing property.
The third type is that the existing active dye is adopted to directly dye the alginate fiber. Chinese patent CN101413207A discloses a dyeing and finishing process for alginate fiber fabric, which introduces a traditional dyeing process directly using reactive dyes, and realizes the coloring of alginate fibers through the accelerating and fixing effects of sodium sulfate and soda ash. And (4) carrying out hole transportation and the like (hole transportation, cinnabar, Donghong, and the like. calcium alginate fiber reactive dyeing process [ J ] dyeing and printing, 2013,39(8):22-24.) by using calcium chloride to replace the traditional sodium sulfate as a dyeing accelerant for dyeing alginate fibers, dyeing the alginate fibers and avoiding the damage of sodium ions to the alginate fibers. Lufang soldiers and the like (Lufang soldiers, Suihexin, cinnabar, and the like. alginic acid fiber reactive dye rare earth dyeing [ J ] printing and dyeing, 2009,35(24):11-14.) adopt cerium nitrate to replace sodium sulfate, and various types of reactive dyes are adopted to finish dyeing alginic acid fibers. Chinese patent CN103981744A discloses a salt-free dyeing process for calcium alginate fibers, which comprises the steps of firstly adopting an aluminum sulfate aqueous solution to carry out pretreatment on the calcium alginate fibers, then adopting direct dye to carry out salt-free dyeing, and finally adopting a calcium chloride aqueous solution to carry out color fixation treatment, thereby achieving the effect of dyeing the calcium alginate fibers.
The fourth type is that the seaweed fiber is dyed by adopting the dye containing polyamine skeleton structure. Chinese patent CN105332291A discloses a dyeing method of calcium alginate fiber, which mainly utilizes dye containing polyethylene polyamine skeleton structure to make the dye carry cationic charge in dye bath with certain pH value, thereby realizing that the dye and calcium alginate fiber with negative charge are adsorbed and fixed by ionic bond combination. The research on the novel dye for the alginate fibers [ J ] wool spinning technology, 2017,45, 8, 40-43.) adopts the polyamine dye to carry out dyeing experiments on the calcium alginate fibers, and reports the corresponding dyeing process in the research.
The fifth type is that macromolecular dye containing carboxyl groups is adopted to dye the alginate fibers. Chinese patent CN108342912A discloses a method for dyeing alginate fibers with polycarboxylic acid type dyes, which requires adding different kinds of metal ions during the dyeing process, and uses the metal ions as a connector, and the metal ions, the alginate fibers and polycarboxylic acid type macromolecular dyes can form complex bonds, so as to dye the alginate fibers with polycarboxylic acid type dyes. Chinese patent CN108396563A discloses a process for pad dyeing of alginate fiber/cotton fiber blended fabric by polycarboxylic acid type macromolecular dye, wherein the polycarboxylic acid type macromolecular dye dyes the cotton fiber through ester bonds formed between the polycarboxylic acid type macromolecular dye and the cotton fiber, and the polycarboxylic acid type macromolecular dye dyes the alginate fiber through complex bonds formed by metal ions and the alginate fiber, so that the polycarboxylic acid type macromolecular dye dyes the alginate fiber/cotton fiber blended fabric.
The method makes a powerful contribution to the dyeing and finishing process of the alginate fibers, but has defects in the actual application process. The available dyes have large molecular weight and few varieties, the bonding between the dyes and the fibers is not firm, the dyeing process is complicated, and the like, which still hinders the development of the alginate fibers in the field of clothes. Therefore, the efficient dyeing technology of alginate fiber is still a research hotspot and difficulty.
Disclosure of Invention
The invention aims to provide an anthraquinone structure carboxylic acid type dye for dyeing alginate fibers, which has the advantages of small molecular weight, high dye uptake and good color fastness; the invention also provides a preparation method and a dyeing process of the dye.
The invention relates to anthraquinone structure carboxylic acid type dye for dyeing alginate fibers, which has a structural formula as follows:
Figure BDA0002322962130000031
wherein R is1Is CH2COOH or CH2CH2COOH；
R2Is CH2COOH or CH2CH2COOH, and R2And R1The same;
R3is H, CH3Cl, Br or CN;
R4is H, Cl, Br or CH3；
R5Is H, NO2、CH3Cl, Br or CN.
The preparation method of the anthraquinone structure carboxylic acid type dye for dyeing the alginate fibers comprises the following steps:
(1) mixing the amino-containing anthraquinone dye intermediate, halogenated carboxylic ester, a catalyst and a solvent, and heating and refluxing to react to obtain the ester-containing anthraquinone dye intermediate;
(2) adding ethanol and NaOH into the intermediate containing ester group anthraquinone dye to carry out hydrolysis reaction, and then separating out solid by hydrochloric acid to obtain the anthraquinone structure carboxylic acid dye for dyeing the alginate fibers.
Wherein:
in the step (1), the halogenated carboxylic ester is ethyl bromoacetate, methyl bromoacetate or ethyl 3-bromopropionate; the dosage of ethyl bromoacetate is 50-100mmol based on 10mmol of amino-containing anthraquinone dye intermediate.
In the step (1), the catalyst is potassium iodide and N, N-diisopropylethylamine; wherein the molar dosage of the potassium iodide is 5-10% of that of the amino-containing anthraquinone dye intermediate, and the molar dosage of the N, N-diisopropylethylamine is 10-15% of that of the amino-containing anthraquinone dye intermediate.
In the step (1), the solvent is acetonitrile, and the dosage of the solvent is 60-100mL based on 10mmol of amino-containing anthraquinone dye intermediate; the reaction time at reflux is 18 to 24 hours, preferably 24 hours.
In the step (1), obtaining a dark brown solution after reflux reaction, carrying out rotary evaporation on acetonitrile, adding distilled water into the product, extracting the product for multiple times by using dichloromethane, taking an organic phase, and carrying out rotary evaporation to collect the product to obtain the intermediate of the anthraquinone dye containing ester groups.
In the step (2), based on 10mmol of amino-containing anthraquinone dye intermediate, the dosage of ethanol is 60-100mL, the dosage of NaOH is 50-70mmol, preferably 60mmol, and the concentration of hydrochloric acid is 3-6mol/L, preferably 6 mol/L; the time for the hydrolysis reaction is 12 to 18 hours, preferably 18 hours.
And (2) after the reaction is finished, performing rotary evaporation on ethanol, dissolving the product in distilled water, filtering, extracting with dichloromethane for multiple times, taking a water phase, and separating out a solid by using hydrochloric acid to obtain the anthraquinone structure carboxylic acid type dye for dyeing the alginate fibers.
The dyeing process of anthraquinone structure carboxylic acid type dye for dyeing alginate fiber uses Ca in alginate fiber2+Is a linker, passing Ca2+Can form complex bonds with alginate fibers and anthraquinone structure carboxylic acid dyes, and realize the dye-uptake of the alginate fibers by the anthraquinone structure carboxylic acid dyes for dyeing the alginate fibers.
The specific dyeing process comprises the following steps: dissolving anthraquinone structure carboxylic acid type dye in water, adjusting pH value to obtain dye solution, adding alginate fiber into the dye solution for dyeing, soap boiling, water washing and air drying.
Wherein:
the mass ratio of anthraquinone structure carboxylic acid type dye to alginate fiber for dyeing alginate fiber is 1-8: 100;
the mass ratio of the water to the alginate fibers is 10-50: 1;
and regulating the pH value to 3-8 by using a pH value regulator, wherein the pH value regulator is a hydrochloric acid solution or an ammonia water solution.
Dyeing temperature is 30-90 ℃, and dyeing time is 30-90 min;
soap boiling 1-4 ‰ neutral soap liquid at 90-95 deg.C for 10-15 min.
Compared with the existing polycarboxylic acid type macromolecular dye for dyeing the alginate fibers, the anthraquinone structure carboxylic acid type dye for dyeing the alginate fibers has larger performance improvement and change of the dyeing principle in the following aspects:
(1) the anthraquinone structure carboxylic acid type dye has a dicarboxylic acid group and a tertiary amine group, lone pair electrons in the tertiary amine group can promote the dicarboxylic acid group, and the activity of the dicarboxylic acid group is enhanced, so that the anthraquinone structure carboxylic acid type dye can act together with the dicarboxylic acid group to realize the complexing effect with calcium ions in the alginate fibers; and the polycarboxylic acid type macromolecular dye only depends on the complexation of the carboxylic acid groups on the macromolecular chains and metal ions additionally added into the alginate fibers.
(2) The space distance and the existing state between two carboxyl groups in the anthraquinone structure carboxylic acid type dye are greatly different from the space distance of the carboxylic acid groups of the polymaleic anhydride in the polycarboxylic acid type macromolecular dye, and the reduction of the space distance ensures that the two carboxyl groups are completely involved in complexation when the anthraquinone structure carboxylic acid type dye is complexed with ions in alginate fibers, so that the complex capacity is strong, and the permeability and the solubility are high; and only a small amount of carboxyl in the polymaleic anhydride can participate in complexation, and the complexation capability is poor, so that other metal ions need to be additionally added to participate in the reaction in the dyeing process.
(3) The dicarboxylic acid group is directly introduced into the dye parent, so that the dye and the fiber are directly combined, the polycarboxylic acid type macromolecular dye is obtained by grafting the dye parent onto a polymaleic anhydride macromolecular chain, the dye parent is not directly combined with the fiber, but the polymaleic anhydride macromolecular chain is used as a bridge group, and the dye and the fiber are indirectly combined.
The invention has the following beneficial effects:
the anthraquinone structure carboxylic acid type dye for dyeing the alginate fibers realizes the formation of a plurality of complex bonds with calcium ions in the alginate fibers by utilizing the combined action of dicarboxylic acid groups and tertiary amine groups, so that the dye can be firmly combined with the alginate fibers; the molecular structure of the anthraquinone structure carboxylic acid type dye for dyeing the alginate fibers is small, so that the permeability and the level dyeing performance of the dye in the fibers are obviously improved; the dicarboxylic acid structure contained in the anthraquinone structure carboxylic acid type dye structure for dyeing the alginate fibers ensures that the dye has good water solubility, the dye liquor is simple to prepare, and the concentration of the dye liquor is obviously improved, thereby being beneficial to improving the dyeing depth and the dye uptake of the dye.
The anthraquinone structure carboxylic acid type dye is characterized in that a dicarboxylic acid structure is directly introduced into a dye matrix, and compared with a polycarboxylic acid type macromolecular dye containing a macromolecular chain segment, the molecular weight and the space volume of the dye are obviously reduced, so that the water solubility and the permeability of the dye are effectively improved, and the steps and the cost for synthesizing the dye are greatly reduced.
In addition, Ca inside the alginate fibers2+Ca is bonded with hydroxyl and carboxyl in alginate fiber in the form of complex bond2+Then forms a complex bond with carboxyl in the carboxylic acid type dye with the anthraquinone structure through Ca2+The anthraquinone structure carboxylic acid type dye is used as a connector to dye the alginate fibers. Due to the strong complexing ability and high permeability and solubility of calcium ions in the anthraquinone structure carboxylic acid type dye and the alginate fibers, other metal ions are not required to be additionally added in the dyeing process of the dye to improve the binding force of the dye and the alginate fibers, so that the dyeing steps and cost are greatly simplified, the problems of color light change, strong damage and hand feeling change of the fibers caused by the addition of various metal ions are effectively avoided, and the original structure, hand feeling and various performances of the alginate fibers are well reserved.
The dyed alginate fiber has high dye uptake, small strength loss, uniform color and bright color, and can completely meet the requirements of industrial application of the alginate fiber. Meanwhile, the dyeing process is simple, the conditions are mild, and the process is similar to the traditional dyeing process, so that the equipment does not need to be updated on a large scale, and the production cost is effectively saved.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a carboxylic acid type dye of anthraquinone structure for dyeing the alginate fiber prepared in example 1;
FIG. 2 is a nuclear magnetic resonance carbon spectrum of a carboxylic acid type dye having an anthraquinone structure for dyeing the alginate fiber prepared in example 1.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
(1) Synthesis of intermediate of ester group-containing anthraquinone dye
2.23g (10mmol) of 2-aminoanthraquinone, 11.1mL (16.7g, 100mmol) of ethyl bromoacetate, 0.10g (0.6mmol) of potassium iodide and 0.142g (1.1mmol) of N, N-diisopropylethylamine are respectively weighed and put into a three-neck flask, 80mL of acetonitrile is added, heating and stirring are carried out, reflux reaction is carried out for 24 hours, dark brown solution is obtained, acetonitrile is evaporated in a rotary manner, distilled water is added, extraction is carried out for a plurality of times by using dichloromethane, an organic phase is taken, and the product is collected by rotary evaporation, so as to obtain the intermediate of the anthraquinone dye containing ester.
The reaction equation is as follows:
Figure BDA0002322962130000051
(2) synthesis of anthraquinone structure carboxylic acid type dye for dyeing alginate fibers
Adding 80mL of ethanol and 2.4g (60mmol) of NaOH into the intermediate containing ester group anthraquinone dye collected in the step (1), carrying out reflux reaction for 18h, carrying out rotary evaporation of the ethanol after the reflux is finished, dissolving the product in 50mL of distilled water, filtering, extracting with dichloromethane for three times, taking a water phase, and precipitating a solid by using 6mol/L hydrochloric acid to obtain the anthraquinone structure carboxylic acid type dye for dyeing the alginate fibers.
The reaction equation is as follows:
Figure BDA0002322962130000061
the structural formula of the anthraquinone structure carboxylic acid type dye for dyeing the alginate fibers is as follows:
Figure BDA0002322962130000062
the nuclear magnetic resonance hydrogen spectrum is shown in figure 1,1H NMR(400MHz,D2O)δ7.53(d,J＝8.6Hz,1H),7.42(s,1H),7.35(s,1H),7.21(s,2H),6.79(s,1H),6.64(d,J＝8.3Hz,1H),3.97(s,4H)。
the nuclear magnetic resonance carbon spectrum is shown in figure 2,13C NMR(101MHz,D2O)δ184.53,182.08,177.33,153.27,134.54,133.90,133.61,132.45,131.87,129.61,126.26,126.01,120.80,116.08,108.48,55.55。
the alginate fibers were dyed with the anthraquinone structure carboxylic acid type dye obtained in example 1, and the dyeing process and the dye uptake test process were as follows:
dissolving 0.1g of anthraquinone structure carboxylic acid type dye in 100mL of water, adjusting the pH value to 6 by using 1 wt.% of ammonia water solution to obtain a dye solution, adding 0.5g of pretreated alginate fiber into 10mL of dye solution, dyeing for 60min at 50 ℃, taking out the alginate fiber after dyeing, soaking the alginate fiber in 4 per mill of neutral soap solution, soaping for 10min at 95 ℃, fully washing the alginate fiber with water, and drying in the air. And (3) taking the equivalent amount of the soap cooking liquor before dyeing and the equivalent amount of the soap cooking liquor residual liquid after dyeing, fixedly accommodating the soap cooking liquor and the soap cooking liquor residual liquid in a 250mL volumetric flask, measuring absorbance at the maximum absorption wavelength of the dye by using an ultraviolet-visible spectrophotometer, and calculating the dye uptake of the dye by using the Lambert-beer law.
Example 2
(1) Synthesis of intermediate of ester group-containing anthraquinone dye
Respectively weighing 2.51g (10mmol) of 2-amino-4, 8-dimethylanthraquinone, 8.87mL (13.36g, 80mmol) of ethyl bromoacetate, 0.133g (0.8mmol) of potassium iodide and 0.168g (1.3mmol) of N, N-diisopropylethylamine in a three-neck flask, adding 60mL of acetonitrile, heating and stirring, carrying out reflux reaction for 18h to obtain a dark brown solution, carrying out rotary evaporation on the acetonitrile, adding distilled water, carrying out multiple extraction with dichloromethane, taking an organic phase, and carrying out rotary evaporation on the collected product to obtain the intermediate containing the ester group anthraquinone dye.
The reaction equation is as follows:
Figure BDA0002322962130000071
(2) synthesis of anthraquinone structure carboxylic acid type dye for dyeing alginate fibers
Adding 60mL of ethanol and 2.0g (50mmol) of NaOH into the intermediate containing ester-group anthraquinone dye collected in the step (1), carrying out reflux reaction for 15h, carrying out rotary evaporation on the ethanol after the reflux is finished, dissolving the product in 50mL of distilled water, filtering, extracting with dichloromethane for three times, taking a water phase, and precipitating a solid by using 4mol/L hydrochloric acid to obtain the anthraquinone structure carboxylic acid type dye for dyeing the alginate fibers.
The reaction equation is as follows:
Figure BDA0002322962130000072
the structural formula of the anthraquinone structure carboxylic acid type dye for dyeing the alginate fibers is as follows:
Figure BDA0002322962130000073
the alginate fibers were dyed with the anthraquinone structure carboxylic acid type dye obtained in example 2, and the dyeing process and the dye uptake test process were as follows:
dissolving 0.1g of anthraquinone structure carboxylic acid type dye in 100mL of water, adjusting the pH value to 4 by using 1 wt.% of ammonia water solution to obtain a dye solution, adding 0.5g of pretreated alginate fiber into 10mL of dye solution, dyeing for 90min at 35 ℃, taking out the alginate fiber after dyeing, soaking the alginate fiber in 4 per mill of neutral soap solution, soaping for 12min at 93 ℃, fully washing the alginate fiber with water, and drying in the air. And (3) taking the equivalent amount of the soap cooking liquor before dyeing and the equivalent amount of the soap cooking liquor residual liquid after dyeing, fixedly accommodating the soap cooking liquor and the soap cooking liquor residual liquid in a 250mL volumetric flask, measuring absorbance at the maximum absorption wavelength of the dye by using an ultraviolet-visible spectrophotometer, and calculating the dye uptake of the dye by using the Lambert-beer law.
Example 3
(1) Synthesis of intermediate of ester group-containing anthraquinone dye
2.23g (10mmol) of 2-aminoanthraquinone, 12.8mL (18.1g, 100mmol) of ethyl 3-bromopropionate, 0.166g (1mmol) of potassium iodide and 0.194g (1.5mmol) of N, N-diisopropylethylamine are respectively weighed and put into a three-neck flask, 100mL of acetonitrile is added, heating and stirring are carried out, reflux reaction is carried out for 20 hours, dark brown solution is obtained, acetonitrile is evaporated in a rotary manner, distilled water is added, extraction is carried out for a plurality of times by using dichloromethane, an organic phase is taken, and the product is collected by rotary evaporation, so as to obtain the intermediate of the anthraquinone dye containing ester.
The reaction equation is as follows:
Figure BDA0002322962130000081
(2) synthesis of anthraquinone structure carboxylic acid type dye for dyeing alginate fibers
Adding 100mL of ethanol and 2.8g (70mmol) of NaOH into the intermediate containing ester group anthraquinone dye collected in the step (1), carrying out reflux reaction for 12h, carrying out rotary evaporation of the ethanol after the reflux is finished, dissolving the product in 50mL of distilled water, filtering, extracting with dichloromethane for three times, taking a water phase, and precipitating a solid by using 5mol/L hydrochloric acid to obtain the anthraquinone structure carboxylic acid type dye for dyeing the alginate fibers.
The reaction equation is as follows:
Figure BDA0002322962130000082
the structural formula of the anthraquinone structure carboxylic acid type dye for dyeing the alginate fibers is as follows:
Figure BDA0002322962130000083
the alginate fibers were dyed with the anthraquinone structure carboxylic acid type dye obtained in example 3, and the dyeing process and the dye uptake test process were as follows:
dissolving 0.1g of anthraquinone structure carboxylic acid type dye in 100mL of water, adjusting the pH value to 8 by using 1 wt.% hydrochloric acid solution to obtain a dye solution, adding 0.5g of pretreated alginate fiber into 10mL of dye solution, dyeing for 30min at 90 ℃, taking out the alginate fiber after dyeing, soaking the alginate fiber in 4 per mill of neutral soap solution, soaping for 15min at 90 ℃, fully washing the alginate fiber with water, and drying in the air. And (3) taking the equivalent amount of the soap cooking liquor before dyeing and the equivalent amount of the soap cooking liquor residual liquid after dyeing, fixedly accommodating the soap cooking liquor and the soap cooking liquor residual liquid in a 250mL volumetric flask, measuring absorbance at the maximum absorption wavelength of the dye by using an ultraviolet-visible spectrophotometer, and calculating the dye uptake of the dye by using the Lambert-beer law.
Comparative example 1
Example 1 in patent CN108342912A was taken as comparative example 1.
Comparative example 2
Example 1 in patent CN105332291A was taken as comparative example 2.
The dye obtained in examples 1-3 and comparative examples 1-2 was used to dye alginate fibers, and the dye uptake, strength and soaping fastness were measured, and the undyed alginate fibers were used to measure strength. The strength performance after dyeing is determined by reference to GB/T14337-2008; the soaping fastness is determined according to GB/T3921-2008; the dye uptake is measured by the spectrophotometer for the absorbance values of the dye solution before and after dyeing, and is calculated by using the Lambert-beer law. The data of the specific measurement are shown in Table 1.
TABLE 1 Performance data Table
Examples Breaking strength Rate of change of strength Dye uptake Fastness to soaping
Example 1 3.79cN/dtex Increase by 5.3 percent 96％ 4 stage
Example 2 3.52cN/dtex The reduction is 2.2 percent 90％ Grade 3-4
Example 3 3.66cN/dtex Increase by 1.7 percent 92％ 4 stage
Comparative example 1 3.48cN/dtex The reduction is 3.3 percent 81％ 4 stage
Comparative example 2 3.35cN/dtex The reduction is 6.9 percent 81％ Grade 3-4
Undyed alginate fibres 3.60cN/dtex —— —— ——
As is apparent from Table 1, the dye uptake of examples 1 to 3 was larger than that of comparative example 1, and the fiber strength loss was smaller than that of comparative example 1. Although the carboxylic acid type dyes of examples 1 to 3 and comparative example 1 were adsorbed and fixed to the alginate fibers by metal complex bonds, the carboxylic acid type dyes of anthraquinone structure of examples 1 to 3 and comparative exampleCompared with the polycarboxylic acid type macromolecular dye in the 1, the polycarboxylic acid type macromolecular dye has simpler structure and smaller molecular weight, the smaller molecular weight can enable the dye to be more easily adsorbed and permeated in the alginate fiber, and the dye with more quantity can also be combined with the alginate fiber through metal complex bonds; in addition, the macromolecular carboxylic acid type dye in the comparative example 1 needs to add extra metal ions to enhance the combination of complex bonds during dyeing, while the anthraquinone structure carboxylic acid type dye in the examples 1 to 3 does not need to add extra metal ions, and the dye can be directly combined with Ca inside the alginate fibers2+Form firmer complex bond, avoid the loss of the strength performance of the alginate fiber. Thus, the dye uptake was higher in examples 1-3, and the breaking strength loss was smaller or even higher.
As is apparent from Table 1, examples 1 to 3 all had higher dye uptake than comparative example 2 and lower breaking strength loss than comparative example 2. This is because the dyes in examples 1 to 3 are anthraquinone structure carboxylic acid type dyes, and are bonded to the alginate fibers by the form of metal complex bonds; while the dye in comparative example 2 is a polyamine type dye, ionically bonded to the alginate fiber. The strength of the complex bond is higher than that of the ionic bond. The dye and alginate fiber are combined more firmly through the complex bond, so that the dye uptake is higher, and the breaking strength loss is smaller and even improved in the examples 1 to 3.

Claims (10)

1. An anthraquinone structure carboxylic acid type dye for dyeing alginate fibers is characterized in that the structural formula is as follows:
Figure 956051DEST_PATH_IMAGE001
wherein R is1Is CH2COOH or CH2CH2COOH；
R2Is CH2COOH or CH2CH2COOH, and R2And R1The same;
R3is H, CH3Cl, Br or CN;
R4is H, Cl, Br or CH3；
R5Is H, NO2、CH3Cl, Br or CN.
2. A method for preparing carboxylic acid type dye with anthraquinone structure for dyeing alginate fiber according to claim 1, characterized by comprising the following steps:
(1) mixing the amino-containing anthraquinone dye intermediate, halogenated carboxylic ester, a catalyst and a solvent, and heating and refluxing to react to obtain the ester-containing anthraquinone dye intermediate;
(2) adding ethanol and NaOH into the intermediate containing ester group anthraquinone dye to perform hydrolysis reaction, and then separating out solid by hydrochloric acid to obtain anthraquinone structure carboxylic acid dye for dyeing alginate fibers;
in the step (1), the halogenated carboxylic ester is ethyl bromoacetate, methyl bromoacetate or ethyl 3-bromopropionate; the catalyst is potassium iodide and N, N-diisopropylethylamine.
3. The method for preparing carboxylic acid type dye with anthraquinone structure for dyeing alginate fiber according to claim 2, characterized in that: in the step (1), the dosage of the halogenated carboxylic ester is 50-100mmol based on 10mmol of the amino-containing anthraquinone dye intermediate.
4. The method for preparing carboxylic acid type dye with anthraquinone structure for dyeing alginate fiber according to claim 2, characterized in that: in the step (1), in the catalyst, the molar amount of potassium iodide is 5-10% of that of the amino-containing anthraquinone dye intermediate, and the molar amount of N, N-diisopropylethylamine is 10-15% of that of the amino-containing anthraquinone dye intermediate.
5. The method for preparing carboxylic acid type dye with anthraquinone structure for dyeing alginate fiber according to claim 2, characterized in that: in the step (1), the solvent is acetonitrile, and the dosage of the solvent is 60-100mL based on 10mmol of amino-containing anthraquinone dye intermediate; the reaction time is 18-24 hours under reflux.
6. The method for preparing carboxylic acid type dye with anthraquinone structure for dyeing alginate fiber according to claim 2, characterized in that: in the step (2), the dosage of ethanol is 60-100mL, the dosage of NaOH is 50-70mmol and the concentration of hydrochloric acid is 3-6mol/L based on 10mmol of amino-containing anthraquinone dye intermediate; the time of the hydrolysis reaction is 12 to 18 hours.
7. A dyeing process of carboxylic acid type dye with anthraquinone structure for dyeing alginate fiber as claimed in claim 1, characterized in that: ca in alginate fiber2+Is a linker, passing Ca2+Can form complex bonds with alginate fibers and anthraquinone structure carboxylic acid dyes, and realize the dye-uptake of the alginate fibers by the anthraquinone structure carboxylic acid dyes for dyeing the alginate fibers.
8. The dyeing process of carboxylic acid type dye with anthraquinone structure for dyeing alginate fiber according to claim 7, characterized in that: dissolving anthraquinone structure carboxylic acid type dye in water, adjusting pH value to obtain dye solution, adding alginate fiber into the dye solution for dyeing, soap boiling, water washing and air drying.
9. The dyeing process of carboxylic acid type dye with anthraquinone structure for dyeing alginate fiber according to claim 8, characterized in that: the mass ratio of anthraquinone structure carboxylic acid type dye to alginate fiber for dyeing alginate fiber is 1-8: 100; the mass ratio of the water to the alginate fibers is 10-50: 1; and regulating the pH value to 3-8 by using a pH value regulator, wherein the pH value regulator is a hydrochloric acid solution or an ammonia water solution.
10. The dyeing process of carboxylic acid type dye with anthraquinone structure for dyeing alginate fiber according to claim 8, characterized in that: dyeing temperature is 30-90 ℃, and dyeing time is 30-90 min; soap boiling 1-4 ‰ neutral soap liquid at 90-95 deg.C for 10-15 min.
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