S-triazine type reactive dye, its modification method and application

Abstract

The application belongs to the technical field of dye preparation, and particularly relates to a s-triazine type reactive dye and a modification method and application thereof. The s-triazine type reactive dye modification method provided by the application is characterized by comprising the following steps: S1, mixing the s-triazine type reactive dye with an alkaline substance in the presence of an oil phase, and heating to obtain a modified s-triazine type reactive dye, wherein the oil phase is an aprotic polar solvent, and the alkaline substance comprises an organic base. The aprotic polar solvent is used as a solvent environment in the application, which can effectively dissolve the organic base and make the organic base exhibit nucleophilicity instead of alkalinity. Meanwhile, the amino group of the organic base is used to react with the s-triazine type reactive dye through a nucleophilic substitution reaction, so that the s-triazine type reactive dye is modified.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of dye preparation, and particularly relates to a s-triazine type reactive dye and a modification method and application thereof. BACKGROUND

[0002] Reactive dye is a new type of dye, and the industrial production of reactive dye originates from cellulose fiber. The reactive dye has bright color, complete color spectrum, excellent fastness, simple dyeing process, and low energy consumption, and has become the most widely used dye in the world. The dye molecule contains a reactive group that can react with fiber, and can form a covalent bond with fiber during dyeing to form a "dye-fiber" whole. The structure of the reactive dye molecule is generally W-D-B-Re, wherein W is a water-soluble group, such as -SO3Na; D is the parent structure or chromophore of the reactive dye; B is the connecting group between the parent structure and the active group of the reactive dye, also known as the bridge group, generally -NH-; Re is the active group of the reactive dye. The s-triazine type reactive dye occupies a very important position in various reactive dyes. The above-mentioned reactive dye is reactive, has good dyeing effect, but has poor stability, especially the X type reactive dye needs to be dyed at low temperature, has poor fixation, is easy to hydrolyze, and has serious color loss after washing.

[0003] The prior art discloses a preparation of a storage-stable reactive liquid dye, and a storage-stable reactive dye is prepared by nanofiltration desalination, but the fixation effect of the reactive dye is not improved. SUMMARY

[0004] Therefore, the technical problem to be solved by the present application is to overcome the poor fixation effect of the reactive dye in the prior art, so as to provide a s-triazine type reactive dye and a modification method and application thereof, improve the fixation capacity of the reactive dye, and avoid color loss after washing after dyeing.

[0005] In one aspect, the present application provides a modification method of a s-triazine type reactive dye, comprising the following steps:

[0006] S1, in the presence of an oil phase, mixing the s-triazine type reactive dye with an alkaline substance, heating to obtain a modified s-triazine type reactive dye, wherein the oil phase comprises an aprotic polar solvent, and the alkaline substance comprises an organic amine.

[0007] In one embodiment, the organic amine in step S1 comprises at least one of a binary amine and a ternary amine.

[0008] Optionally, the organic amine comprises at least one of a polyethylene glycol diamine, ethylenediamine, and diethylenetriamine.

[0009] In one embodiment, the oil phase comprises at least one of a fatty amide organic compound and an organic sulfur compound.

[0010] Optionally, the oil phase comprises at least one of N,N-dimethylformamide, N-methylpyrrolidone, N,N-dimethylpropyleneurea and dimethylsulfoxide.

[0011] In one embodiment, the mass ratio of the triazine type reactive dye to the basic substance is (3-5):(6-15).

[0012] In one embodiment, the mass ratio of the triazine type reactive dye to the oil phase is 1:(3-6) g:mL.

[0013] In one embodiment, the triazine type reactive dye comprises at least one of K type reactive dye, KD type reactive dye and X type reactive dye.

[0014] Optionally, the X type reactive dye comprises at least one of reactive yellow 86, reactive blue 4 or reactive red 11.

[0015] Optionally, the K type reactive dye comprises at least one of reactive turquoise blue K-GL and reactive dark blue K-R.

[0016] Optionally, the KD type reactive dye comprises at least one of reactive brilliant red KD-8B and reactive yellow KD-3G.

[0017] In one embodiment, the basic substance further comprises an inorganic base.

[0018] Optionally, the inorganic base comprises at least one of hydroxide and basic carbonate.

[0019] Preferably, the inorganic base comprises at least one of sodium hydroxide, potassium hydroxide and potassium carbonate.

[0020] Optionally, the mass ratio of the inorganic base to the organic amine in the basic substance is 1:(2-10).

[0021] In one embodiment, the stirring rate when the triazine type reactive dye is mixed with the basic substance is 300-500 rpm, and the stirring time is 1.5-5 h.

[0022] Optionally, the stirring time is 3-5 h.

[0023] In one embodiment, the heating temperature in step S1 is 95-110°C.

[0024] In one embodiment, the modification method further comprises S2, solid-liquid separation of the modified triazine type reactive dye, and drying to obtain a solid reactive dye.

[0025] The method for solid-liquid separation comprises the steps of reducing pressure distillation of the modified triazine type reactive dye to obtain a concentrate, and washing the concentrate,

[0026] Optionally, the step of washing comprises washing the precipitate with at least one of anhydrous ethanol or distilled water.

[0027] Optionally, the drying temperature is 40-60°C, and the drying time is 1-6h.

[0028] In another aspect, the present application provides a triazine type reactive dye prepared by the method for modifying the triazine type reactive dye, which can be applied to textile and microsphere dyeing.

[0029] In one embodiment, the triazine type reactive dye is applied to microsphere dyeing, which comprises the steps of mixing the modified triazine type reactive dye, a carboxyl microsphere solution and a condensing agent to obtain a mixed solution, adjusting the pH value of the mixed solution, and stirring to obtain a colored microsphere solution.

[0030] Optionally, the carboxyl microspheres can be commercially available or self-made, wherein the self-made carboxyl microspheres can be polyvinyl alcohol-acrylic acid salt polymers, and the commercially available carboxyl microspheres can be prepared from styrene and methacrylic acid.

[0031] Optionally, the carboxyl microsphere solution comprises a mixture of carboxyl microspheres and a solvent.

[0032] Optionally, the solvent comprises at least one of physiological saline and phosphate buffer.

[0033] Optionally, the volume concentration of the carboxyl microspheres in the carboxyl microsphere solution is 25-50%.

[0034] In one embodiment, the condensing agent comprises a carbodiimide condensing agent.

[0035] Optionally, the carbodiimide condensing agent comprises at least one of ethyl [3-(dimethylamino) propyl] carbodiimide hydrochloride, dicyclohexyl carbodiimide and diisopropyl carbodiimide.

[0036] In one embodiment, the volume ratio of the carboxyl microspheres to the mass of the modified triazine type reactive dye is 1:(1-6), with the unit of L:g.

[0037] In one embodiment, the mass ratio of the modified triazine type reactive dye to the condensing agent is 1:(1-10).

[0038] In one embodiment, the pH value of the mixed solution is adjusted to 8-12.

[0039] In one of the embodiments, the stirring time is 2-5 hours and the stirring temperature is 10-35℃.

[0040] In one of the embodiments, the spherulitic dyeing of the s-triazine type reactive dye also comprises a fixing step of the colored spherulitic liquid,

[0041] Optionally, the fixing step comprises heating the colored spherulitic liquid, solid-liquid separation, and washing to obtain fixed spherulites,

[0042] Optionally, the fixing step is repeated 2-5 times,

[0043] Optionally, the heating temperature is 100-110℃ and the heating time is 15-30 minutes,

[0044] Optionally, the solid-liquid separation is performed by sieving to obtain the colored spherulites,

[0045] Optionally, the sieving is performed by using a screen,

[0046] Optionally, the screen has a mesh size of 300-500 mesh.

[0047] Optionally, the washing step comprises mixing the colored spherulites after the solid-liquid separation with physiological saline and stirring at a speed of 100-500 rpm,

[0048] Optionally, the washing step is repeated 2-4 times in a single fixing step.

[0049] The technical scheme of the present application has the following advantages:

[0050] 1. The s-triazine type reactive dye modification method provided by the present application comprises the following steps: S1, in the presence of an oil phase, mixing the s-triazine type reactive dye with a basic substance and heating to obtain a modified s-triazine type reactive dye, wherein the oil phase is an aprotic polar solvent, and the basic substance comprises an organic amine. The present application uses an aprotic polar solvent as a solvent environment, which can effectively dissolve the organic amine and make the organic amine exhibit nucleophilicity rather than basicity. At the same time, the amino group of the organic amine reacts with the s-triazine type reactive dye through nucleophilic substitution, thereby modifying the reactive dye and improving the stability of the s-triazine type reactive dye and its fixing ability.

[0051] 2. The s-triazine type reactive dye modification method provided by the present application, wherein the organic amine is at least one of a di-amine and a tri-amine. The present application uses di-amine and tri-amine as the basic substance, which on one hand modifies the s-triazine type reactive dye through the amino group at one end of the di-amine and tri-amine, and on the other hand, the amino group at the other end of the di-amine and tri-amine is combined with the dyeing object, thereby firmly combining the reactive dye with the dyeing object and improving the fixing effect of the reactive dye.

[0052] 3. The s-triazine type reactive dye modification method provided by the present application, wherein the alkaline substance further comprises an inorganic base. The present application uses a combination of organic amine and inorganic base. The combination of organic amine and inorganic base can not only improve the yield of the dye, but also improve the activation degree of the dye and increase the dyeing effect of the dye.

[0053] 4. The s-triazine type reactive dye modification method provided by the present application, wherein the stirring time of the s-triazine type reactive dye mixed with the alkaline substance is 1.5-5 hours, and the stirring time is optionally 3-5 hours. The s-triazine type reactive dye modification method provided by the present application can improve the yield of the modified reactive dye.

[0054] 5. The s-triazine type reactive dye prepared by the s-triazine type reactive dye modification method provided by the present application, which can realize dyeing of carboxyl microspheres, comprising the following steps: dissolving the modified s-triazine type reactive dye in a solvent to obtain a dyeing solution, mixing the dyeing solution, a carboxyl microsphere solution and a condensing agent, adjusting the pH value of the mixed solution, and stirring to obtain a colored microsphere solution. The present application uses the modified s-triazine type reactive dye to dye the carboxyl microspheres. Under the action of the condensing agent, the amino group of the modified s-triazine type reactive dye is combined with the carboxyl group of the carboxyl microspheres, so that the modified s-triazine type reactive dye can be firmly combined with the carboxyl microspheres, the dyeing stability and the fixation rate are improved, and the problem of color fading of the carboxyl microspheres after washing can be avoided.

[0055] 6. The application of the s-triazine type reactive dye provided by the present application in microsphere dyeing, wherein the fixation step is repeated 2-5 times, which can improve the stability of the dyeing. When the fixation step is repeated 2 times, the dyeing provided by the present application can basically realize no color fading. The cleaning times in the fixation step are 2-4 times, which can better remove the unreacted dye. BRIEF DESCRIPTION OF DRAWINGS

[0056] In order to more clearly illustrate the specific embodiments of the present application or the technical solutions in the prior art, the drawings needed in the following specific embodiments or prior art description will be briefly introduced. Obviously, the drawings in the following description are some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative labor.

[0057] Figure 1 is a real object picture of the fixation microspheres prepared by application example 1 and preserved for 90 days, wherein a is the carboxyl microspheres dyed by the modified reactive dye prepared by example 1, b is the carboxyl microspheres dyed by the modified reactive dye prepared by example 7, c is the carboxyl microspheres dyed by the modified reactive dye prepared by example 8, and d is normal saline;

[0058] Figure 2: This is the ultraviolet absorption spectrum of each test solution in Experimental Example 2 of the present invention, where A is test solution 2, B is test solution 3, C is test solution 4, and D is test solution 1. DETAILED DESCRIPTION

[0059] The following examples are provided for a better understanding of the present invention and are not intended to limit the best mode of implementation. They do not limit the content and scope of protection of the present invention. Any product identical or similar to the present invention obtained by anyone under the guidance of the present invention or by combining the features of the present invention with other prior arts shall fall within the scope of protection of the present invention.

[0060] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in this field can be used. If the manufacturer of the reagents or instruments is not specified, they are all commercially available conventional reagents.

[0061] The present invention takes s-triazine type reactive dyes with reactive groups as research objects, including K type reactive dyes containing monochloro-s-triazine, KD type reactive dyes containing bis-monochloro-s-triazine structures, and X type reactive dyes containing dichloro-s-triazine structures. Taking K type reactive dyes as an example, ethylenediamine with double amino groups at the end is used to modify the K type reactive dyes in the presence of an oil phase. The modification reaction formula is shown in the following formula (I). It can be seen that ethylenediamine with double amino groups at the end can react with the reactive dye, wherein the amino group at one end of the ethylenediamine with double amino groups combines with the reactive dye, thereby achieving the modification of the reactive dye.

[0062]

[0063] It is a K-type reactive dye, in which R is -NH2, -NHCH3, -NHAr, -N(CH3)Ar, carbonyl group, etc.

[0064] Furthermore, in the present invention, in the presence of a carbon diamine condensing agent, the carboxyl microspheres are colored with a modified reactive dye. The coloring reaction is shown in formula (II). It can be seen that the other amino group of the double-terminal amino group-containing ethylenediamine that is not bound to the reactive dye can be combined with the carboxyl microspheres, thereby achieving firm coloring of the modified reactive dye on the carboxyl microspheres.

[0065]

[0066] In the application example of the present invention, the carboxyl microspheres are 300PS carboxyl microspheres were purchased from Suzhou Zhiyi Microsphere Technology Co., Ltd., composed of styrene and methacrylic acid, with a particle size of 300 μm.

[0067] Example 1

[0068] The embodiment provides a modification method of s-triazine type reactive dyes, and specific steps and methods are as follows.

[0069] (1) 5g of reactive yellow 86, 1.5g of sodium hydroxide and 8g of ethylenediamine were weighed and added into a three-necked flask, 20mL of N,N-dimethylformamide was added as an oil phase, the three-necked flask was heated to 95 DEG C in an oil bath, and stirring and dispersion were uniform; under the condition of uniform stirring at 400r / min, reaction was carried out for 5h. Since the reaction temperature is high, the three-necked flask is connected with a condenser during the reaction process, ice water is circulated to condense volatile matter backflow, and the reaction is carried out in a fume hood to ensure the safety of the experiment.

[0070] (2) After the reaction was completed, the three-necked flask was transferred to a water bath pot which was heated to 80 DEG C, a reduced pressure distillation device was connected, the reaction liquid was distilled to a solid paste, 20mL of distilled water was used to wash the paste-like reaction liquid from the three-necked flask into a glass beaker, after stirring and dissolving, 200mL of anhydrous ethanol was added to precipitate the product, filter residue was obtained, the filter residue was again alcohol precipitated with 200mL of anhydrous ethanol, and after the filter residue was again filtered, the product was dried at 50 DEG C for 4h, and a solid reactive dye was prepared.

[0071] The solid reactive dye prepared in the embodiment has a yield of 70.2%.

[0072] Example 2

[0073] The embodiment provides a modification method of s-triazine type reactive dyes, and specific steps and methods are as follows.

[0074] (1) 5g of reactive yellow 86, 4g of potassium carbonate and 10g of diethylenetriamine were weighed and added into a three-necked flask, 20mL of N-methylpyrrolidone was added as an oil phase, the three-necked flask was heated to 110 DEG C in an oil bath, and stirring and dispersion were uniform; under the condition of uniform stirring at 400r / min, reaction was carried out for 3h. Since the reaction temperature is high, the three-necked flask is connected with a condenser during the reaction process, ice water is circulated to condense volatile matter backflow, and the reaction is carried out in a fume hood to ensure the safety of the experiment.

[0075] (2) After the reaction was completed, the three-necked flask was transferred to a water bath pot which was heated to 80 DEG C, a reduced pressure distillation device was connected, the reaction liquid was distilled to a solid paste, 20mL of distilled water was used to wash the paste-like reaction liquid from the three-necked flask into a glass beaker, after stirring and dissolving, 200mL of anhydrous ethanol was added to precipitate the product, filter residue was obtained, the filter residue was again alcohol precipitated with 200mL of anhydrous ethanol, and after the filter residue was again filtered, the product was dried at 50 DEG C for 2h, and a solid reactive dye was prepared.

[0076] The solid reactive dye prepared in the embodiment has a yield of 81.4%.

[0077] Example 3

[0078] The embodiment provides a s-triazine type reactive dye modification method, and specific steps and methods are as follows.

[0079] (1) 3g of reactive blue 4, 2g of potassium hydroxide and 6g of ethylenediamine are weighed and added into a three-necked flask, 15mL of N-methylpyrrolidone is added as an oil phase, the three-necked flask is heated to 110 DEG C in an oil bath, and stirring and dispersion are uniform; under the condition of uniform stirring at 400r / min, reaction is carried out for 3h. Since the reaction temperature is high, the three-necked flask is connected with a condenser during the reaction process, ice water is circulated to condense volatile matter backflow, and the reaction is carried out in a fume hood, so that the experiment is safe.

[0080] (2) After the reaction is completed, the three-necked flask is transferred into a water bath pot which has been heated to 80 DEG C, a reduced pressure distillation device is connected, the reaction liquid is distilled into a solid paste, 20mL of distilled water is used to wash the paste-like reaction product from the three-necked flask into a glass beaker, after stirring and dissolving, 200mL of anhydrous ethanol is added to precipitate the product, filtration is carried out to obtain filter residue, the filter residue is again alcohol precipitated with 200mL of anhydrous ethanol, and filtration is again carried out; the product is dried at 50 DEG C for 2h, and a solid reactive dye is prepared.

[0081] The solid reactive dye prepared in the embodiment has a yield of 83.6%.

[0082] Example 4

[0083] The embodiment provides a s-triazine type reactive dye modification method, and specific steps and methods are as follows.

[0084] (1) 5g of reactive blue 4, 2g of sodium hydroxide and 15g of polyethylene glycol (200) diamine are weighed and added into a three-necked flask, 20mL of N,N-dimethylformamide is added as an oil phase, the three-necked flask is heated to 95 DEG C in an oil bath, and stirring and dispersion are uniform; under the condition of uniform stirring at 400r / min, reaction is carried out for 3h. Since the reaction temperature is high, the three-necked flask is connected with a condenser during the reaction process, ice water is circulated to condense volatile matter backflow, and the reaction is carried out in a fume hood, so that the experiment is safe.

[0085] (2) After the reaction is completed, the three-necked flask is transferred into a water bath pot which has been heated to 80 DEG C, a reduced pressure distillation device is connected, the reaction liquid is distilled into a solid paste, 20mL of distilled water is used to wash the paste-like reaction product from the three-necked flask into a glass beaker, after stirring and dissolving, 200mL of anhydrous ethanol is added to precipitate the product, filtration is carried out to obtain filter residue, the filter residue is again alcohol precipitated with 200mL of anhydrous ethanol, and filtration is again carried out; the product is dried at 50 DEG C for 2h, and a solid reactive dye is prepared.

[0086] The solid reactive dye prepared in the embodiment has a yield of 75.8%.

[0087] Example 5

[0088] The embodiment provides a s-triazine type reactive dye modification method, and specific steps and methods are as follows.

[0089] (1) 5g of reactive red 11, 2g of sodium hydroxide and 6g of ethylenediamine were weighed and added into a three-necked flask, 20mL of N,N-dimethylacrylamide was added as an oil phase, the three-necked flask was heated to 105 DEG C in an oil bath, and stirring and dispersion were uniformly carried out, and reaction was carried out for 5h under the condition of uniform stirring at 300r / min. Since the reaction temperature is high, the three-necked flask is connected with a condenser tube during the reaction process, ice water is circulated to condense volatile matter backflow, and the reaction is carried out in a fume hood to ensure the safety of the experiment.

[0090] (2) After the reaction is completed, the three-necked flask is transferred to a water bath pot which has been heated to 80 DEG C, a reduced pressure distillation device is connected, the reaction liquid is distilled to a solid paste, 20mL of distilled water is used to wash the pasty reaction product from the three-necked flask into a glass beaker, the product is precipitated after stirring and dissolving, 200mL of anhydrous ethanol is added, the filter residue is obtained after suction filtration, the filter residue is alcohol precipitated with 200mL of anhydrous ethanol again, suction filtration is carried out again, the product is dried at 40 DEG C for 6h, and the solid reactive dye is prepared.

[0091] The solid reactive dye prepared in the embodiment has a yield of 80.4%.

[0092] Example 6

[0093] The embodiment provides a s-triazine type reactive dye modification method, and specific steps and methods are as follows.

[0094] (1) 5g of reactive red 11, 2g of sodium hydroxide and 6g of ethylenediamine were weighed and added into a three-necked flask, 20mL of N,N-dimethylacrylamide was added as an oil phase, the three-necked flask was heated to 105 DEG C in an oil bath, and stirring and dispersion were uniformly carried out, and reaction was carried out for 5h under the condition of uniform stirring at 300r / min. Since the reaction temperature is high, the three-necked flask is connected with a condenser tube during the reaction process, ice water is circulated to condense volatile matter backflow, and the reaction is carried out in a fume hood to ensure the safety of the experiment.

[0095] (2) After the reaction is completed, the three-necked flask is transferred to a water bath pot which has been heated to 80 DEG C, a reduced pressure distillation device is connected, the reaction liquid is distilled to a solid paste, 20mL of distilled water is used to wash the pasty reaction product from the three-necked flask into a glass beaker, the product is precipitated after stirring and dissolving, 200mL of anhydrous ethanol is added, the filter residue is obtained after suction filtration, the filter residue is alcohol precipitated with 200mL of anhydrous ethanol again, suction filtration is carried out again, the product is dried at 40 DEG C for 6h, and the solid reactive dye is prepared.

[0096] The solid reactive dye prepared in the embodiment has a yield of 80.4%.

[0097] Example 7

[0098] The present example provides a method for modifying a s-triazine type reactive dye. The specific steps and methods are the same as those of Example 1, except that the stirring reaction time in step (1) is 3 h.

[0099] The solid reactive dye prepared in the present example has a yield of 81.6%.

[0100] Example 8

[0101] The present example provides a method for modifying a s-triazine type reactive dye. The specific steps and methods are the same as those of Example 1, except that the stirring reaction time in step (1) is 1.5 h.

[0102] The solid reactive dye prepared in the present example has a yield of 41.8%.

[0103] Example 9

[0104] The present example provides a method for modifying a s-triazine type reactive dye. The specific steps and methods are the same as those of Example 1, except that 5 g of Reactive Deep Blue K-R, 1.5 g of sodium hydroxide, and 15 g of ethylenediamine are added to the three-necked flask, and 15 mL of dimethyl sulfoxide is added as the oil phase.

[0105] Example 10

[0106] The present example provides a method for modifying a s-triazine type reactive dye. The specific steps and methods are the same as those of Example 1, except that 5 g of Reactive Yellow KD-3G, 1.5 g of sodium hydroxide, and 8 g of ethylenediamine are added to the three-necked flask, and 30 mL of N,N-dimethylformamide is added as the oil phase.

[0107] Example 11

[0108] The present example provides a method for modifying a s-triazine type reactive dye. The specific steps and methods are the same as those of Example 1, except that an equal amount of Reactive Turquoise Blue K-GL is used to replace the Reactive Yellow 86 in step (1).

[0109] Example 12

[0110] The present example provides a method for modifying a s-triazine type reactive dye. The specific steps and methods are the same as those of Example 1, except that an equal amount of Reactive Brilliant Red KD-8B is used to replace the Reactive Yellow 86 in step (1).

[0111] Comparative Example 1

[0112] This comparative example provides a method for modifying s-triazine type reactive dyes. The specific steps and methods are the same as those in Example 1, except that an equal mass of sodium hydroxide is used to replace the ethylenediamine in step (1) of Example 1. That is, 5 g of Reactive Yellow 86 and 9.5 g of sodium hydroxide are added to a three-necked flask, and then 20 mL of N,N-dimethylformamide is added as the oil phase. The mixture is heated to 95° C. in an oil bath in the three-necked flask, stirred and dispersed uniformly, and reacted for 5 h under uniform stirring at 400 r / min.

[0113] Comparative Example 2

[0114] This comparative example provides a method for modifying s-triazine type reactive dyes. The specific steps and methods are the same as those in Example 1, except that an equal mass of tetrachloroethylene is used to replace the ethylenediamine in step (1) of Example 1. That is, 5 g of Reactive Yellow 86, 1.5 g of sodium hydroxide and 8 g of tetrachloroethylene are added to a three-necked flask, and then 20 mL of N,N-dimethylformamide is added as an oil phase. The mixture is heated to 95° C. in an oil bath in the three-necked flask, stirred and dispersed uniformly, and reacted at a constant stirring speed of 400 r / min for 5 h.

[0115] Comparative Example 3

[0116] This comparative example provides a method for modifying s-triazine type reactive dyes. The specific steps and methods are the same as those in Example 1, except that an equal mass of polyurethane is used to replace the ethylenediamine in step (1) of Example 1. That is, 5 g of Reactive Yellow 86, 1.5 g of sodium hydroxide and 8 g of polyurethane are added to a three-necked flask, and then 20 mL of N,N-dimethylformamide is added as the oil phase. The mixture is heated to 95° C. in an oil bath in the three-necked flask, stirred and dispersed uniformly, and reacted for 5 h under uniform stirring at 400 r / min.

[0117] Comparative Example 4

[0118] This comparative example provides a method for modifying s-triazine type reactive dyes. The specific steps and methods are the same as those in Example 1, except that tetrachloroethylene and polyurethane are used instead of ethylenediamine in step (1) of Example 1. That is, 5 g of Reactive Yellow 86, 1.5 g of sodium hydroxide, 6 g of polyurethane and 2 g of tetrachloroethylene are added to a three-necked flask, and then 20 mL of N,N-dimethylformamide is added as an oil phase. The mixture is heated to 95° C. in an oil bath in the three-necked flask, stirred and dispersed uniformly, and reacted for 5 h under uniform stirring at 400 r / min.

[0119] Comparative Example 5

[0120] The comparative example provides a method for modifying a s-triazine type reactive dye. The specific steps and methods are the same as those of Example 1, except that ethanol is used instead of N,N-dimethylformamide in step (1) of Example 1, i.e., 5 g of reactive yellow 86, 1.5 g of sodium hydroxide, and 8 g of ethylenediamine are added to a three-necked flask, 20 mL of ethanol is then added, the three-necked flask is heated to 95°C in an oil bath, and the mixture is stirred and dispersed uniformly. The reaction is carried out at a stirring speed of 400 r / min for 5 h.

[0121] Application Example 1

[0122] Into a glass beaker containing 100 mL of physiological saline, 100 mL of carboxyl microspheres are added, and 0.1 g of the solid reactive dye prepared in Example 1, 7, and 8 and 0.6 g of ethyl [3-(dimethylamino) propyl] carbodiimide hydrochloride are weighed and added to the beaker. The pH of the reaction solution is adjusted to 11 using a 2 mol / L sodium hydroxide solution, and the reaction solution is colored at 25°C under magnetic stirring at a speed of 400 r / min for 3 h to obtain a colored microsphere solution.

[0123] The colored microsphere solution prepared in this application example is heated to a boiling temperature of 100°C, and the reaction solution is cooled after 15 min of boiling. The wet spheres are separated using a 400-mesh sieve and then transferred to a glass beaker containing 200 mL of physiological saline. The solution is stirred at a speed of 200 rpm for 10 min to remove uncolored dyes. The stirring and washing steps are repeated twice, for a total of three times. The fixing step is repeated four times, for a total of five times. The wet spheres are separated using a 400-mesh sieve to obtain fixed microspheres.

[0124] The colored microspheres after fixing in this application example do not fade significantly when the second fixing is completed, and the carboxyl microspheres with fixed reactive dyes do not fade when the fifth fixing is completed.

[0125] Application Example 2

[0126] Into a glass beaker containing 75 mL of phosphate buffer, 25 mL of carboxyl microspheres are added, and 0.1 g of the solid reactive dye prepared in Example 3 and 0.1 g of diisopropyl carbodiimide are weighed and added to the beaker. The pH of the reaction solution is adjusted to 12 using a 2 mol / L sodium hydroxide solution, and the reaction solution is colored at 10°C under magnetic stirring at a speed of 400 r / min for 2 h.

[0127] The colored microspheres solution prepared in this application example was heated to a boiling temperature of 110°C, and after 30 minutes from the start of boiling, the reaction solution was cooled. The wet spheres were separated using a 400-mesh sieve, then transferred to a glass beaker and 200 mL of normal saline was added. The solution was stirred at a speed of 100 rpm for 10 minutes, and the above washing step was repeated three times. The uncolored dye was removed, and the washing step was repeated a total of four times. The above fixing step was repeated four times, and the fixing step was repeated a total of five times. The wet spheres were separated using a 400-mesh sieve to obtain fixed microspheres.

[0128] The colored microspheres after fixing in this application example did not substantially fade when the second fixing was completed, and the carboxyl microspheres colored with reactive dyes did not fade when the fourth fixing was completed.

[0129] Application Example 3

[0130] To a glass beaker containing 40 mL of normal saline, 17 mL of carboxyl microspheres were added, and 0.1 g of the solid reactive dye prepared in Example 3 and 1 g of dicyclohexyl carbodiimide were weighed and added to the beaker. The pH of the reaction solution was adjusted to 8 using a 2 mol / L sodium hydroxide solution, and the reaction solution was colored at 35°C for 5 h under magnetic stirring at a speed of 400 r / min.

[0131] The colored microspheres solution prepared in this application example was heated to a boiling temperature of 100°C, and after 20 minutes from the start of boiling, the reaction solution was cooled. The wet spheres were separated using a 400-mesh sieve, then transferred to a glass beaker and 200 mL of normal saline was added. The solution was stirred at a speed of 500 rpm for 30 minutes, and the above washing step was repeated three times. The uncolored dye was removed, and the washing step was repeated a total of four times. The above fixing step was repeated twice, and the fixing step was repeated a total of three times. The wet spheres were separated using a 400-mesh sieve to obtain fixed microspheres.

[0132] The colored microspheres after fixing in this application example did not substantially fade when the second fixing was completed, and the carboxyl microspheres colored with reactive dyes did not fade when the third fixing was completed.

[0133] Application Example 4

[0134] To a glass beaker containing 100 mL of normal saline, 100 mL of carboxyl microspheres were added, and 0.1 g of the solid reactive dye prepared in Example 1-1 and 0.6 g of ethyl [3-(dimethylamino) propyl] carbodiimide hydrochloride were weighed and added to the beaker. The pH of the reaction solution was adjusted to 11 using a 2 mol / L sodium hydroxide solution, and the reaction solution was colored at room temperature for 3 h under magnetic stirring at a speed of 400 r / min.

[0135] The colored microsphere solution prepared in the application example was heated to a boiling temperature of 100℃, and the reaction solution was cooled after 15 minutes from the start of boiling. The wet spheres were separated using a 400-mesh sieve and then transferred to a glass beaker and 200 mL of normal saline was added. The mixture was stirred at a speed of 200 rpm for 10 minutes to remove the uncolored dye. The stirring and washing steps were repeated twice, for a total of three times. The dye fixing step was repeated four times, for a total of five times. The wet spheres were separated using a 400-mesh sieve to obtain the dye-fixed microspheres.

[0136] Experimental Example 1

[0137] One mL of the dye-formed microspheres prepared in Example 1 and 7 mL of normal saline were respectively filled into a Westlin bottle, which was then subjected to moist heat sterilization at 121℃ for 30 minutes. After that, the bottle was placed in a comprehensive pharmaceutical stability test box and subjected to accelerated aging at 60℃ for 90 days. Then, the bottle was taken out and observed. It was found that Figure 1 , and it can be seen that, compared with normal saline, the dye-formed microspheres prepared in the application example were colorless and transparent under naked eye observation. Therefore, it can be seen that the color fastness of the reactive dye colored on the carboxyl microspheres is good.

[0138] Experimental Example 2

[0139] 0.25 g of Reactive Yellow 86 was weighed and added to 100 mL of normal saline to obtain a mixture, 1 mL of the mixture was taken out using a pipette and added to a glass beaker, and then 99 mL of normal saline was added to dilute the reactive dye to a test solution 1 with a concentration of 25 mg / L.

[0140] The solid reactive dye prepared in Example 1 was taken out and added to 100 mL of normal saline to obtain a mixture, 1 mL of the mixture was taken out using a pipette and added to a glass beaker, and then 99 mL of normal saline was added to dilute the solid reactive dye to a test solution 2 with a concentration of 25 mg / L.

[0141] After the dye-fixed microspheres prepared in Example 1 of the application example were stored at room temperature for 100 days, 0.25 g of the dye-fixed microspheres stored for 100 days was weighed and added to 100 mL of normal saline to obtain a mixture, 1 mL of the mixture was taken out using a pipette and added to a glass beaker, and then 99 mL of normal saline was added to dilute the dye-fixed microspheres to a test solution 3 with a concentration of 25 mg / L.

[0142] After the dye-fixed microspheres prepared in Example 1 of the application example were stored in a comprehensive pharmaceutical stability test box at 60℃ for 144 days, 0.25 g of the dye-fixed microspheres stored for 144 days was weighed and added to 100 mL of normal saline to obtain a mixture, 1 mL of the mixture was taken out using a pipette and added to a glass beaker, and then 99 mL of normal saline was added to dilute the dye-fixed microspheres to a test solution 4 with a concentration of 25 mg / L.

[0143] The test liquids 1-4 were scanned using a UV spectrophotometer in the range of 330-600 nm to obtain the absorption curves, as shown in Figure 2 .

[0144] It can be seen that the absorbance of the unmodified reactive dye and the modified reactive dye has no substantial change, both have the highest absorption value at 420 nm, and the absorption value of the carboxyl microsphere physiological saline storage solution placed at room temperature for 100 days and aged for 144 days has little change at 420 nm, so it can be judged that the modified reactive dye colored carboxyl microsphere can be stored for a long time.

[0145] Experimental Example 3

[0146] The fixing microspheres obtained from the modified reactive dyes prepared by the application examples 4 through the examples 1-12 and the comparative examples 1-5 were taken, and 5 ml of the supernatant after the first boiling was taken, wherein, the absorbance of the examples 1, 2 and 6-8 was detected at UV-λ max =426 nm; the absorbance of the examples 3 and 4 was detected at UV-λ max =595 nm; the absorbance of the example 5 was detected at UV-λ max =525 nm; the absorbance of the example 9 was detected at UV-λ max =570 nm; the absorbance of the example 10 was detected at UV-λ max =632 nm; the absorbance of the example 11 was detected at UV-λ max =610 nm; the absorbance of the example 12 was detected at UV-λ max =524.5 nm, and the detection results are shown in Table 1.

[0147] Table 1 Absorbance of the residual dye liquid in the supernatant after the first boiling of the fixing microspheres

[0148] Group Absorbance Group Absorbance Example 1 0.054 Example 10 0.046 Example 2 0.041 Example 11 0.058 Example 3 0.038 Example 12 0.053 Example 4 0.056 Comparative Example 1 0.231 Example 5 0.050 Comparative Example 2 0.159 Example 6 0.087 Comparative Example 3 0.210 Example 7 0.048 Comparative Example 4 0.223 Example 8 0.106 Comparative Example 5 0.178 Example 9 0.062

[0149] According to the data in Table 1, it can be seen that the residual dye liquid in the supernatant after the first boiling of the fixing microspheres formed by the modified reactive dyes prepared by the examples 1-12 of the application is far lower than that of the fixing microspheres formed by the modified reactive dyes prepared by the comparative examples 1-5, which proves that the fixing effect of the modified reactive dyes prepared by the examples of the application is better.

[0150] Obviously, the above examples are only examples for clearly illustrating, but not limiting the embodiments. For those skilled in the art, other different forms of changes or variations can be made on the basis of the above description. Here, it is not necessary and impossible to enumerate all the embodiments. The obvious changes or variations derived therefrom are still within the protection scope of the application.

Claims

1. An application of s-triazine type reactive dyes in microsphere dyeing, characterized in that: The method comprises the following steps: mixing a modified s-triazine type reactive dye, a carboxyl microsphere solution and a condensing agent to obtain a mixed solution, adjusting the pH value of the mixed solution, and stirring to obtain a colored microsphere solution; The modification method of s-triazine type reactive dye comprises the following steps: S1, in the presence of an oil phase, mixing a s-triazine type reactive dye with an alkaline substance, and heating to obtain a modified s-triazine type reactive dye, wherein the oil phase includes an aprotic polar solvent and the alkaline substance includes an organic amine.

2. The use of the s-triazine type reactive dye in microsphere dyeing according to claim 1, characterized in that: The organic amine in step S1 includes at least one of a diamine and a triamine; and / or, The oil phase comprises at least one of a fatty amide compound and an organic sulfur compound; and / or, The mass ratio of the s-triazine type reactive dye to the alkaline substance is (3-5):(6-15); and / or, The mass ratio of the s-triazine type reactive dye to the volume ratio of the oil phase is 1:(3-6), expressed in g:mL; and / or, The s-triazine type reactive dye includes at least one of K type reactive dye, KD type reactive dye and X type reactive dye; and / or, The alkaline substance further includes an inorganic base; and / or, When the s-triazine type reactive dye is mixed with the alkaline substance, the stirring rate is 300-500 rpm and the stirring time is 1.5-5 hours. The stirring time is 3 to 5 hours; and / or, The heating temperature in step S1 is 95-110°C.

3. The application of s-triazine type reactive dyes in microsphere dyeing according to claim 2, characterized in that: The organic amine includes at least one of polyethylene glycol diamine, ethylenediamine, and diethylenetriamine; and / or, The oil phase comprises at least one of N,N-dimethylformamide, N-methylpyrrolidone, N,N-dimethylpropyleneurea and dimethyl sulfoxide; and / or, The X-type reactive dye comprises at least one of Reactive Yellow 86, Reactive Blue 4 or Reactive Red 11; and / or, The K-type reactive dye includes at least one of reactive turquoise blue K-GL and reactive dark blue KR; and / or The KD type reactive dye includes at least one of Reactive Brilliant Red KD-8B and Reactive Yellow KD-3G; and / or, The inorganic base includes at least one of hydroxide and alkaline carbonate; and / or, The mass ratio of the inorganic base to the organic amine in the alkaline substance is 1:(2-10); and / or, The modification method further comprises S2, separating the modified s-triazine type reactive dye from solid and liquid, and drying to obtain a solid reactive dye.

4. The use of the s-triazine type reactive dye in microsphere dyeing according to claim 3, characterized in that: The inorganic base includes at least one of sodium hydroxide, potassium hydroxide, and potassium carbonate; and / or The solid-liquid separation method comprises the steps of distilling the modified s-triazine type reactive dye under reduced pressure to obtain a concentrate, and washing the concentrate. The step of washing the concentrate comprises washing the concentrate with at least one of anhydrous ethanol or distilled water; and / or, The drying temperature is 40-60°C and the drying time is 1-6 hours.

5. The use of the s-triazine type reactive dye in microsphere dyeing according to claim 1, characterized in that: The carboxyl microsphere solution includes a mixture of carboxyl microspheres and a solvent. The solvent includes at least one of physiological saline and phosphate buffer, The volume concentration of carboxyl microspheres in the carboxyl microsphere solution is 25-50%; and / or, The condensing agent includes a carbodiimide condensing agent; and / or, The volume ratio of the carboxyl microspheres to the modified s-triazine type reactive dye is 1:(1-6), in units of L:g; and / or, The mass ratio of the modified s-triazine type reactive dye to the condensation agent is 1:(1-10).

6. The use of the s-triazine type reactive dye in microsphere dyeing according to claim 5, characterized in that: The carbodiimide condensing agent includes at least one of ethyl [3- (dimethylamino) propyl] carbodiimide hydrochloride, dicyclohexylcarbodiimide, and diisopropylcarbodiimide; and / or, Adjusting the pH value of the mixed solution to 8-12; and / or, The stirring time is 2 to 5 hours, and the stirring temperature is 10 to 35°C.

7. The use of the s-triazine type reactive dye in microsphere dyeing according to claim 6, characterized in that: The method also includes the step of fixing the color of the colored microsphere liquid. The color fixing step includes heating the colored microsphere liquid, separating the solid and liquid, and washing to obtain the fixed color microspheres. The fixing step is repeated 2 to 5 times. The heating temperature is 100-110°C and the heating time is 15-30 minutes. Solid-liquid separation is carried out by sieving to obtain colored microspheres. The washing step includes mixing the solid-liquid separated colored microspheres with physiological saline and stirring at a speed of 100 to 500 rpm. The washing in a single fixation step is repeated 2 to 4 times.

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