CN112679980B - High-performance double-color-body brilliant blue reactive dye and preparation method thereof - Google Patents
High-performance double-color-body brilliant blue reactive dye and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-performance double-color-body brilliant blue reactive dye and a preparation method thereof, belonging to the technical field of reactive dyes, and comprising a general formula (I), wherein X is F or Cl; m is-H or an alkali metal; the R is1、R4is-H or-CH3(ii) a The R is2、R3is-H or-SO3H and X are Cl; m is Na; in the general structural formula (I), R is1、R2、R4When is-H, R3is-SO3H; the R is1、R3、R4is-CH3When R is2is-SO3H; x is Cl; m is Na. The reactive blue dye has the advantages that the absorption wavelengths of two color bodies with different structures can be effectively superposed, the synergistic hyperchromic effect of the two color bodies is greatly increased, the gorgeous degree of the dye color is improved, the two color bodies do not contain heavy metal ions, the environmental protection property of the reactive blue dye is greatly improved, the problem that the existing reactive blue dye is inconsistent in directness, exhaustion rate, reactivity and the like during intermolecular color matching is solved, and the reactive blue dye has high lifting power.
Description
Technical Field
The invention relates to the technical field of reactive dyes, in particular to a high-performance double-color-body brilliant blue reactive dye and a preparation method thereof.
Background
The reactive dye has rich varieties and bright colors, and the molecular structure of the reactive dye contains reactive groups which can chemically react with hydroxyl groups on cellulose fibers, amino groups on protein fibers and other groups and are combined with the fibers through covalent bonds, so that various fastness properties of the dyed fibers are excellent. Currently, most reactive dye varieties on the market are typically single-color body reactive dyes such as reactive yellow FG (C.I. reactive yellow 42), reactive orange KN-2G (C.I. reactive orange 72), reactive red 5-B (C.I. reactive red 35), P-6GS bright yellow (C.I. reactive yellow 95), P-3R brilliant blue (C.I. reactive blue 49), and the like.
In addition to the single-chromophore reactive dyes, when a single dye molecule structure contains two chromophores, the dyes are double-chromophore reactive dyes. Different from the single-color body reactive dye, the double-color body reactive dye has higher molar extinction coefficient and stronger lifting force because of containing two color bodies. The reactive dye has unique color performance because the reactive dye contains different color bodies.
At present, when the reactive dye is applied, the color and the chromatic light can be regulated and controlled through the compounding of different dye molecules, so that the application requirement is met. However, in the traditional compounding of the small-molecule reactive dye, the compatibility, the directness, the reactivity, the exhaustion rate and the like of different dye molecules need to be considered. This makes many reactive dyes impossible to use in combination. The reactive dye containing two different color bodies essentially belongs to intramolecular color matching, and the intramolecular color matching does not need to consider the compatibility, the directness, the solubility and the like of a single dye color body, which is different from intermolecular color matching. Particularly, for reactive blue dyes, the final reactive dyes have larger molecular physical property difference due to different chromophoric structures, so that effective compound use is difficult to carry out, meanwhile, the better the diffusivity of the dyes is, the larger the diffusion coefficient is, the more uniform the distribution of the dyes on fibers is, the higher the probability of bonding the dyes with the fibers is, the higher the reaction rate and the fixation efficiency are, the better the level dyeing and the degree of penetration dyeing are, the better the diffusivity performance is, and the larger the molecules are, the more difficult the molecules are to diffuse depending on the structure and the size of solid dye powder, so that the development of the monomolecular reactive blue dyes with double chromophoric bodies has wide application prospect.
CN 109021614A reports a phthalocyanine azo-based double-color body reactive dye with high fixation rate, which utilizes phthalocyanine color body and monoazo red color body containing J acid monoazo orange or H acid to carry out intramolecular compounding; CN107760060A discloses a high sunstruck turquoise active dye compound, which is also prepared by intramolecular combination of phthalocyanine color bodies and yellow color bodies. The two types of double-color body blue dyes use two color body combinations with different hues, CN 109021614A reports that the blue color body is combined with orange or red color body, CN107760060A reports that the blue color body is combined with yellow color body, the phthalocyanine color body dye is emerald blue (green blue), the absorption wavelength range is 640nm-690nm, the J acid monoazo orange dye is 460 nm-490 nm, the H acid monoazo red dye is 520nm-550nm, and the yellow absorption wavelength range is 390nm-440 nm. Therefore, in the dye obtained by compounding the phthalocyanine color bodies and the other color bodies, the absorption wavelength ranges of the two color bodies in the molecular structure are difficult to achieve the synergistic effect of homochromatic superposition, the chromatic light of the final dye color can be only subjected to micro-regulation and control through the color bodies of the other colors, and the improvement performance of the dye cannot be effectively improved. When the reactive dye is applied to fiber dyeing, the brilliance is the most basic requirement, the H acid monoazo dye is usually red, the H acid disazo dye is navy blue, and both the formazan chromophore and the phthalocyanine chromophore contain heavy metal ions, so that a novel double-chromophore brilliant blue reactive dye is developed, the molecular structure does not contain heavy metal ions, the two chromophores are brilliant blue, the absorption wavelength ranges can be effectively superposed, and high dye lifting performance and color performance can be expected to be obtained.
Disclosure of Invention
1. Technical problem to be solved
The technical problem to be solved by the invention is to provide a high-performance double-chromophore brilliant blue reactive dye and a preparation method thereof, wherein the absorption wavelengths of two chromophores with different structures in the reactive blue dye can be effectively superposed, and the two chromophores do not contain heavy metal ions, so that the environmental protection property of the reactive blue dye is greatly improved, and the problem of inconsistency of directness, exhaustion rate, reactivity and the like in intermolecular color matching of the existing reactive blue dye is solved, and the reactive blue dye not only has high lifting power, but also has excellent light fastness.
2. Technical scheme
In order to solve the problems, the invention adopts the following technical scheme:
a high-performance double-color-body brilliant blue reactive dye is characterized in that: the reactive blue dye is a compound shown in a structural general formula I;
in the formula I, X is F or Cl; m is-H or an alkali metal; the R is1、R4is-H or-CH3(ii) a The R is2、R3is-H or-SO3H；
Further, R is shown in the structural general formula I1、R4is-H or-CH3(ii) a The R is2、R3is-H or-SO3H; x is Cl; m is Na.
Further, in the general structural formula I, R is1、R2、R4When is-H, R3is-SO3H; the R is1、R3、R4is-CH3When R is2is-SO3H; x is Cl; m is Na.
Further, the commercial coloring agent comprises 75-85% by mass of active blue dye, 5-15% by mass of dispersing agent, 0.1-0.5% by mass of dustproof agent and 5-15% by mass of anhydrous sodium sulphate.
Further, the diffusing agent is a methyl naphthalene sulfonic acid formaldehyde condensate, and the dustproof agent is a water-soluble high molecular compound.
Further, the commercial dye is used for dyeing cellulose fibers, which are hydroxyl-and/or nitrogen-containing cellulose fibers.
Further, the cellulose fiber is cotton, viscose, hemp or a plurality of blended fiber fabrics thereof.
Further, the preparation method of the compound shown in the structural general formula I is carried out according to the following process, and the specific steps comprise:
(1) diazotization reaction
Adding 4-aminodiphenylamine-2-sulfonic acid into water, adjusting the pH value of the solution to 7.2-7.8 by using baking soda, adding sodium nitrite, stirring to obtain a mixed solution, slowly adding the mixed solution into a hydrochloric acid aqueous solution cooled to below 10 ℃, continuing to react for 30-60 minutes after the dropwise addition is finished, detecting no 4-aminodiphenylamine-2-sulfonic acid as a reaction end point by using an Ehrlich reagent, and removing excessive nitrous acid by using the sulfamic acid to prepare 4-aminodiphenylamine-2-sulfonic acid diazonium salt; the molar ratio of the 4-aminodiphenylamine-2-sulfonic acid to the sodium nitrite is 1: 1.01-1.03; the mol ratio of the 4-aminodiphenylamine-2-sulfonic acid to the hydrochloric acid is 1: 2.5-2.8;
(2) coupling reaction
Adding the 4-aminodiphenylamine-2-sulfonic acid diazonium salt prepared in the step (1) into an aqueous solution of H acid, controlling the pH value of the reaction to be between 7 and 8, keeping the pH value of the reaction solution to be between 7 and 8, reacting at the temperature of 5 to 10 ℃ for 2 to 4 hours, detecting that no diazonium salt and a coupling component are used as reaction end points through a ring infiltration method, and preparing the monoazo dye of the H acid after the reaction is finished; the molar ratio of the 4-aminodiphenylamine-2-sulfonic acid diazonium salt to the H acid is 1: 1-0.98: 1;
(3) monocondensation of cyanuric chloride or cyanuric fluoride
Pulping cyanuric chloride or cyanuric fluoride for half an hour, slowly dripping the monoazo dye solution of the H acid prepared in the step (2) into the pulping liquid of the cyanuric chloride or the cyanuric fluoride, controlling the reaction pH value to be between 4 and 5, keeping the temperature to be between 0 and 5 ℃, keeping the reaction for 1 to 2 hours under the condition, detecting the monoazo dye of the H acid prepared in the step (2) as a reaction end point through thin-layer chromatography, and preparing a reaction liquid containing a condensation product of the cyanuric chloride or the cyanuric fluoride; the molar ratio of the cyanuric chloride or the cyanuric fluoride to the monoazo dye of the H acid is 1: 1-1.03: 1;
(4) dimeric reaction of cyanuric chloride or cyanuric fluoride
Dissolving blue chromophore a1 containing anthraquinone chromophore in water, slowly dropwise adding into the condensed product reaction liquid of cyanuric chloride or cyanuric fluoride prepared in the step (3), controlling the reaction temperature to be 45-55 ℃, controlling the pH value to be 5-6, keeping the reaction for 4-6 hours under the condition, detecting no blue chromophore as a reaction end point through thin layer chromatography and liquid chromatography, drying at 75 ℃ after the reaction is finished, and grinding the dye through grinding equipment to obtain the active dye solid powder shown in the final compound (I); the molar ratio of the blue chromophore a1 of the anthraquinone chromophore to the cyanuric chloride or the cyanuric fluoride mono-condensation product is 0.97: 1-1.03: 1.
The grinding equipment adopted in the preparation method of the active blue dye comprises a device body, wherein a supporting seat is welded on the back of the device body, a driving motor is installed at the middle position of the top of the supporting seat, the output end of the driving motor is connected with a rotating shaft, the other end of the rotating shaft penetrates through the supporting seat and is connected with the top of the device body through a bearing, an annular grinding cavity is fixed at the top of the device body outside the rotating shaft, a connecting port is uniformly formed in the bottom of the annular grinding cavity, a discharging channel is connected inside the device body at the position of the connecting port, an extruding cylinder is vertically welded inside the discharging channel, a triangular piston seat is connected inside the extruding cylinder in a sliding mode, a telescopic sleeve is vertically welded at the vertex angle position of the triangular piston seat, the other end of the telescopic sleeve extends to the top of the extruding cylinder, and air inlets are formed in the bottoms of two sides of the telescopic sleeve, the bottom of the extrusion cylinder is provided with an exhaust port, both sides of the extrusion cylinder are provided with discharge ports, the top end inside the connector is slidably connected with a first wave-shaped electromagnetic plate, the trough positions of the first wave-shaped electromagnetic plate are uniformly provided with discharge holes, the bottom of the first wave-shaped electromagnetic plate is fixed with the other end of a telescopic sleeve, the telescopic sleeve is communicated with the discharge holes, both sides of the rotating shaft are welded with hinged shafts, the inside of each hinged shaft is hinged with a second hinged rod, a limiting plate is welded above the hinged position of the second hinged rod and the hinged shaft, the other end of the second hinged rod is connected with an annular grinding block, the bottom of the annular grinding block is uniformly fixed with a second wave-shaped electromagnetic plate which is mutually matched with the inside of the connector, the top of the annular grinding block is provided with a feed inlet, and a transmission case is welded on the rotating shaft above the hinged shafts, and the toroidal cavity has been seted up to the transmission case outside the pivot inside, the spout has been seted up at the transmission case top of toroidal cavity position department, and the equidistant welding in toroidal cavity top of spout both sides has the lug, adjacent two inside all sliding connection of cavity between the lug has the connecting block, and the vertical welding in top of connecting block has the connecting rod, the other end of connecting rod passes the spout and extends to the top of transmission case and articulates there is hinge bar one, and hinge bar one's intermediate position department has the bracing piece through articulated shaft articulation, the other end of bracing piece welds each other with the top of supporting seat, the other end of hinge bar one all welds and strikes the head.
Preferably, the second wave-shaped electromagnetic plate and the first wave-shaped electromagnetic plate are symmetrically arranged, and the wave crests of the second wave-shaped electromagnetic plate and the wave crests of the first wave-shaped electromagnetic plate correspond to each other.
3. Advantageous effects
(1) The anthraquinone chromophore has two main absorption peaks in an absorption waveband of 520-660 nm, wherein the two main absorption peaks are respectively about 580nm and 630nm, the difference is 50nm, the absorption peak intensity ratio is about 1:1, the peak type distribution is wider, H acid monoazo blue has only one maximum absorption peak in the absorption waveband of 500-670 nm, the absorption peak intensity is about 592nm, the absorption peak intensity is higher, and the two main absorption peaks can be effectively complemented when the two main absorption peaks are compounded with the anthraquinone chromophore in molecules to play a role in synergy and hyperchromism; meanwhile, the molecular structure of the reactive blue dye is innovative, the reactive blue dye can be directly used for dyes of cellulose fibers and protein fibers, and the problem that the compatibility of the dyes needs to be considered when the traditional reactive blue dye is compounded and applied does not exist; meanwhile, the provided reactive blue dye contains two different brilliant blue color bodies, namely a monoazo brilliant blue color body taking H acid as a coupling component and a brilliant blue color body taking anthraquinone as a color body; the difference between the reactive blue dye and the traditional reactive blue dye lies in that the absorption wavelength ranges of the two color bodies are basically consistent, the absorption wavelength range of the anthraquinone color body is 520nm-660nm, the absorption wavelength range of the H acid monoazo dye is 500nm-670nm, and the absorption wavelengths of the two color bodies can be effectively superposed.
(2) Compared with the traditional active blue dye, the phthalocyanine active dye in the traditional active blue dye is prepared by copper phthalocyanine raw material through chlorosulfonation and other reaction steps, the phthalein in the traditional active blue dye not only contains heavy metal ions, but also is usually a mixture, therefore, the finally prepared double-color dye is also a mixture with a complex structure, and the repeatability and the stability of the application performance are poor, while the blue active dye in the application is prepared from anthraquinone color body and H acid monoazo dye, and the anthraquinone color body and the H acid monoazo dye do not contain heavy metal ions, so the environmental protection performance of the active blue dye in the application can be greatly improved, and meanwhile, the absorption wavelengths of the anthraquinone color body and the H acid monoazo dye in the application can be effectively superposed, so the synergistic hyperchromic effect of the two color bodies can be greatly improved, the gorgeous degree of the dye color is improved, so that the prepared reactive dye is more suitable for fiber dyeing.
(3) The blue reactive dye provided by the invention has two color bodies in a molecular structure, and has high molar extinction coefficient, high solubility, good cotton staining fastness and light fastness and obvious lifting force on the premise that the absorption wavelengths of the anthraquinone color body and the H acid monoazo dye can be effectively superposed to improve the gorgeous degree of the dye color and the two color bodies do not contain heavy metal ions. Meanwhile, the blue reactive dye contains anthraquinone color bodies, so that the light fastness performance of the final blue reactive dye is remarkably improved, and the blue reactive dye has a wide application prospect.
(4) In the process of grinding the interior of the annular grinding cavity by the annular grinding block, the first wave-shaped electromagnetic plate is driven to ascend along the connecting port by the adsorbability of the first wave-shaped electromagnetic plate and the second wave-shaped electromagnetic plate when the second wave-shaped electromagnetic plate which is uniformly arranged at the bottom of the annular grinding block passes through the first wave-shaped electromagnetic plate which slides in the connecting port, so that the wave trough of the first wave-shaped electromagnetic plate corresponds to the wave crest of the second wave-shaped electromagnetic plate, the pigment is extruded, the grinding effect is improved, the telescopic sleeve and the triangular piston seat are driven to slide along the interior of the extrusion cylinder by the ascending of the first wave-shaped electromagnetic plate, air in the extrusion cylinder above the triangular piston seat enters the interior of the telescopic sleeve through the air inlet and blows the discharge hole at the position of the wave trough of the first wave-shaped electromagnetic plate, when the wave crest of the first wave-shaped electromagnetic plate corresponds to the wave crest of the second wave-shaped electromagnetic plate, at the moment, the wave trough of the first wave-shaped electromagnetic plate and the wave trough of the second wave-shaped electromagnetic plate form a closed cavity, the dye in the cavity is blown up under the blowing effect of the discharge hole, the dye is prevented from blocking the discharge hole, the dye is convenient to unload, meanwhile, when the second wave-shaped electromagnetic plate is separated from the first wave-shaped electromagnetic plate, the first wave-shaped electromagnetic plate moves downwards without the adsorption effect of the second wave-shaped electromagnetic plate, and the triangular piston seat is completely contacted with the bottom surface inside the extrusion cylinder, in the descending process of the triangular piston seat, the air suction effect is generated inside the extrusion cylinder above the triangular piston seat under the action of negative pressure, and meanwhile, the dye falling at the wave trough of the first wave-shaped electromagnetic plate is sucked out from the positions of the discharge holes of 150 meshes to 200 meshes under the air suction effect and enters the inside of the telescopic sleeve, inhale the inside of flexible cover inside dyestuff from air inlet and discharge gate position department and discharge passage's inside when triangle-shaped piston seat contacts with the inside bottom surface of recipient completely, accelerated the speed of the ejection of compact on the one hand, utilize the mutually supporting between wave type electromagnetic plate one and the wave type electromagnetic plate two to improve the effect of grinding, convenient to use simultaneously.
(5) The invention drives the transmission case to rotate in the rotating process of the rotating shaft, meanwhile, lugs are fixed on the tops of the transmission case at the two sides of the sliding groove at equal intervals, in the rotating process of the transmission case along with the rotating shaft, the connecting block in the transmission case slides along the inside of the transmission case, and moves up and down under the action of the lugs fixed at equal intervals, meanwhile, the connecting block and the first hinge rod are hinged through the connecting rod, the middle position of the first hinge rod is hinged with the supporting rod through the hinge shaft, so that the first hinge rod is driven to move up and down in the up and down movement process of the connecting block and the top of the annular grinding block is hammered through the knocking head, meanwhile, the top of the hinge shaft connecting the second hinge rod with the rotating shaft is welded with the limiting plate, the second hinge rod and the annular grinding block can only extrude downwards, and the bottom of the annular grinding block can generate the hammering effect on the dye in the annular grinding cavity under the hammering effect, further improving the grinding effect of the dye and being convenient to use.
Drawings
FIG. 1 is a reaction scheme of the present invention;
FIG. 2 is a schematic view of the internal structure of the device body according to the present invention;
FIG. 3 is a schematic top view of the annular grinding chamber and annular grinding blocks of the present invention;
FIG. 4 is a schematic bottom view of the ring mill block of the present invention;
FIG. 5 is an enlarged view of the structure at A in FIG. 2;
FIG. 6 is a schematic view of the internal side of the connection port according to the present invention;
FIG. 7 is a schematic top view of the transmission case of the present invention;
FIG. 8 is a schematic view of the connection structure of the rotating shaft and the hinge shaft according to the present invention.
Reference numerals: 1. a device body; 2. a discharge channel; 3. an annular milling chamber; 4. a ring-shaped grinding block; 5. a transmission case; 6. a bump; 7. a support bar; 8. a connecting rod; 9. a drive motor; 10. a supporting seat; 11. a rotating shaft; 12. a first hinge rod; 13. a knocking head; 14. a second hinge rod; 15. hinging a shaft; 16. an extrusion cylinder; 17. a triangular piston seat; 18. a connecting port; 19. a first wave-shaped electromagnetic plate; 20. a telescopic sleeve; 21. connecting blocks; 22. a chute; 23. a discharge hole; 24. a wave type electromagnetic plate II; 25. a discharge port; 26. an exhaust port; 27. an air inlet; 28. a limiting plate; 29. and (4) feeding a material inlet.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1
As shown in figure 1, the high-performance double-color-body brilliant blue reactive dye and the preparation method thereof are shown in figure 1,
in the formula I, X is F or Cl; m is-H or an alkali metal; r1、R4is-H or-CH3；R2、R3is-H or-SO3H；
In this example, R in the general formula I1、R4is-H or-CH3；R2、R3is-H or-SO3H; x is Cl; m is Na.
In this example, in the general structural formula I, R1、R2、R4When is-H, R3is-SO3H；R1、R3、R4is-CH3When R is2is-SO3H; x is Cl; m is Na.
In this embodiment, the commercial coloring agent includes 75% by mass of a reactive blue dye, 5% by mass of a diffusing agent, 0.1% by mass of a dust-proofing agent, and 5% by mass of anhydrous sodium sulfate.
In this example, the diffusing agent was a methyl naphthalene sulfonic acid formaldehyde condensate, and the dust-proofing agent was a water-soluble polymer compound.
In this example, commercial dyes are used for dyeing of cellulose fibers, which are hydroxyl-and/or nitrogen-containing cellulose fibers.
In this embodiment, the cellulose fiber is cotton, viscose, hemp or a blended fabric thereof.
In this example, the preparation of the compound of general structural formula i was carried out according to the following procedure, which specifically comprises the steps of:
(1) diazotization reaction
Adding 4-aminodiphenylamine-2-sulfonic acid into water, adjusting the pH value of the solution to 7.2-7.8 by using baking soda, adding sodium nitrite, stirring to obtain a mixed solution, slowly adding the mixed solution into a hydrochloric acid aqueous solution cooled to below 10 ℃, continuing to react for 30-60 minutes after the dropwise addition is finished, detecting no 4-aminodiphenylamine-2-sulfonic acid as a reaction end point by using an Ehrlich reagent, and removing excessive nitrous acid by using the sulfamic acid to prepare 4-aminodiphenylamine-2-sulfonic acid diazonium salt; the molar ratio of the 4-aminodiphenylamine-2-sulfonic acid to the sodium nitrite is 1: 1.01; the mol ratio of the 4-aminodiphenylamine-2-sulfonic acid to the hydrochloric acid is 1: 2.5;
(2) coupling reaction
Adding the 4-aminodiphenylamine-2-sulfonic acid diazonium salt prepared in the step (1) into an aqueous solution of H acid, controlling the pH value of the reaction to be between 7 and 8, keeping the pH value of the reaction solution to be between 7 and 8, reacting at the temperature of 5 to 10 ℃ for 2 to 4 hours, detecting the reaction end point of no diazonium salt and a coupling component by a ring permeation method, and preparing the monoazo dye of the H acid after the reaction is finished; the molar ratio of the 4-aminodiphenylamine-2-sulfonic acid diazonium salt to the H acid is 1: 1;
(3) monocondensation of cyanuric chloride or cyanuric fluoride
Pulping cyanuric chloride or cyanuric fluoride for half an hour, slowly dripping the monoazo dye solution of the H acid prepared in the step (2) into the pulping liquid of the cyanuric chloride or the cyanuric fluoride, controlling the reaction pH value to be between 4 and 5, keeping the temperature to be between 0 and 5 ℃, keeping the reaction for 1 to 2 hours under the condition, detecting the monoazo dye of the H acid prepared in the step (2) as a reaction end point through thin-layer chromatography, and preparing a reaction liquid containing a condensation product of the cyanuric chloride or the cyanuric fluoride; the molar ratio of the cyanuric chloride or the cyanuric fluoride to the monoazo dye of the H acid is 1: 1;
(4) dimeric reaction of cyanuric chloride or cyanuric fluoride
Dissolving a blue chromophore a1 (a blue chromophore obtained by m-bis reaction of bromamine acid and bromamine acid) containing anthraquinone chromophore in water, slowly dropwise adding the blue chromophore into the reaction solution of the cyanuric chloride or cyanuric fluoride polycondensate prepared in the step (3), controlling the reaction temperature to be 45-55 ℃ and the pH value to be 5-6, keeping the reaction for 4-6 hours under the condition, detecting no blue chromophore as a reaction end point through thin layer chromatography and liquid chromatography, drying at 75 ℃ after the reaction is finished, and grinding the dye through grinding equipment to obtain the active dye solid powder shown in the final compound (I); the molar ratio of the blue chromophore a1 of the anthraquinone chromophore to the melamine or monocondensate of the melamine was 0.97: 1.
As shown in fig. 2-8, a method for preparing a high-performance double-color-body brilliant blue reactive dye, wherein in step (4), the dye is ground by a grinding device, the grinding device comprises a device body 1, a support base 10 is welded on the back of the device body 1, a driving motor 9 is installed at the middle position of the top of the support base 10, the output end of the driving motor 9 is connected with a rotating shaft 11, the other end of the rotating shaft 11 penetrates through the support base 10 and is connected with the top of the device body 1 through a bearing, an annular grinding cavity 3 is fixed at the top of the device body 1 outside the rotating shaft 11, connectors 18 are uniformly arranged at the bottom of the annular grinding cavity 3, a discharge channel 2 is connected inside the device body 1 at the positions of the connectors 18, an extrusion cylinder 16 is vertically welded inside the discharge channel 2, and a triangular piston seat 17 is slidably connected inside the extrusion cylinder 16, and the vertex angle position of the triangular piston seat 17 is vertically welded with a telescopic sleeve 20, and the other end of the telescopic sleeve 20 extends to the top of the extrusion cylinder 16, the bottoms of both sides of the telescopic sleeve 20 are both provided with air inlets 27, the bottom of the extrusion cylinder 16 is provided with an air outlet 26, both sides of the extrusion cylinder 16 are both provided with a discharge hole 25, the top end inside the connecting port 18 is slidably connected with a first wave-shaped electromagnetic plate 19, the trough position of the first wave-shaped electromagnetic plate 19 is uniformly provided with a discharge hole 23, the bottom of the first wave-shaped electromagnetic plate 19 is fixed with the other end of the telescopic sleeve 20, the telescopic sleeve 20 is communicated with the discharge hole 23, both sides of the rotating shaft 11 are welded with a hinge shaft 15, the inside of the hinge shaft 15 is hinged with a second hinge rod 14, a limit plate 28 is welded above the hinge position of the second hinge rod 14 and the hinge shaft 15, the other end of the hinge rod 14 is connected with an annular grinding block 4, the bottom of the annular grinding block 4 is uniformly fixed with a wave type electromagnetic plate two 24 which is mutually matched with the inside of the connecting port 18, the wave type electromagnetic plate two 24 and the wave type electromagnetic plate one 19 are mutually symmetrically arranged, the wave peaks and the wave peaks of the wave type electromagnetic plate two 24 and the wave type electromagnetic plate one 19 are mutually corresponding, the top of the annular grinding block 4 is provided with a feed inlet 29, a transmission case 5 is welded on a rotating shaft 11 above a hinged shaft 15, an annular cavity is arranged inside the transmission case 5 outside the rotating shaft 11, a sliding groove 22 is arranged at the top of the transmission case 5 at the position of the annular cavity, lugs 6 are welded at the top of the annular cavity at two sides of the sliding groove 22 at equal intervals, a connecting block 21 is slidably connected inside the cavity between two adjacent lugs 6, a connecting rod 8 is vertically welded at the top of the connecting block 21, the other end of the connecting rod 8 penetrates through the sliding groove 22 to extend to the top of the transmission case 5 and is hinged with a hinged rod one 12, and the middle position department of articulated rod one 12 articulates through the articulated shaft has bracing piece 7, and the other end of bracing piece 7 and the top of supporting seat 10 are welded each other, and the other end of articulated rod one 12 all welds and strikes head 13.
Example 2
The present embodiment is different from embodiment 1 in that:
in this embodiment, the commercial coloring agent includes 85% by mass of a reactive blue dye, 15% by mass of a diffusing agent, 0.5% by mass of a dust-proofing agent, and 15% by mass of anhydrous sodium sulfate;
in this example, the molar ratio of 4-aminodiphenylamine-2-sulfonic acid to sodium nitrite was 1: 1.01; the mol ratio of the 4-aminodiphenylamine-2-sulfonic acid to the hydrochloric acid is 1: 2.5;
in this example, the molar ratio of 4-aminodiphenylamine-2-sulfonate diazonium salt to H acid was 1: 1;
in this example, the molar ratio of cyanuric chloride or cyanuric fluoride to monoazo dye of H acid is 1: 1;
in this example, the blue chromophore a1 obtained by the M-bis reaction with bromamine acid in preparation step (4) was replaced with a blue chromophore obtained by the reaction of bromamine acid with M acid;
in this example, the molar ratio of the blue chromophore a1 of the anthraquinone chromophore to the monoacid of cyanuric chloride or cyanuric fluoride is 0.97: 1.
Example 3
The present embodiment is different from embodiment 1 in that:
in this embodiment, the commercial coloring agent includes 85% by mass of a reactive blue dye, 15% by mass of a diffusing agent, 0.5% by mass of a dust-proofing agent, and 15% by mass of anhydrous sodium sulfate.
In this example, the molar ratio of 4-aminodiphenylamine-2-sulfonic acid to sodium nitrite was 1: 1.03; the mol ratio of the 4-aminodiphenylamine-2-sulfonic acid to the hydrochloric acid is 1: 2.8;
in this example, the molar ratio of 4-aminodiphenylamine-2-sulfonate diazonium salt to H acid was 0.98: 1;
in this example, the molar ratio of cyanuric chloride or cyanuric fluoride to monoazo dye of H acid was 1.03: 1;
in this example, the molar ratio of the blue chromophore a1 of the anthraquinone chromophore to the monoacid of cyanuric chloride or cyanuric fluoride is 1.03: 1.
Example 4
The present embodiment is different from embodiment 1 in that:
in this example, the molar ratio of 4-aminodiphenylamine-2-sulfonic acid to sodium nitrite was 1: 1.03; the mol ratio of the 4-aminodiphenylamine-2-sulfonic acid to the hydrochloric acid is 1: 2.8;
in this example, the molar ratio of 4-aminodiphenylamine-2-sulfonate diazonium salt to H acid was 0.98: 1;
in this example, the molar ratio of cyanuric chloride or cyanuric fluoride to monoazo dye of H acid was 1.03: 1;
in this example, the molar ratio of the blue chromophore a1 of the anthraquinone chromophore to the monoacid of cyanuric chloride or cyanuric fluoride is 1.03: 1.
Verification test
2g of the commercial dye in each of the above examples 1-4 was added with 8g of urea, 2.5g of baking soda, 60g of sodium alginate paste, 1g of anti-staining salt and 26.5g of water to prepare an active blue printing paste, a cotton fabric was printed, dried at 85 ℃, steamed for 7 minutes at 100 ℃ (70% relative humidity), washed with water and dried to obtain a dyed fabric, and the product performance test results are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, the reactive blue dye provided by the invention not only has high solubility, but also has good cotton staining fastness and light fastness which reach 4-5 grades, and after the molecular structure of the reactive dye is innovatively designed, the reactive blue dye has good promotion performance, and compared with the use amount of 1% of the dye, the strength is promoted by about 3 times when the dye is used in 5%.
The specific action principle of the grinding equipment adopted in the step (4) of the preparation method of the reactive blue dye is as follows:
firstly, dried dye is led into the interior of the annular grinding cavity 3 from the position of the feed inlet 29, then an external power supply is used for providing electric support for the driving motor 9, the driving motor 9 drives the rotating shaft 11 to rotate, the annular grinding block 4 is driven to rotate along the interior of the annular grinding cavity 3 through the hinge rod II 14 in the rotating process of the rotating shaft 11, the dye entering the interior of the annular grinding cavity 3 is ground, in the process of grinding the interior of the annular grinding cavity 3 by the annular grinding block 4, the wave-shaped electromagnetic plate II 24 uniformly arranged at the bottom of the annular grinding block 4 drives the wave-shaped electromagnetic plate I19 to ascend along the connecting port 18 through the adsorbability of the two magnets of the wave-shaped electromagnetic plate I19 and the wave-shaped electromagnetic plate II 24 when passing through the wave-shaped electromagnetic plate I19 sliding in the connecting port 18, so that the wave trough of the wave-shaped electromagnetic plate I19 corresponds to the wave crest of the wave-shaped electromagnetic plate II 24, the pigment is extruded, the grinding effect is improved, the telescopic sleeve 20 and the triangular piston seat 17 are driven to slide along the interior of the extrusion cylinder 16 by the ascending of the first wavy electromagnetic plate 19, air in the extrusion cylinder 16 above the triangular piston seat 17 enters the telescopic sleeve 20 through the air inlet 27 and blows air to the discharge hole 23 at the position of the trough of the first wavy electromagnetic plate 19, when the wave crest of the first wavy electromagnetic plate 19 corresponds to the wave crest of the second wavy electromagnetic plate 24, the trough of the first wavy electromagnetic plate 19 and the trough of the second wavy electromagnetic plate 24 form a closed cavity, the dye in the cavity is blown up under the blowing effect of the discharge hole 23, the dye is prevented from blocking the discharge hole 23, the dye is convenient to unload, and when the second wavy electromagnetic plate 24 is separated from the position of the first wavy electromagnetic plate 19, under the adsorption action of the first wave-shaped electromagnetic plate 19 without the second wave-shaped electromagnetic plate 24, the first wave-shaped electromagnetic plate 19 moves downwards, the triangular piston seat 17 is completely contacted with the bottom surface inside the extrusion cylinder 16, in the descending process of the triangular piston seat 17, the inside of the extrusion cylinder 16 above the triangular piston seat 17 generates air suction effect under the action of negative pressure, meanwhile, the dye falling at the wave trough position of the first wave-shaped electromagnetic plate 19 is sucked out from the discharge hole 23 positions of 150 meshes to 200 meshes under the air suction effect and enters the inside of the telescopic sleeve 20, when the triangular piston seat 17 is completely contacted with the bottom surface inside the extrusion cylinder 16, the dye sucked into the inside of the telescopic sleeve 20 is discharged into the inside of the discharge channel 2 from the positions of the air inlet 27 and the discharge hole 25 and is discharged through the other end of the discharge channel 2, and simultaneously, the transmission case 5 is driven to rotate in the rotating process of the rotating shaft 11, meanwhile, lugs 6 are fixed on the tops of the transmission boxes 5 on two sides of the sliding groove 22 at equal intervals, in the process that the transmission boxes 5 rotate along with the rotating shaft 11, the connecting block 21 inside the transmission box 5 slides along the inside of the transmission box 5, and moves up and down in an up-and-down fluctuating mode under the action of the lugs 6 fixed at equal intervals, meanwhile, the connecting block 21 and the first hinge rod 12 are hinged through the connecting rod 8, the middle position of the first hinge rod 12 is hinged with the supporting rod 7 through the hinge shaft, so that the first hinge rod 12 is driven to move up and down in the up-and-down fluctuating motion process of the connecting block 21, the top of the annular grinding block 4 is hammered through the hammering head 13, meanwhile, a limiting plate 28 is welded on the top of the hinge shaft 15 connected with the rotating shaft 11 through the second hinge rod 14, the second hinge rod 14 and the annular grinding block 4 can only extrude downwards, and the bottom of the annular grinding block 4 can hammered dyes inside the annular grinding cavity 3, further improving the grinding effect of the dye and being convenient to use.
It should be understood by those skilled in the art that the above embodiments are only for illustrating the present invention and are not to be used as a limitation of the present invention, and that changes and modifications to the above embodiments are within the scope of the claims of the present invention as long as they are within the spirit and scope of the present invention.
Claims (9)
1. A high-performance double-color-body brilliant blue reactive dye is characterized in that: the reactive blue dye is a compound shown in a structural general formula I;
in the formula I, X is F or Cl; m is-H or an alkali metal; the R is1、R2、R4When is-H, R3is-SO3H; the R is1、R3、R4is-CH3When R is2is-SO3H。
2. The high performance dual chromophore brilliant blue reactive dye of claim 1, wherein: x is Cl; m is Na.
3. The commercial dyeing agent prepared from the high-performance double-color-body brilliant blue reactive dye according to any one of claims 1 to 2, characterized in that: the commercial coloring agent comprises 75-85% of reactive blue dye, 5-15% of dispersing agent, 0.1-0.5% of dustproof agent and 5-15% of anhydrous sodium sulphate by mass.
4. The commercial stain of claim 3, wherein: the dispersing agent is a methyl naphthalene sulfonic acid formaldehyde condensate, and the dustproof agent is a water-soluble high molecular compound.
5. Use of a commercial stain according to claim 4, wherein: the commercial dyeing agent is used for dyeing cellulose fibers, and the cellulose fibers are cellulose fibers containing hydroxyl and/or nitrogen.
6. Use of a commercial stain according to claim 5, wherein: the cellulose fiber is cotton, viscose, hemp or various blended fiber fabrics thereof.
7. The preparation method of the high-performance double-color-body brilliant blue reactive dye as claimed in any one of claims 1-2, characterized in that: the preparation method of the compound shown in the structural general formula I is carried out according to the following process, and comprises the following specific steps:
(1) diazotization reaction
Adding 4-aminodiphenylamine-2-sulfonic acid into water, adjusting the pH value of the solution to 7.2-7.8 by using baking soda, adding sodium nitrite, stirring to obtain a mixed solution, slowly adding the mixed solution into a hydrochloric acid aqueous solution cooled to below 10 ℃, continuing to react for 30-60 minutes after the dropwise addition is finished, detecting that no 4-aminodiphenylamine-2-sulfonic acid is detected by an Ehrlich reagent, and removing excessive nitrous acid through sulfamic acid to prepare 4-aminodiphenylamine-2-sulfonic acid diazonium salt; the molar ratio of the 4-aminodiphenylamine-2-sulfonic acid to the sodium nitrite is 1: 1.01-1.03; the mol ratio of the 4-aminodiphenylamine-2-sulfonic acid to the hydrochloric acid is 1: 2.5-2.8;
(2) coupling reaction
Adding the 4-aminodiphenylamine-2-sulfonic acid diazonium salt prepared in the step (1) into an aqueous solution of H acid, controlling the pH value of the reaction to be between 7 and 8, keeping the pH value of the reaction solution to be between 7 and 8, reacting at the temperature of 5 to 10 ℃ for 2 to 4 hours, detecting that no diazonium salt and a coupling component are used as reaction end points through a ring infiltration method, and preparing the monoazo dye of the H acid after the reaction is finished; the molar ratio of the 4-aminodiphenylamine-2-sulfonic acid diazonium salt to the H acid is 1: 1-0.98: 1;
(3) monocondensation of cyanuric chloride or cyanuric fluoride
Pulping cyanuric chloride or cyanuric fluoride for half an hour, slowly dripping the monoazo dye solution of the H acid prepared in the step (2) into the pulping liquid of the cyanuric chloride or the cyanuric fluoride, controlling the reaction pH value to be between 4 and 5, keeping the temperature to be between 0 and 5 ℃, keeping the reaction for 1 to 2 hours under the condition, detecting the monoazo dye of the H acid prepared in the step (2) as an end point through thin-layer chromatography, and preparing a reaction liquid containing a monoacid product of the cyanuric chloride or the cyanuric fluoride; the molar ratio of the cyanuric chloride or the cyanuric fluoride to the monoazo dye of the H acid is 1: 1-1.03: 1;
(4) dimeric reaction of cyanuric chloride or cyanuric fluoride
Dissolving blue chromophore a1 containing anthraquinone chromophore prepared by reacting bromamine acid with M-bis or M-acid in water, slowly dropwise adding into the cyanuric chloride or cyanuric fluoride polycondensation product reaction liquid prepared in the step (3), controlling the reaction temperature to be 45-55 ℃, controlling the pH value to be 5-6, keeping the reaction for 4-6 hours under the condition, detecting no blue chromophore by thin-layer chromatography and liquid chromatography as a reaction end point, drying at 75 ℃ after the reaction is finished, and grinding the dye by grinding equipment to obtain the active dye solid powder shown in the final compound (I); the molar ratio of the blue chromophore a1 of the anthraquinone chromophore to the cyanuric chloride or the cyanuric fluoride polycondensate is 0.97: 1-1.03: 1; the structural formula of the blue chromophore a1 containing anthraquinone color body is shown in the specification
8. The preparation method of high performance brilliant blue reactive dye with double color bodies according to claim 7, characterized in that, in step (4), the grinding device used for grinding the dye by the grinding device specifically comprises a device body (1), a support seat (10) is welded on the back of the device body (1), a driving motor (9) is installed at the middle position of the top of the support seat (10), the output end of the driving motor (9) is connected with a rotating shaft (11), the other end of the rotating shaft (11) penetrates through the support seat (10) and is connected with the top of the device body (1) through a bearing, an annular grinding cavity (3) is fixed at the top of the device body (1) outside the rotating shaft (11), connecting ports (18) are uniformly formed at the bottom of the annular grinding cavity (3), and discharging channels (2) are connected inside the device body (1) at the positions of the connecting ports (18), and the vertical welding in the inside of discharging channel (2) has recipient (16), the inside sliding connection of recipient (16) has triangle-shaped piston seat (17), and the vertical welding in apex angle position department of triangle-shaped piston seat (17) has telescopic sleeve (20), and the other end of telescopic sleeve (20) extends to the top of recipient (16), air inlet (27) have all been seted up to the bottom of the both sides of telescopic sleeve (20), gas vent (26) have been seted up to the bottom of recipient (16), discharge gate (25) have all been seted up to recipient (16), the top sliding connection in connector (18) inside has wave type electromagnetic plate one (19), and the trough position department of wave type electromagnetic plate one (19) all evenly seted up discharge opening (23), the bottom of wave type electromagnetic plate one (19) is fixed with the other end of telescopic sleeve (20), and telescopic sleeve (20) is linked together with discharge opening (23), articulated shaft (15) have all been welded to the both sides of pivot (11), and the inside of articulated shaft (15) articulates there is articulated rod two (14), limiting plate (28) have all been welded to articulated rod two (14) and the top of articulated shaft (15) articulated position department, the other end of articulated rod two (14) is connected with annular grinding block (4), the bottom of annular grinding block (4) is evenly fixed with the wave type electromagnetic plate two (24) of mutually supporting with connector (18) inside, feed inlet (29) have been seted up at annular grinding block (4) top, the welding has transmission case (5) on pivot (11) of articulated shaft (15) top, and the inside toroidal cavity that has seted up of transmission case (5) in the pivot (11) outside, spout (22) have been seted up at transmission case (5) top of toroidal cavity position department, and equidistant welding in the annular cavity top of spout (22) both sides has lug (6), adjacent two inside sliding connection all has connecting block (21) of cavity between lug (6), and the vertical welding in top of connecting block (21) has connecting rod (8), the other end of connecting rod (8) passes spout (22) and extends to the top of transmission case (5) and articulates there is hinge bar (12), and the intermediate position department of hinge bar (12) articulates through the articulated shaft has bracing piece (7), the other end of bracing piece (7) welds each other with the top of supporting seat (10), the other end of hinge bar (12) all welds and strikes head (13).
9. The method for preparing high-performance double-color-body brilliant blue reactive dye according to claim 8, characterized in that: the wave-shaped electromagnetic plate II (24) and the wave-shaped electromagnetic plate I (19) are symmetrically arranged, and the wave crests of the wave-shaped electromagnetic plate II (24) and the wave crests of the wave-shaped electromagnetic plate I (19) correspond to each other.
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