CN112679981B - High-temperature high-chlorine-resistance active red dye for cotton and preparation method thereof - Google Patents
High-temperature high-chlorine-resistance active red dye for cotton and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-temperature high-chlorine-resistance active red dye for cotton, which comprises a compound shown as a structural general formula I, wherein R is shown in the structural general formula I1is-H or-SO3H; the R is2is-H; x is Cl; m is Na and the preparation method comprises the following steps; (1) preparing J acid X-type red reactive dye; (2) preparation of reactive red dye for high-temperature chlorine-resistant cotton. According to the invention, diethylenetriamine is selected as a linking group, two J acid type monoazo red reactive dyes are linked together to form a final reactive red dye, the diethylenetriamine is not on a J acid type monoazo red chromophore through the separation effect of a triazine ring, the color performance of the final dye is not influenced, and a fatty chain secondary amine group reserved in a diethylenetriamine structure in a molecule of the final reactive red dye contains lone pair electrons, has higher activity, can preferentially react with effective chlorine in an environmental medium, and avoids the damage of a covalent bond between a dye chromophoric system and a dye-fiber by the effective chlorine.
Description
Technical Field
The invention relates to the technical field of reactive dyes, in particular to a reactive red dye for high-temperature high-chlorine-resistance cotton and a preparation method thereof.
Background
The reactive dye has complete chromatogram and rich varieties, is widely applied to the dye application of cellulose fibers and protein fibers, and can react with hydroxyl on the cellulose fibers or amino on the protein fibers under the alkaline condition to be covalently bonded on the fibers due to the reactive groups contained in the molecular structure of the reactive dye, so that the wet rubbing fastness of the fibers dyed by the reactive dye is excellent.
Reactive dyes dyed fibers, when the dyed fabric is immersed in water containing reactive chlorine, discoloration and fading can occur, possibly because some parts of the dye (e.g., -N ═ are poorly stable to chlorine and are easily destroyed by reactive chlorine oxidation. It is believed that the poor fastness to chlorine of the reactive dyes is due to the reactive chlorine breaking the covalent bonds between the dye and the fiber and even destroying the dye's chromophoric system, resulting in changes in the depth and shade of the fabric. Therefore, how to overcome the problem and develop some new dye structures, the effective chlorine can avoid damaging the color system of the dye and the bonding bond between the effective chlorine and the fiber, and the improvement of the chlorine resistance of the dyed fabric becomes a difficult problem to be continuously solved by the dye and printing and dyeing industry.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the active red dye for the high-temperature high-chlorine-resistance cotton and the preparation method thereof. Therefore, the reactive red dye has the advantages of common reactive dyes, has excellent high fastness to chlorine, and has wide application prospect.
In order to achieve the purpose, the invention provides the following technical scheme: a reactive red dye for high-temperature chlorine-resistant cotton 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.
Preferably, R is as described in structural formula I1is-H or-SO3H; the R is2is-H; x is Cl; m is Na.
Preferably, the commercialized dye comprises 75-85% of active red dye, 5-15% of dispersing agent, 0.1-0.5% of dustproof agent and 5-15% of anhydrous sodium sulphate by mass percent.
Preferably, the dust-proofing agent is a water-soluble polymer compound.
Preferably, the commercial dye is used for dyeing of cellulose fibers, which are hydroxyl-and/or nitrogen-containing cellulose fibers.
Preferably, the cellulose fiber is cotton, viscose, hemp or a blended fabric of a plurality of cotton, viscose and hemp.
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) preparation of J acid X-type red reactive dye
A1: pulping cyanuric chloride or cyanuric fluoride for half an hour, slowly and dropwisely adding a J acid compound a solution into the cyanuric chloride or cyanuric fluoride pulping solution, controlling the reaction pH value to be 2-3, keeping the temperature at 0-5 ℃, keeping the reaction for 1-2 hours under the condition, detecting that no J acid compound a is taken as a reaction end point by an Ehrlich reagent, and preparing a reaction solution of a polycondensation product b of cyanuric chloride and the J acid compound a;
a2: adding 100% folded p-anisidine ortho-sulfonic acid compound c, crushed ice and a small amount of water into a beaker, grinding the ice for 2 hours, adding HCL solution, continuously stirring and reacting for 1 hour, slowly dropwise adding sodium nitrite solution, continuously reacting for 30-60 minutes after dropwise adding is finished, detecting no p-anisidine ortho-sulfonic acid compound c as a reaction end point by using an Ehrlich reagent, and removing excessive nitrous acid through sulfamic acid to prepare diazonium salt d of the p-anisidine ortho-sulfonic acid compound c;
a3: slowly adding the diazonium salt d in the step A2 into the reaction solution of the condensation product b in the step A1, adjusting the pH value of the solution to 6-7 by using baking soda, keeping the temperature at 5-10 ℃, reacting for 2-4 hours, detecting that no diazonium salt and a coupling component are used as reaction end points by a ring penetration method, and preparing a J-acid X-type red reactive dye e after the reaction is finished;
wherein the molar ratio of the cyanuric chloride or the cyanuric fluoride to the J acid compound a in the step A1 is 1: 1-1.03: 1; in the step A2, the molar ratio of the p-anisidine ortho-sulfonic acid compound c to the hydrochloric acid is 1: 1.05-1.1; in the step A2, the molar ratio of the p-anisidine ortho-sulfonic acid compound c to the sodium nitrite is 1: 1.01-1.03; in the step A3, the molar ratio of the diazonium salt d to the condensation product b is 1: 1-1.02: 1;
(2) preparation of reactive red dye for high-temperature chlorine-resistant cotton
B1: adding 100% of diethylenetriamine into the J acid X-type red reactive dye e prepared in the step (1), heating to 30-40 ℃, regulating the pH value of a reaction system to about 7, keeping the reaction condition for continuous reaction for 1-2 hours, detecting the reaction end point through thin layer chromatography or liquid phase, drying at 75 ℃ after the reaction is finished, and grinding to obtain the final reactive dye solid powder f shown in the general formula I, wherein the molar ratio of the diethylenetriamine to the J acid X-type red reactive dye e is 0.48: 1-0.51: 1.
A pulping device in a preparation method of an active red dye for high-temperature high-chlorine-resistance cotton comprises a main body unit and a pulping unit, wherein the main body unit comprises a bottom plate, a positioning seat arranged at the top of the bottom plate and an L-shaped fixing piece detachably arranged at the top of the bottom plate on one side of the positioning seat, and a beaker placing groove is arranged at the top of the positioning seat; the pulping unit comprises a fixing assembly, a rotating assembly, a deflection assembly and a pulping assembly, wherein the fixing assembly comprises a fixing box vertically arranged at the top end of one side, close to the positioning seat, of the L-shaped fixing piece and a fixing barrel arranged at the bottom of the fixing box through a connecting plate, and first discharge holes are uniformly formed in the outer side wall of the bottom of the fixing barrel along the circumferential direction of the fixing barrel; the rotating assembly comprises a driving rod which is vertically arranged in the fixed box and is coaxial with the fixed cylinder, a motor which is arranged in the fixed box and is connected with the driving rod through a chain mechanism, a rotating cylinder which is arranged in the fixed cylinder and is in clearance fit with the fixed cylinder, and a rotating rod which is vertically arranged at the middle position of the bottom of the rotating cylinder and penetrates through the fixed cylinder, wherein discharge holes II are uniformly formed in the outer side of the bottom of the rotating cylinder, the center of the bottom end in the rotating cylinder inclines towards the outer side edge, and the bottom end of the driving rod extends to be fixedly connected with the middle position of the bottom end in the rotating cylinder; the deflection assembly comprises two side plates symmetrically fixed at the bottom end of the rotating rod, two rectangular deflection blocks symmetrically hinged between the two side plates, a pair of pull rods hinged on opposite sides of the two rectangular deflection blocks, a positioning rod hinged at one end of the pull rod away from the rectangular deflection blocks, and a circular track arranged at the bottom of the fixing cylinder and coaxial with the rotating rod, wherein the top of the positioning rod extends into the circular track and is provided with clamping balls, the circular track is alternately provided with wave troughs and wave crests along the circumferential direction of the circular track, the upper half of the cross section of the circular track is provided with clamping parts matched with the clamping balls, and the lower half of the cross section of the circular track is provided with positioning parts matched with the positioning rods; the pulping component comprises a first stirring rod vertically and rotatably arranged at the bottom end of a rectangular deflection block, an arc-shaped rack arranged at the bottom of the rectangular deflection block and concentric with a hinging shaft of the rectangular deflection block, a bevel gear arranged at the outer side of the first stirring rod and meshed with the arc-shaped rack, an oscillating ball hinged at the bottom end of the first stirring rod, a first fan plate uniformly arranged at the outer side of the first stirring rod along the circumferential direction of the first stirring rod, a fixed block vertically arranged at the bottom end of the opposite sides of the two rectangular deflection blocks, a second stirring rod vertically arranged at the bottom of the rectangular deflection block and parallel to the first stirring rod through a damping rotating shaft, and a second fan plate uniformly arranged at the outer side of the second stirring rod along the circumferential direction of the second stirring rod, wherein micropores are uniformly arranged on the second fan plate, the oscillating ball is hollow, a counterweight ball is arranged in the oscillating ball, and convex columns are uniformly arranged at the outer side of the oscillating ball, the bottom outside the fixed cylinder is provided with a protective cylinder, and the bottom of the protective cylinder is flush with the bottom of the side plate.
Preferably, the articulated shaft of rectangle deflection piece and pull rod and the articulated shaft of pull rod and locating lever are parallel with the tangent line of circular track.
Compared with the prior art, the invention has the beneficial effects that:
(1) the reactive red dye provided by the invention contains two monochlorotriazine reactive groups, can be used for dyeing fibers at high temperature, and in order to increase the stability of azo bonds in a reactive red dye chromogen system, p-anisidine-2, 5-disulfonic acid or p-anisidine-2-sulfonic acid is selected as a diazo component, a J acid compound is selected as a coupling component, the prepared reactive red dye is a monoazo structure containing J acid, meanwhile, the monoazo dye taking the J acid as the coupling component is orange, but the methoxy group on the diazo component has a strong electron-donating effect, so that the branched monoazo dye is a bright red dye.
(2) The ortho-position of the azo bond in the molecular structure of the dye has a sulfonic group, and the azo bond can form a hydrogen bond with the azo bond, so that the stability of the azo bond is improved, and the azo bond can effectively resist the oxidation of available chlorine in an environmental medium.
(3) The invention selects diethylenetriamine as a linking group to link two J acid monoazo red reactive dyes together to form the final reactive red dye, the diethylenetriamine does not exist on a J acid monoazo red color body through the separation effect of a triazine ring and does not influence the color performance of the final dye, the aliphatic chain secondary amine group reserved in the diethylenetriamine structure in the molecule of the final reactive red dye contains lone pair electrons, has higher activity and can preferentially react with effective chlorine in an environmental medium to avoid the damage of the covalent bond between a dye color system and dye-fiber by the effective chlorine, thereby further improving the capacity of the final reactive red dye for resisting the effective chlorine and obviously improving the chlorine resistance of dyed fabrics, namely, the reactive red dye of the invention not only has the advantages of the traditional reactive dye, but also has obvious high chlorine resistance, has wide application prospect.
(4) According to the invention, the fixing cylinder is arranged at the bottom of the fixing box through the connecting plate, the first discharge holes are uniformly formed in the outer side wall of the bottom of the fixing cylinder along the circumferential direction of the fixing cylinder, the rotary cylinder in clearance fit with the fixing cylinder is arranged in the fixing cylinder, the second discharge holes are uniformly formed in the outer side of the bottom of the rotary cylinder, during pulping, cyanuric chloride is placed in the rotary cylinder to be separated from water and ice, and when the second discharge holes of the rotary cylinder and the first discharge holes of the fixing cylinder coincide with each other along with the rotation of the rotary cylinder, cyanuric chloride is slowly added into the flask to be mixed with the water and the ice under the centrifugal action, so that the problems that much cyanuric chloride and little water are adhered into a bulk state in initial mixing, the slurry is not uniform, and the dye effect is influenced are avoided.
(5) The invention symmetrically hinges a rectangular deflection block between two side plates, hinges a pair of pull rods at the opposite sides of the two rectangular deflection blocks, hinges a positioning rod at one end of the pull rod far away from the rectangular deflection block, and hinges a circular track coaxial with the rotation rod at the bottom of a fixed cylinder, the top of the positioning rod extends to the inside of the circular track and is provided with a clamping ball, the circular track is alternately provided with a trough and a wave crest along the circumferential direction, the upper half part of the cross section of the circular track is provided with a clamping part matched with the clamping ball, the lower half part of the cross section of the circular track is provided with a positioning part matched with the positioning rod, when in use, the positioning rod slides in the circular track, because the circular track is alternately provided with the trough and the wave crest along the circumferential direction, the positioning rod continuously moves up and down in the rotation process, and when the positioning rod continuously moves up and down in the rotation process, can drive the rectangle piece that deflects through the pull rod and constantly take place to deflect to make the making beating subassembly in circular motion stirring process, constantly take place to deflect, improve stirring effect.
(5) The invention arranges an arc rack concentric with the hinge shaft of the rectangular deflection block at the bottom of the rectangular deflection block, a bevel gear meshed with the arc rack at the outer side of a stirring rod, a vibration ball at the bottom of the stirring rod, a first fan plate at the outer side of the stirring rod along the circumferential direction, a fixed block at the bottom of the opposite side of the two rectangular deflection blocks, a second stirring rod parallel to the first stirring rod at the bottom of the rectangular deflection block through a damping rotating shaft, and a second fan plate at the outer side of the stirring rod along the circumferential direction, wherein, the second fan plate is provided with micropores, the vibration ball is hollow, a counterweight ball is arranged in the vibration ball, convex columns are arranged on the outer side of the vibration ball, when in use, the first stirring rod deflects synchronously during the continuous deflection of the rectangular deflection block, and the bevel gear on the first stirring rod is meshed with the arc rack, when the stirring rod rotates, namely the stirring rod rotates continuously in the process of circular motion around the rotating rod, the stirring rod also rotates continuously in the process of deflecting, the oscillating ball generates deflection when the stirring rod deflects, ice can be crushed, the deflection improves the stirring effect, in addition, as the counterweight ball is arranged in the oscillating ball, the counterweight ball collides with the oscillating ball, the deflection degree of the oscillating ball is improved, the oscillating ball vibrates per se, the cyanuric chloride in the slurry is prevented from forming a conglobation image, the stirring rod I can stir the slurry one by one when the stirring rod rotates continuously in the process of deflecting and rotating around the rotating rod, the fan plate on the outer side of the stirring rod I can push the fan plate II through the fan plate I, the stirring rod II rotates, and in the process of pushing the fan plate II through the fan plate I, the first fan plate can press and extrude the slurry in the flask to the second fan plate after gathering the slurry, so that the slurry can pass through the micropores of the second fan plate, and the bonded and agglomerated cyanuric chloride in the obtained pulping liquid is avoided.
Drawings
FIG. 1 is a reaction scheme of the present invention;
FIG. 2 is a schematic structural view of a pulping apparatus of the present invention;
FIG. 3 is a schematic view of a portion of the structure of FIG. 2 at A;
FIG. 4 is a schematic view of the circular track structure of the beating device of the present invention;
fig. 5 is a structural schematic diagram of a beating assembly of the beating device of the invention.
In the figure: 1. a base plate; 2. positioning seats; 3. an L-shaped fixing member; 4. a beaker placing groove; 5. a fixing assembly; 51. a fixing box; 52. a connecting plate; 53. a fixed cylinder; 54. a first discharge hole; 6. a rotating assembly; 61. a drive rod; 62. a chain mechanism; 63. a motor; 64. a rotating drum; 65. rotating the rod; 66. a discharge hole II; 7. a deflection assembly; 71. a side plate; 72. a rectangular deflection block; 73. a pull rod; 74. positioning a rod; 75. a circular track; 76. blocking the ball; 77. a clamping part; 78. positioning; 8. a beating assembly; 81. a first stirring rod; 82. an arc-shaped rack; 83. a bevel gear; 84. oscillating the ball; 85. a first fan plate; 86. a fixed block; 87. a second stirring rod; 88. a second fan plate; 89. a counterweight ball; 810. a convex column.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
The embodiment provided by the invention comprises the following steps: a high-temperature high-chlorine-resistance reactive red dye for cotton is a compound shown in a structural general formula I-1;
the preparation method of the compound shown in the structural general formula I-1 is carried out according to the following process, and comprises the following specific steps:
(1) preparation of J acid X-type red reactive dye
A1: placing 19.2g of cyanuric chloride with the bending of 100% in a rotary drum of a pulping device, adding 200g of ice and 20ml of water into a 1000ml beaker, placing the beaker under the pulping device, pulping to a viscous state, adding 23.9g of 2-amino-5-naphthol-7-sulfonic acid (J acid) with the bending of 100% and 600ml of water into the 1000ml beaker, adjusting the pH of the system to about 6.8 by using 15% NaOH solution, stirring and dissolving, slowly adding the obtained solution into the above cyanuric chloride pulping liquid, controlling the reaction conditions to be 0-5 ℃ and pH to be 2-3, continuously reacting for 60 minutes under the conditions, and detecting no J acid compound a as a reaction end point by using an Ehrlich reagent to obtain a primary condensation product solution of cyanuric chloride and J acid;
a2: adding 20.3g of p-anisidine-2-sulfonic acid with the refractive index of 100%, 200g of ice and 20ml of water into a 1000ml beaker, carrying out ice grinding for 2 hours, adding 12.2g of industrial hydrochloric acid (30%), continuously stirring for reaction for 1 hour, dissolving 7.1g of sodium nitrite solid with the refractive index of 100% into 30ml of water, slowly dripping into the system, keeping the reaction solution as congo red test paper in a slight blue color and KI test paper in a slight blue color in the dripping process, keeping the temperature of the reaction system at 0-5 ℃ after finishing dripping, continuously reacting for 1 hour, detecting no p-anisidine ortho-sulfonic acid compound c as a reaction endpoint through an Ehrlich reagent, and removing excessive nitrous acid by using sulfamic acid after the reaction is finished to prepare a diazonium salt solution of p-anisidine-2-sulfonic acid;
a3: adding the diazonium salt solution of the p-anisidine-2-sulfonic acid into a primary condensation product solution of cyanuric chloride and J acid, controlling the pH value of the reaction to be between 6 and 7, keeping the temperature at 8 ℃, keeping the reaction for 3 hours under the condition, detecting no diazonium salt and coupling components as reaction end points by a ring penetration method, and preparing the J acid X-type red reactive dye after the reaction is finished;
(2) preparation of reactive red dye for high-temperature chlorine-resistant cotton
B1: and (2) dropwise adding 5.15g of diethylenetriamine with the volume of 100% into the X-type red reactive dye solution of J acids prepared in the step (1), heating to 35 ℃, regulating and controlling the pH value of the reaction system to be about 7, keeping the reaction condition for continuous reaction for 2 hours, and detecting the reaction end point through thin-layer chromatography or liquid phase. And after the reaction is finished, drying at 75 ℃, and grinding to obtain the final high-temperature active red dye I-1 solid powder for the high-chlorine-resistance cotton.
Preparation of commercial dye
The commercial active red dye is prepared by mixing the active red dye I-1, a dispersing agent (a methyl naphthalene sulfonic acid formaldehyde condensation compound, the condensation degree is 4, and the sulfonation degree is 2), an aqueous high-molecular dustproof agent and anhydrous sodium sulphate according to the mass percentage of 85%, 5%, 0.1% and 9.9%.
As shown in fig. 2-5, the beating device in step a1 in the preparation method of the high-temperature-resistant reactive red dye for high-chlorine cotton specifically comprises a main body unit and a beating unit, wherein the main body unit comprises a bottom plate 1, a positioning seat 2 arranged at the top of the bottom plate 1 and an L-shaped fixing piece 3 detachably arranged at the top of the bottom plate 1 at one side of the positioning seat 2, wherein the top of the positioning seat 2 is provided with a beaker placing groove 4; the pulping unit comprises a fixing assembly 5, a rotating assembly 6, a deflection assembly 7 and a pulping assembly 8, wherein the fixing assembly 5 comprises a fixing box 51 vertically arranged at the top end of one side, close to the positioning seat 2, of the L-shaped fixing piece 3 and a fixing cylinder 53 arranged at the bottom of the fixing box 51 through a connecting plate 52, and first discharge holes 54 are uniformly formed in the outer side wall of the bottom of the fixing cylinder 53 along the circumferential direction of the fixing cylinder; the rotating assembly 6 comprises a driving rod 61 vertically arranged inside the fixed box 51 and coaxial with the fixed cylinder 53, a motor 63 arranged inside the fixed box 51 and connected with the driving rod 61 through a chain mechanism 62, a rotating cylinder 64 arranged inside the fixed cylinder 53 and in clearance fit with the fixed cylinder 53, and a rotating rod 65 vertically arranged in the middle of the bottom of the rotating cylinder 64 and penetrating through the fixed cylinder 53, wherein the outer side of the bottom of the rotating cylinder 64 is uniformly provided with a second discharge hole 66, the center of the bottom end inside the rotating cylinder 64 is inclined to the outer side edge, and the bottom end of the driving rod 61 extends to be fixedly connected with the middle of the bottom end inside the rotating cylinder 64; the deflection assembly 7 assembly comprises two side plates 71 symmetrically fixed at the bottom end of the rotating rod 65, two rectangular deflection blocks 72 symmetrically hinged between the two side plates 71, a pair of pull rods 73 hinged on opposite sides of the two rectangular deflection blocks 72, a positioning rod 74 hinged at one end of the pull rod 73 far away from the rectangular deflection blocks 72, and a circular track 75 provided with the bottom of the fixing cylinder 53 and coaxial with the rotating rod 65, wherein the top of the positioning rod 74 extends into the circular track 75 and is provided with a clamping ball 76, the circular track 75 is alternately provided with a wave trough and a wave crest along the circumference thereof, the upper half part of the cross section of the circular track 75 is provided with a clamping part 77 mutually matched with the clamping ball 76, and the lower half part of the cross section of the circular track 75 is provided with a positioning part 78 mutually matched with the positioning rod 74; the pulping component 8 comprises a first stirring rod 81 vertically and rotatably arranged at the bottom end of a rectangular deflection block 72, an arc-shaped rack 82 which is arranged at the bottom of the rectangular deflection block 72 and is concentric with a hinged shaft of the rectangular deflection block 72, a bevel gear 83 which is arranged at the outer side of the first stirring rod 81 and is meshed with the arc-shaped rack 82, an oscillating ball 84 which is hinged at the bottom end of the first stirring rod 81, a first fan plate 85 which is uniformly arranged at the outer side of the first stirring rod 81 along the circumferential direction of the first stirring rod 81, a fixed block 86 which is vertically arranged at the bottom end of the opposite sides of the two rectangular deflection blocks 72, a second stirring rod 87 which is vertically arranged at the bottom of the rectangular deflection block 72 and is parallel to the first stirring rod 81 through a damping rotating shaft, and a second fan plate 88 which is uniformly arranged at the outer side of the second stirring rod 87 along the circumferential direction of the second stirring rod 87, wherein micropores are uniformly arranged on the second fan plate 88, the oscillating ball 84 is hollow, and the oscillating ball 89 is arranged inside the oscillating ball 84, the outer side of the oscillating ball 84 is uniformly provided with convex columns 810, the hinged shafts of the rectangular deflection block 72 and the pull rod 73 and the hinged shafts of the pull rod 73 and the positioning rod 74 are parallel to the tangent line of the circular track 75, the bottom end of the outer side of the fixed cylinder 53 is provided with a protective cylinder, and the bottom end of the protective cylinder is flush with the bottom end of the side plate.
Example two
The embodiment provided by the invention comprises the following steps: a high-temperature high-chlorine-resistance reactive red dye for cotton is a compound shown in a structural general formula I-2;
in this example, the preparation method of reactive dye I-2 and the beating device in step a1 in the preparation method of reactive dye are the same as in example 1, except that N-methyl J acid replaces J acid in step a1 of preparation of I-1 to prepare the corresponding reactive red dye, and reactive dye I-2 replaces reactive dye I-1 to prepare the corresponding commercial dye.
EXAMPLE III
The embodiment provided by the invention comprises the following steps: a reactive red dye for high-temperature high-chlorine-resistance cotton is a compound shown as a structural general formula I-3:
in this example, the preparation method of the reactive dye I-3 and the beating device in the step a1 in the preparation method of the reactive dye are the same as those in example 1, except that p-anisidine-2, 5-disulfonic acid is used to prepare the corresponding reactive red dye instead of the p-anisidine-2-sulfonic acid in the preparation step (1) of I-1, and the reactive dye I-3 is used to prepare the corresponding commercial dye instead of the reactive dye I-1.
Example four
The embodiment provided by the invention comprises the following steps: a reactive red dye for high-temperature high-chlorine-resistance cotton is a compound shown in a structural general formula I-4:
in this example, the preparation method of the reactive dye I-4 and the beating device in the step a1 in the preparation method of the reactive dye are the same as those in example 1, except that p-anisidine-2, 5-disulfonic acid and N-methyl J acid are used to replace p-anisidine-2-sulfonic acid and J acid in the preparation step (1) of I-1 to prepare the corresponding reactive red dye, and the reactive dye I-4 is used to replace the reactive dye I-1 to prepare the corresponding commercial dye.
EXAMPLE five
In the reactive dye, the preparation method of the reactive dye and the preparation method of the reactive dye in the embodiment, the beating device in the step A1 is the same as that in the embodiment 1, except that:
in this example, the reactive red dye was mixed with a dispersing agent (a methyl naphthalene sulfonic acid formaldehyde condensate, degree of condensation 4, degree of sulfonation 2), an aqueous polymer dustproof agent and anhydrous sodium sulfate in a ratio of 80 mass%, 10 mass%, 0.5 mass%, and 9.5 mass% to obtain a commercial reactive red dye.
EXAMPLE six
The active dye, the preparation method of the active dye and the beating device in the step A1 in the preparation method of the active dye in the embodiment are the same as those in the embodiment 1, except that:
in this example, the reactive red dye was mixed with a dispersing agent (a methyl naphthalene sulfonic acid formaldehyde condensate, degree of condensation 4, degree of sulfonation 2), an aqueous polymer dustproof agent, and anhydrous sodium sulfate in a ratio of 85 mass%, 8 mass%, 0.1 mass%, and 6.9 mass% to obtain a commercial reactive red dye.
Verification test
2g of the commercial dye in each of examples 1-6, 2g of the commercial dye, 8g of urea, 2.5g of sodium bicarbonate, 60g of sodium alginate paste, 1g of anti-dyeing salt and 26.5g of water were added to prepare an active red printing paste, the 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 red dye cotton provided by the invention has good color fastness, which reaches more than 4 grades; the reactive red dye has the color fixation rate of more than 83 percent, is higher than the color fixation rate of the traditional reactive dye by more than 10 percent, and has good chlorine resistance and fastness of more than level 4 after the innovative design of the molecular structure of the reactive dye.
The preparation method of the active red dye for high-temperature chlorine-resistant cotton comprises the following specific action principles of the beating device adopted in the step A1: before application, a flask is placed inside a flask placing groove 4, a pulping unit extends into the flask, an L-shaped fixing part 3 is fixed through a bolt, water and ice are placed inside the flask, cyanuric chloride is placed inside a rotary drum 64, when the device is applied, a motor 63 is started, the motor 63 rotates to drive a driving rod 61 to rotate through a chain mechanism 62, the driving rod 61 rotates to drive the rotary drum 64 to rotate, along with the rotation of the rotary drum 64, when a second discharge hole 66 of the rotary drum 64 is overlapped with a first discharge hole 54 of a fixed drum 53, cyanuric chloride is slowly added into the flask to be mixed with the water and the ice under the centrifugal effect, the phenomenon that much cyanuric chloride and little water are added in initial mixing to cause the cyanuric chloride to be bonded into a bulk shape, so that the serous is not uniform and the effect of a dye is influenced, when the rotary drum 64 rotates, a rotary rod 65 at the bottom of the rotary rod rotates, and when the rotary rod 65 rotates, the positioning rod 74 slides in the circular track 75, because the circular track is alternately provided with wave troughs and wave crests along the circumferential direction, the positioning rod 74 continuously moves up and down in the rotating process, when the positioning rod 74 continuously moves up and down in the rotating process, the rectangular deflection block 72 can be driven to continuously deflect through the pull rod 73, so that the pulping component continuously deflects in the circumferential motion stirring process, the stirring effect is improved, in the continuous deflection process of the rectangular deflection block 72, the first stirring rod 81 also synchronously deflects, the bevel gear 83 on the first stirring rod 81 is meshed with the arc-shaped rack 82, when the first stirring rod 81 rotates, namely, the first stirring rod 81 continuously deflects and rotates in the circumferential motion process around the rotating rod 65, and the oscillating ball 84 generates deflection when the first stirring rod 81 deflects, on one hand, the ice can be crushed, on the other hand, the stirring effect is improved due to the deflection, and as the counterweight ball 89 is arranged in the oscillating ball 84, the deflection degree of the oscillating ball is improved due to the collision between the counterweight ball 89 and the oscillating ball 84, on the other hand, the oscillating ball per se vibrates, the cyanuric chloride in the slurry is prevented from forming a conglomerate shape, while the first stirring rod 81 continuously deflects and rotates during the circular motion around the rotating rod 65, the first fan plate 85 on the outer side can stir the slurry, the second fan plate 88 can be pushed by the first fan plate 85 on the other side, so that the second stirring rod 87 rotates, while the first fan plate 85 pushes the second fan plate 88, the first fan plate 85 can gather the slurry in the flask and press the second fan plate 88 to generate extrusion, so that the slurry passes through the micropores of the second fan plate 88, and the bonded and agglomerated cyanuric chloride in the obtained slurry is avoided.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and/or modifications of the invention can be made, and equivalents and modifications of some features of the invention can be made without departing from the spirit and scope of the invention.
Claims (9)
1. The reactive red dye for the high-temperature high-chlorine-resistance cotton is characterized by being a compound shown as a structural general formula I:
in the above formula I, R1is-H or-SO3H; the R is2is-H; the X is F or Cl; m is-H or an alkali metal.
2. The reactive red dye for high-temperature high-chlorine-resistance cotton according to claim 1, wherein: in the general structural formula I, X is Cl; m is Na.
3. The commercial dye prepared from the reactive red dye for high-temperature chlorine-resistant cotton according to any one of claims 1-2, wherein the reactive red dye comprises the following components in percentage by weight: the commercial dye comprises 75-85% of reactive red 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 dye according to claim 3, characterized in that: 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 the commercial dye according to claim 4, characterized in that: the commercial dye is used for dyeing cellulose fibers, and the cellulose fibers are cellulose fibers containing hydroxyl and/or nitrogen.
6. Use of the commercial dye according to claim 5, characterized in that: the cellulose fiber is cotton, viscose, hemp or various blended fiber fabrics thereof.
7. The preparation method of the active red dye for high-temperature high-chlorine-resistance cotton as claimed in any one of claims 1 to 2, wherein the method comprises the following steps: the preparation method of the compound shown in the structural general formula I is carried out according to the following flow, and comprises the following specific steps;
(1) preparation of J acid X-type red reactive dye
A1: pulping cyanuric chloride or cyanuric fluoride for half an hour, slowly and dropwisely adding a J acid compound a solution into the cyanuric chloride or cyanuric fluoride pulping solution, controlling the reaction pH value to be 2-3, keeping the temperature at 0-5 ℃, keeping the reaction for 1-2 hours under the condition, detecting that no J acid compound a is taken as a reaction end point by an Ehrlich reagent, and preparing a reaction solution of a polycondensation product b of cyanuric chloride and the J acid compound a;
a2: adding 100% folded p-anisidine ortho-sulfonic acid compound c, crushed ice and a small amount of water into a beaker, grinding the ice for 2 hours, adding HCL solution, continuously stirring and reacting for 1 hour, slowly dropwise adding sodium nitrite solution, continuously reacting for 30-60 minutes after dropwise adding is finished, detecting no p-anisidine ortho-sulfonic acid compound c as a reaction end point by using an Ehrlich reagent, and removing excessive nitrous acid through sulfamic acid to prepare diazonium salt d of the p-anisidine ortho-sulfonic acid compound c;
a3: slowly adding the diazonium salt d in the step A2 into the reaction solution of the condensation product b in the step A1, adjusting the pH value of the solution to 6-7 by using baking soda, keeping the temperature at 5-10 ℃, reacting for 2-4 hours, detecting that no diazonium salt and a coupling component are used as reaction end points by a ring penetration method, and preparing a J-acid X-type red reactive dye e after the reaction is finished;
wherein the molar ratio of the cyanuric chloride or the cyanuric fluoride to the J acid compound a in the step A1 is 1: 1-1.03: 1; in the step A2, the molar ratio of the p-anisidine ortho-sulfonic acid compound c to the hydrochloric acid is 1: 1.05-1.1; in the step A2, the molar ratio of the p-anisidine ortho-sulfonic acid compound c to the sodium nitrite is 1: 1.01-1.03; in the step A3, the molar ratio of the diazonium salt d to the condensation product b is 1: 1-1.02: 1;
(2) preparation of reactive red dye for high-temperature chlorine-resistant cotton
B1: adding 100% diethylenetriamine into the J acid X-type red reactive dye e prepared in the step (1), heating to 30-40 ℃, regulating the pH value of a reaction system to 7, keeping the reaction condition for continuous reaction for 1-2 hours, detecting the reaction end point through thin layer chromatography or liquid phase, drying at 75 ℃ after the reaction is finished, and grinding to obtain the final reactive dye solid powder f shown in the general formula I, wherein the molar ratio of the diethylenetriamine to the J acid X-type red reactive dye e is 0.48: 1-0.51: 1.
8. The preparation method of the reactive red dye for high-temperature high-chlorine-resistance cotton according to claim 7, wherein the reactive red dye comprises the following components in percentage by weight: the pulping device adopted for pulping the cyanuric chloride or the cyanuric fluoride in the step A1 specifically comprises a main body unit and a pulping unit, wherein the main body unit comprises a bottom plate (1), a positioning seat (2) arranged at the top of the bottom plate (1) and an L-shaped fixing piece (3) detachably arranged at the top of the bottom plate (1) on one side of the positioning seat (2), and the top of the positioning seat (2) is provided with a beaker placing groove (4); the pulping unit comprises a fixing assembly (5), a rotating assembly (6), a deflecting assembly (7) and a pulping assembly (8), wherein the fixing assembly (5) comprises a fixing box (51) vertically arranged at the top end of one side, close to the positioning seat (2), of the L-shaped fixing piece (3) and a fixing cylinder (53) arranged at the bottom of the fixing box (51) through a connecting plate (52), and first discharge holes (54) are uniformly formed in the outer side wall of the bottom of the fixing cylinder (53) along the circumferential direction of the fixing cylinder; the rotating assembly (6) comprises a driving rod (61) which is vertically arranged in the fixed box (51) and coaxial with the fixed cylinder (53), a motor (63) which is arranged in the fixed box (51) and connected with the driving rod (61) through a chain mechanism (62), a rotating cylinder (64) which is arranged in the fixed cylinder (53) and in clearance fit with the fixed cylinder (53), and a rotating rod (65) which is vertically arranged at the middle position of the bottom of the rotating cylinder (64) and penetrates through the fixed cylinder (53), wherein discharge holes II (66) are uniformly formed in the outer side of the bottom of the rotating cylinder (64), the center of the bottom end in the rotating cylinder (64) is inclined towards the outer side edge, and the bottom end of the driving rod (61) extends to be fixedly connected with the middle position of the bottom end in the rotating cylinder (64); the deflection assembly (7) assembly comprises two side plates (71) symmetrically fixed at the bottom end of the rotating rod (65), two rectangular deflection blocks (72) symmetrically hinged between the two side plates (71), a pair of pull rods (73) hinged at the opposite sides of the two rectangular deflection blocks (72), a positioning rod (74) hinged at one end of the pull rod (73) far away from the rectangular deflection block (72) and a circular track (75) arranged at the bottom of the fixed cylinder (53) and coaxial with the rotating rod (65), wherein the top of the positioning rod (74) extends to the inside of the circular track (75) and is provided with a ball clamping (76), the circular track (75) is alternately provided with wave troughs and wave crests along the circumference thereof, the upper half part of the cross section of the circular track (75) is provided with a clamping part (77) which is matched with the clamping ball (76), the lower half part of the cross section of the circular track (75) is provided with a positioning part (78) matched with the positioning rod (74); the pulping component (8) comprises a first stirring rod (81) vertically and rotatably arranged at the bottom end of the rectangular deflection block (72), an arc-shaped rack (82) which is arranged at the bottom of the rectangular deflection block (72) and is concentric with a hinge shaft of the rectangular deflection block (72), bevel gears (83) which are arranged at the outer side of the first stirring rod (81) and are meshed with the arc-shaped rack (82), oscillating balls (84) which are hinged at the bottom end of the first stirring rod (81), first fan plates (85) which are uniformly arranged at the outer side of the first stirring rod (81) along the circumferential direction of the first stirring rod (81), fixed blocks (86) which are vertically arranged at the bottom ends of the two opposite sides of the rectangular deflection block (72), second stirring rods (87) which are vertically arranged at the bottom of the rectangular deflection block (72) and are mutually parallel to the first stirring rod (81) through a damping rotating shaft, and second fan plates (88) which are uniformly arranged at the outer side of the second stirring rods (87) along the circumferential direction of the second stirring rods (87), wherein, evenly be provided with the micropore on fan board two (88), the inside cavity of vibration ball (84), and the inside of vibration ball (84) is provided with counter weight ball (89), the outside of vibration ball (84) evenly sets up projection (810), the bottom in the fixed cylinder (53) outside is provided with a protection section of thick bamboo, protection section of thick bamboo's bottom and curb plate bottom parallel and level.
9. The preparation method of the reactive red dye for high-temperature high-chlorine-resistance cotton according to claim 8, wherein the reactive red dye comprises the following components in percentage by weight: the articulated shaft of the rectangular deflection block (72) and the pull rod (73) and the articulated shaft of the pull rod (73) and the positioning rod (74) are parallel to the tangent line of the circular track (75).
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| FR2634773B1 (en) * | 1988-08-01 | 1991-01-25 | Sandoz Sa | NOVEL DISAZOIC COMPOUNDS, THEIR PREPARATION AND THEIR USE AS REACTIVE DYES |
| DE4140117C1 (en) * | 1991-12-05 | 1993-01-28 | Bayer Ag, 5090 Leverkusen, De | |
| DE4415313A1 (en) * | 1994-05-02 | 1995-11-09 | Hoechst Ag | Mixtures of fiber-reactive dyes and their use for dyeing fiber materials |
| GB9523575D0 (en) * | 1995-11-17 | 1996-01-17 | Zeneca Ltd | Organic chemical compounds and processes |
| GB9608488D0 (en) * | 1996-04-25 | 1996-07-03 | Zeneca Ltd | Compositions, processes and uses |
| JPH1158944A (en) * | 1997-08-12 | 1999-03-02 | Nippon Kayaku Co Ltd | Aqueous ink set, coloring material and coloring method |
| US6068667A (en) * | 1999-05-05 | 2000-05-30 | Everlight Usa, Inc. | Mixtures of symmetrical and unsymmetrical red reactive dyes |
| JP2001019881A (en) * | 1999-07-07 | 2001-01-23 | Nippon Kayaku Co Ltd | Red aqueous ink composition and colored body |
| EP1081196B1 (en) * | 1999-08-30 | 2002-07-24 | Ciba SC Holding AG | Process for colouring and printing polyamid containing materials |
| CN100404629C (en) * | 2002-12-27 | 2008-07-23 | 上海染料化工八厂 | Red dye composition and its preparation and use |
| GB0321437D0 (en) * | 2003-09-12 | 2003-10-15 | Dystar Textilfarben Gmbh & Co | High light fastness reactive red dyes |
| CN101481537A (en) * | 2008-01-08 | 2009-07-15 | 明德国际仓储贸易(上海)有限公司 | Novel chemically-reactive dye with N,N-dialkylamino bridging group |
| CN105273437B (en) * | 2015-10-20 | 2017-05-17 | 湖北华丽染料工业有限公司 | Red reactive dye as well as preparation method and application thereof |
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