Reactive dye with ultra-high fixation rate and ultra-high staining fastness for printing and pad dyeing, and preparation method and application thereof

Abstract

The present invention discloses a series of reactive dyes with ultra-high fixation rates and ultra-high staining fastness for printing and pad dyeing. The reactive dyes are represented by the general structural formula (I). The reactive dyes of the present invention contain two monoazo chromophores of identical structure and two or more reactive groups, which increases the probability of reaction between the dye and the fiber, resulting in an ultra-high fixation rate for the final dye. Furthermore, the spatial structure of the dye molecules is regulated by the steric hindrance and charge effects of the bridge group, causing spatial distortion and non-coplanarity of the dye molecules. This also reduces the directness of the dye molecular structure and its affinity with the fiber, thereby allowing unfixed dye to easily fall off the fiber surface and imparting ultra-high staining fastness to the dye. This overcomes the low fixation rates and poor staining fastness of existing commercial reactive dyes used for printing and pad dyeing of cellulosic fibers, and has broad application prospects. #imgabs0#

Description

Technical Field

[0001] The invention relates to the technical field of reactive dyes, in particular to reactive dyes with ultra-high fixation rate and ultra-high staining fastness for printing and pad dyeing, and a preparation method and application thereof. Background Art

[0002] Reactive dyes are an important class of organic synthetic dyes that react with cellulose fibers to form covalent bonds. Therefore, cellulose fibers colored with reactive dyes exhibit excellent wet fastness. However, because reactive dyes typically use water as a medium, hydrolysis side reactions can also occur. Currently, the fixation rate of reactive dyes on fibers is typically only between 50-80%. Large amounts of dye residue in dyeing wastewater not only waste resources but also further pollute the environment. Improving the dye fixation rate can not only effectively increase dye utilization, but also reduce the amount of dye residue in printing and dyeing wastewater. Therefore, how to improve the utilization rate of reactive dyes has long been a focus of attention in academia and the industry.

[0003] In the molecular structure design of reactive dyes, increasing the number of reactive groups can increase the probability of dye molecules reacting with fibers. For dyes containing multiple reactive groups, as long as at least one reactive group is capable of reacting with the fiber, the reactive dye can covalently bond to the fiber. Therefore, increasing the number of reactive groups in a reactive dye theoretically improves the dye's fixation rate on the fiber. However, in addition to the probability of reactive groups reacting with the fiber, other factors also influence the fixation rate of reactive dyes on the fiber, such as the dye's substantivity, reactivity, exhaustion rate, and dyeing process, all of which significantly influence the dye's fixation rate. For example, in exhaust dyeing, even if the reactive dye has a large number of reactive groups in its molecular structure, if the dye's substantivity is low and the dye-fiber affinity is weak, the dye's exhaustion rate will also be low. These dye molecules will not be able to react effectively with the fiber, and the multiple reactive groups will ultimately hydrolyze, resulting in a low dye fixation rate. Therefore, while increasing the number of reactive groups in the reactive dye molecular structure, how to control the physical properties of the entire reactive dye molecule to meet the requirements of the final dyeing process remains a technical challenge in the industry's development.

[0004] During the use of reactive dyes, unreacted and hydrolyzed dye will fall from printed and dyed fibers during the soaping process. This fallen dye can stain other white fibers, resulting in poor color fastness. Especially after the print fixation process, the dye that falls during soaping can stain the white background of the fabric, making the pattern color unclear and affecting product quality. Multiple soaping and hydrolysis cycles are required to alleviate this white background staining problem. This problem is closely related to the dye structure, and currently commercial dyes, especially yellow, orange, and red, all face this difficult-to-solve problem.

[0005] In the design of multi-reactive dyes, connecting the active groups through a bridge group is the most common method. The CAS registered structure of the molecular part of such a dye structure is shown below:

[0006]

[0007] At present, the compounds used as bridge groups generally include 3,5-diaminobenzoic acid (CN 107501998 A), p-phenylenediamine, 4,4'-diaminostilbene-disulfonic acid (DSD acid), 1,4-phenylenediamine-2-sulfonic acid (US 4845202), m-phenylenediamine, 2,4-diaminobenzenesulfonic acid (m-bis), 3,5-diaminobenzenesulfonic acid, 4-methyl-3,5-diaminobenzenesulfonic acid, 4-chloro-3,5-diaminobenzenesulfonic acid, 2-chloro-3,5-diaminobenzenesulfonic acid (EP 0387579A2), o-phenylenediamine, ethylenediamine, hydroxyethylethylenediamine, 2-methyl-1,4-phenylenediamine (Dyes and Dyeing, 2005, 42: 23-27), and 4,4-diaminobenzidine-2,2-disulfonic acid (CN117106322A). In these dye molecular structures, the primary function of bridging groups is to connect the dye chromophores, resulting in multiple active groups within the final dye molecule. However, once these bridging groups connect the chromophores to form a complete dye molecule, the molecular weight of the dye increases significantly, significantly altering various physical properties such as substantivity, affinity, solubility, reactivity, and association. These physical properties significantly impact the final dye's performance, particularly the dyeing process and the fastness properties of the dyed fiber.

[0008] In the application process of reactive dyes, how to obtain both ultra-high fixation rate and ultra-high staining fastness (especially the staining fastness of the dye to the fiber during soaping after the fixation stage is completed) has always been a problem that printing and dyeing companies urgently need to solve. Although two chromophores can be connected by a bridge group so that the final dye molecular structure contains multiple reactive groups, the fixation rate of reactive dyes on fibers does not only depend on the number of reactive groups, but is also related to the physical properties of the dye. The dye molecules obtained after the bridge group connection often have a large molecular weight, and the dye is easy to associate, which not only does not improve the fixation rate, but also makes the staining fastness worse. Therefore, to date, there has been no patent or literature report on the design of the bridge group molecular structure to regulate the final dye molecule performance so that the final dye has an ultra-high fixation rate and ultra-high staining fastness.

[0009] In dye printing and pad dyeing process, if dye is to be made to have ultrahigh fixation rate and ultrahigh staining fastness, need dye to have low directness, few to associate between dye molecule, have enough reactive groups to react with fiber, a small amount of unreacted dye can be easily broken away from fiber, enter in aqueous phase.At present, by bridging group, chromogen is connected, final dye molecule can be made to obtain enough reactive groups, but the directness of dye is large, and association is serious, and the staining fastness to fiber is poor, and a large amount of unreacted dye can be stained on white cloth sample.This is mainly because the coplanarity of whole molecule is increased after current bridging group connects chromogen, makes it easy to associate by hydrogen bond, hydrophobic interaction power etc. between dye molecule, and the affinity between dye molecule and fiber is high, the physical adsorption action force between final unreacted dye molecule and fiber is strong, and the dye that soaping falls off is easily adsorbed with white cloth sample, causes white cloth sample staining serious.

[0010] To prevent unreacted dye from staining white fabric, the affinity between the dye molecules and the fiber needs to be weak, which can be achieved by manipulating the spatial structure and charge distribution of the dye molecules. However, the currently available bridge structures provide little insight into designing dye molecules with ultra-high fixation rates and stain fastness, particularly after the fixation stage, when soaping. Summary of the Invention

[0011] The object of the present invention is to provide a class of reactive dyes with ultra-high color fixation rate and ultra-high color fastness (especially the color fastness of the dye to the fiber during soaping after the color fixation stage is completed) to solve the difficult problem of commercial dyes, especially yellow, orange and red, proposed in the above background technology; another object of the present invention is to provide a method for preparing reactive dyes with ultra-high color fixation rate and ultra-high color fastness; another object of the present invention is to provide an application of reactive dyes with ultra-high color fixation rate and ultra-high color fastness; the technical solution of the present invention addresses the technical problem that the existing technical solution is too single, and provides a solution that is significantly different from the existing technology.

[0012] To achieve the above object, the present invention provides the following technical solutions:

[0013] A class of reactive dyes with ultra-high fixation rate and ultra-high staining fastness, wherein the reactive dyes are compounds represented by the general structural formula (I):

[0014]

[0015] In the general formula (I), A1 and A2 are independently selected from structures IIa or IIb:

[0016]

[0017] D1 and D2 are independently selected from structures IIIa or IIIb:

[0018]

[0019] wherein X is halogen; R1 and R2 are selected from C1-C4 alkyl, C1-C4 alkoxy, -COOM, -CH2COOM or -SO3M; R3 is selected from -H, -OH, C1-C4 alkyl or C1-C4 alkoxy; R4 is selected from -H, -COOM or -SO3M; R5 and R6 are independently selected from: -H, -CH3, -OCH3, -SO3M, -NH2, -NHCH2CH2COOM, -NHCONH2, -NHCOCH3; R7 is -H or -SO3M; R8 is -H, -CH3, -C2H5 or -C6H5; wherein R9, R 10 、R 12 and R 13 is selected from -H, -CH3, -OCH3, -COOM, halogen, -OH, -CN, -NO2, or -SO3M; said R 11 and R 14 Selected from -H, -CH3, -OCH3, -SO2CH2CH2OSO3M, -SO2CH=CH2, -SO2CH2CH2OH, -CONHCH2CH2SO2CH2CH2OSO3M, -CONHCH2CH2SO2CH=CH2, -CONHCH2CH2SO2CH2CH2Cl, -NHCOCH2CH2CH2SO2CH2CH2Cl, -NHCOCH2CH2CH2SO2CH2CH2Cl, -NHCOCH2CH2CH2SO2CH2SO2CH=CH2, -NHCOCHBrCH2Br or -NHCOCBrCH2.

[0020] The M is -H or an alkali metal.

[0021] Furthermore, A1 and A2 are independently selected from structures IIa or IIb:

[0022]

[0023] Said D1 and D2 are independently selected from structure IIIa or IIIb:

[0024]

[0025] wherein X is F or Cl; R1 and R2 are independently selected from C1-C4 alkyl or -SO3M; R3 is selected from -H, C1-C4 alkyl; R4 is selected from -H, or -SO3M; R5 and R6 are independently selected from -H, -SO3M, -NH2, -NHCH2CH2COOM, -NHCONH2; R7 is -H or -SO3M; R8 is -H; wherein R9, R10 、R 12 and R 13 Independently selected from -H, -CH3, -OCH3 or -SO3M; said R 11 and R 14 Independently selected from -H, -SO2CH2CH2OSO3M, -SO2CH=CH2;

[0026] The M is -H or an alkali metal.

[0027] Preferably, M is -H, Na, K or Li.

[0028] Furthermore, in the general structural formula (I), A1 and A2 are independently selected from structures IIa or IIb:

[0029]

[0030] Said D1 and D2 are independently selected from structure IIIa or IIIb:

[0031]

[0032] wherein R1 and R2 are selected from C1-C4 alkyl, -COOM or -SO3M; R3 is selected from -H or C1-C4 alkyl; R4 is selected from -H, -COOM or -SO3M; R5 is -H, -CH3 or -SO3M; R6 is -NH2, -NHCH2CH2COOM, -NHCONH2, -NHCOCH3 or -SO3M; R7 is -H or -SO3M; R8 is -H, -CH3, -C2H5 or -C6H5; R9, R 10 、R 12 and R 13 is selected from -H, -CH3, -OCH3, -COOM, halogen, -OH, -CN, -NO2, or -SO3M; said R 11 and R 14 Selected from -H, -CH3, -OCH3, -SO2CH2CH2OSO3M, -SO2CH=CH2, -SO2CH2CH2OH, -CONHCH2CH2SO2CH2CH2OSO3M, -CONHCH2CH2SO2CH=CH2, -CONHCH2CH2SO2CH2CH2Cl, -NHCOCH2CH2CH2SO2CH2CH2Cl, -NHCOCH2CH2CH2SO2CH2CH2Cl, -NHCOCH2CH2CH2SO2CH2SO2CH=CH2, -NHCOCHBrCH2Br or -NHCOCBrCH2.

[0033] The M is -H or an alkali metal.

[0034] Furthermore, in the general structural formula (I), A1 and A2 are independently selected from structures IIa or IIb:

[0035]

[0036] Said D1 and D2 are independently selected from structure IIIa or IIIb:

[0037]

[0038] wherein R1 and R2 are selected from C1-C4 alkyl or -SO3M; R3 is selected from -H or C1-C4 alkyl; R4 is selected from -H, -COOM or -SO3M; R5 is -H, -CH3 or -SO3M; R6 is -NH2, -NHCH2CH2COOM, -NHCONH2, -NHCOCH3 or -SO3M; R7 is -H or -SO3M; R8 is -H, -CH3 or -C6H5; R9, R 10 、R 12 and R 13 is selected from -H, -CH3, -OCH3, -COOM or -SO3M; said R 11 and R 14 Selected from -H, -SO2CH2CH2OSO3M, -SO2CH=CH2, -SO2CH2CH2OH, -CONHCH2CH2SO2CH2CH2OSO3M, -CONHCH2CH2SO2CH=CH2, -CON HCH2CH2SO2CH2CH2Cl, -NHCOCH2CH2CH2SO2CH2CH2Cl, -NHCOCH2CH2CH2SO2CH=CH2, -NHCOCHBrCH2Br or -NHCOCBrCH2.

[0039] The M is -H or an alkali metal.

[0040] Furthermore, in the general structural formula (I), A1 and A2 are independently selected from structures IIa or IIb:

[0041]

[0042] Said D1 and D2 are independently selected from structure IIIa or IIIb:

[0043]

[0044] wherein R1 and R2 are selected from C1-C4 alkyl or -SO3M; R3 is selected from -H or C1-C4 alkyl; R4 is selected from -H or -SO3M; R5 is -H, -CH3 or -SO3M; R6 is -NH2, -NHCH2CH2COOM, -NHCONH2, -NHCOCH3 or -SO3M; R7 is -H or -SO3M; R8 is -H or -CH3; R9 is -H, -CH3, -OCH3 or -SO3M; R 10 is -H, -OCH3 or -SO3M; said R 11 For -H, -SO2CH2CH2OSO3M, -SO2CH=CH2, -SO2CH2CH2OH, -CONHCH2CH2SO2CH2CH2OSO3M, -CONHCH2CH2SO2CH=CH2, -CONH R 12 -H or -SO3M; R 13 -H or -SO3M; R 14 For -H, -SO2CH2CH2OSO3M, -SO2CH=CH2, -SO2CH2CH2OH, -CONHCH2CH2SO2CH2CH2OSO3M, -CONHCH2CH2SO2CH=CH2, -CON HCH2CH2SO2CH2CH2Cl, -NHCOCH2CH2CH2SO2CH2CH2Cl, -NHCOCH2CH2CH2SO2CH=CH2, -NHCOCHBrCH2Br or -NHCOCBrCH2.

[0045] The M is -H or an alkali metal.

[0046] Furthermore, in the general structural formula (I), A1 and A2 are independently selected from structures IIa or IIb:

[0047]

[0048] Said D1 and D2 are independently selected from structure IIIa or IIIb:

[0049]

[0050] wherein R1 and R2 are selected from C1-C4 alkyl or -SO3M; R3 is selected from -H or C1-C4 alkyl; R4 is selected from -H or -SO3M, and when R1 and R2 are alkyl, R4 is -SO3M; R5 is -H, -CH3 or -SO3M; R6 is -NH2, -NHCH2CH2COOM, -NHCONH2, -NHCOCH3 or -SO3M; R7 is -H or -SO3M; R8 is -H or -CH3; R9 is -H, -CH3, -OCH3 or -SO3M; R 10 is -H, -OCH3 or -SO3M; said R 11 For -H, -SO2CH2CH2OSO3M, -SO2CH=CH2, -CONHCH2CH2SO2CH2CH2OSO3M, -CONHCH2CH2SO2CH=CH2, -NHCOCH2CH2CH2SO2CH2CH2Cl, -NHCOCH2CH2 CH2SO2CH=CH2, -NHCOCHBrCH2Br or -NHCOCBrCH2; R 12 -H or -SO3M; R 13 -H or -SO3M; R 14 For -H, -SO2CH2CH2OSO3M, -SO2CH=CH2, -CONHCH2CH2SO2CH2CH2OSO3M, -CONHCH2CH2SO2CH=CH2, -CONHCH2CH2SO2CH2CH2Cl, -NHCOCH2CH2CH2SO2CH2CH2Cl, -NHCOCH2CH2 CH2SO2CH=CH2, -NHCOCHBrCH2Br or -NHCOCBrCH2.

[0051] The M is -H or an alkali metal.

[0052] Furthermore, in the general structural formula (I), A1 and A2 are independently selected from structures IIa or IIb:

[0053]

[0054] Said D1 and D2 are independently selected from structure IIIa or IIIb:

[0055]

[0056] wherein R1 and R2 are -CH3 or -SO3M; R3 is -H or -CH3; R4 is -H or -SO3M, and when R1 and R2 are -CH3, R4 is -SO3M; R5 is -H, -CH3 or -SO3M; R6 is -NH2, -NHCH2CH2COOM, -NHCONH2, -NHCOCH3 or -SO3M; R7 is -H or -SO3M; R8 is -H or -CH3; R9 is -H, -CH3, -OCH3 or -SO3M; R 10 is -H, -OCH3 or -SO3M; said R 11 is -H, -SO2CH2CH2OSO3M or -SO2CH=CH2; R 12 -H or -SO3M; R 13 -H or -SO3M; R 14 It is -H, -SO2CH2CH2OSO3M or -SO2CH=CH2.

[0057] The M is -H or an alkali metal.

[0058] Furthermore, in the general structural formula (I), A1 and A2 are independently selected from structures IIa or IIb:

[0059]

[0060] Said D1 and D2 are independently selected from structure IIIa or IIIb:

[0061]

[0062] Wherein, when R1 and R2 are -CH3, R3 is -CH3; R4 is -SO3M; R1 and R2 are -SO3M; R3 and R4 are -H; R5 is -H, -CH3 or -SO3M; R6 is -NH2, -NHCH2CH2COOM, -NHCONH2, -NHCOCH3 or -SO3M; R7 is -H or -SO3M; R8 is -H or -CH3; R9 is -H, -CH3, -OCH3 or -SO3M; R 10 is -H, -OCH3 or -SO3M; said R 11 is -H, -SO2CH2CH2OSO3M or -SO2CH=CH2; R 12 -H or -SO3M; R 13 -H or -SO3M; R 14 It is -H, -SO2CH2CH2OSO3M or -SO2CH=CH2.

[0063] The M is -H, Na, K or Li.

[0064] Furthermore, in the general structural formula (I), A1 and A2 are independently selected from structures IIa or IIb:

[0065]

[0066] Said D1 and D2 are independently selected from structure IIIa or IIIb:

[0067]

[0068] Wherein, when R1 and R2 are -CH3, R3 is -CH3; R4 is -SO3M; R1 and R2 are -SO3M; R3 and R4 are -H; R5 is -H, -CH3 or -SO3M; R6 is -NH2, -NHCH2CH2COOM, -NHCONH2, -NHCOCH3 or -SO3M; R7 is -H or -SO3M; R8 is -H or -CH3; R9 is -H, -CH3, -OCH3 or -SO3M; R 10 is -H, -OCH3 or -SO3M; said R 11 is -H, -SO2CH2CH2OSO3M or -SO2CH=CH2; R 12 -H or -SO3M; R 13 -H or -SO3M; R 14 It is -H, -SO2CH2CH2OSO3M or -SO2CH=CH2.

[0069] The M is -H, Na or K.

[0070] Furthermore, in the general structural formula (I), A1 and A2 are independently selected from structures IIa or IIb:

[0071]

[0072] Said D1 and D2 are independently selected from structure IIIa or IIIb:

[0073]

[0074] Wherein, when R1 and R2 are -CH3, R3 is -CH3; R4 is -SO3M; R1 and R2 are -SO3M; R3 and R4 are -H; R5 is -H, -CH3 or -SO3M; R6 is -NH2, -NHCH2CH2COOM, -NHCONH2, -NHCOCH3 or -SO3M; R7 is -H or -SO3M; R8 is -H or -CH3; R9 is -H, -CH3, -OCH3 or -SO3M; R 10 is -H, -OCH3 or -SO3M; said R 11is -H, -SO2CH2CH2OSO3M or -SO2CH=CH2; R 12 -H or -SO3M; R 13 -H or -SO3M; R 14 It is -H, -SO2CH2CH2OSO3M or -SO2CH=CH2.

[0075] The M is -H or Na.

[0076] Furthermore, in the general structural formula (I), A1 and A2 are independently selected from structures IIa or IIb:

[0077]

[0078] Said D1 and D2 are independently selected from structure IIIa or IIIb:

[0079]

[0080] Wherein, when R1 and R2 are -CH3, R3 is -CH3; R4 is -SO3M; R1 and R2 are -SO3M; R3 and R4 are -H; R5 is -H, -CH3 or -SO3M; R6 is -NH2, -NHCH2CH2COOM, -NHCONH2, -NHCOCH3 or -SO3M; R7 is -H or -SO3M; R8 is -H or -CH3; R9 is -H, -CH3, -OCH3 or -SO3M; R 10 is -H, -OCH3 or -SO3M; said R 11 is -H, -SO2CH2CH2OSO3M or -SO2CH=CH2; R 12 -H or -SO3M; R 13 -H or -SO3M; R 14 It is -H, -SO2CH2CH2OSO3M or -SO2CH=CH2.

[0081] The M is Na.

[0082] Furthermore, in A1 and A2, IIa is any of the following structures:

[0083]

[0084] wherein R5 is H, -NH2 or -NHCH2CH2COOM; R6 is -NHCONH2 or -SO3M;

[0085] IIb is any of the following structures:

[0086]

[0087] wherein R7 is H or -SO3M; R8 is H;

[0088] In D1 and D2, IIIa is the following structure:

[0089]

[0090] Among them, R9 and R 10 R is independently H, -CH3, -OCH3 or -SO3M; 11 -SO2CH2CH2OSO3M, -SO2CH=CH2; IIIb is the following structure:

[0091]

[0092] R 12 is H, -CH3, -OCH3 or –SO3M; R 14 -SO2CH2CH2OSO3M, -SO2CH=CH2;

[0093] M is –H, Na, K or Li.

[0094] The present invention provides compounds including but not limited to the following:

[0095]

[0096]

[0097]

[0098] In the above technical solution, it represents a connection key, which has the same meaning as same.

[0099] Preferably, in the above general formulas, In the example, the group connected by *1 is D1-N=N-*1; the group connected by *2 is

[0100] In the example, the group connected by *3 is D1-N=N-*3; the group connected by *4 is

[0101] Another invention provides a method for preparing reactive dyes with ultra-high fixation rate and ultra-high staining fastness. The reactive dyes can be prepared by traditional reactive dye unit reactions, including conventional condensation, diazotization, coupling reaction, etc. There are three common preparation methods, which are respectively according to the following processes:

[0102] Method 1: First prepare the chromophore, then carry out the first condensation reaction with the halogenated s-triazine, and then carry out the second condensation reaction with the bridge group;

[0103]

[0104] In the concentrated hydrochloric acid reaction system, aniline compound a reacts with sodium nitrite solution to obtain diazonium salt b of aniline compound a; in the concentrated hydrochloric acid reaction system, aniline compound c reacts with sodium nitrite solution to obtain diazonium salt d of aniline compound c;

[0105] The diazonium salt b reacts with the coupling component compound e to obtain the chromophore g; the diazonium salt b reacts with the coupling component compound f to obtain the chromophore i; the diazonium salt d reacts with the coupling component compound e to obtain the chromophore h; the diazonium salt d reacts with the coupling component compound f to obtain the chromophore k;

[0106] Chromogen g reacts with cyanuric chloride to obtain a condensation product l of halogenated s-triazine and chromogen g; chromogen h reacts with cyanuric chloride to obtain a condensation product m of halogenated s-triazine and chromogen h; chromogen I reacts with cyanuric chloride to obtain a condensation product n of halogenated s-triazine and chromogen I; chromogen k reacts with cyanuric chloride to obtain a condensation product o of halogenated s-triazine and chromogen k;

[0107] An aromatic amine compound P containing two amino groups reacts with product 1, product m, product n, and product o respectively to prepare a compound represented by general formula (I);

[0108] Method 2: The halogenated s-triazine is first condensed, then reacted with a diazonium salt, and then condensed with a bridge group for a second time;

[0109]

[0110] In the concentrated hydrochloric acid reaction system, aniline compound a reacts with sodium nitrite solution to obtain diazonium salt b of aniline compound a; in the concentrated hydrochloric acid reaction system, aniline compound c reacts with sodium nitrite solution to obtain diazonium salt d of aniline compound c;

[0111] The coupling component compound e reacts with cyanuric chloride to obtain a condensation product w of the halogenated s-triazine and the coupling component compound e;

[0112] The coupling component compound f reacts with cyanuric chloride to obtain a condensation product z of the halogenated s-triazine and the coupling component compound f;

[0113] Diazonium salt b reacts with product w to obtain compound l; diazonium salt b reacts with product z to obtain compound n; diazonium salt d reacts with product w to obtain compound m; diazonium salt d reacts with product z to obtain compound o;

[0114] An aromatic amine compound P containing two amino groups reacts with product 1, product m, product n, and product o respectively to prepare a compound represented by general formula (I);

[0115] Method 3: The halogenated s-triazine is first condensed, then reacted with the bridging group for the second time, and then reacted with the diazonium salt.

[0116]

[0117] The coupling component compound e reacts with cyanuric chloride to obtain a condensation product w of the halogenated s-triazine and the coupling component compound e; the coupling component compound f reacts with cyanuric chloride to obtain a condensation product z of the halogenated s-triazine and the coupling component compound f;

[0118] An aromatic amine compound P containing two amino groups reacts with a compound w to prepare a compound r that can be used in a coupling reaction; an aromatic amine compound P containing two amino groups reacts with a compound z to prepare a compound s that can be used in a coupling reaction;

[0119] In a concentrated hydrochloric acid reaction system, aniline compound a reacts with a sodium nitrite solution to obtain a diazonium salt b of aniline compound a; in a concentrated hydrochloric acid reaction system, aniline compound c reacts with a sodium nitrite solution to obtain a diazonium salt d of aniline compound c;

[0120] The diazonium salt b or the diazonium salt d reacts with the compound r or the compound s respectively to prepare the compound represented by the general formula (I).

[0121] Specifically, the specific steps of the preparation method 1 of the compound of general formula (I) include:

[0122] (1) Preparation of chromophore

[0123] Diazotization reaction: Add aniline compound a (or naphthylamine compound c), crushed ice, and a small amount of water to a beaker and grind with ice for 1 hour. Add concentrated hydrochloric acid to the reaction system and stir for 10-60 minutes. Add sodium nitrite solution dropwise to the reaction system. After the addition is complete, continue the reaction for 1-2 hours. The reaction endpoint is detected using Ehrlich reagent (1 g N,N-dimethylbenzoic acid and 5 mL concentrated hydrochloric acid dissolved in 95 mL ethanol). Excess nitrous acid is removed with sulfamic acid to produce a solution of the diazonium salt b (or d) of aniline compound a (or naphthylamine compound c).

[0124] The molar ratio of the compound a (or c) to sodium nitrite is 1:1 to 1:1.02; the molar ratio of the compound a (or c) to hydrochloric acid is 1:0.5 to 1:2.8.

[0125] Coupling reaction: A solution of diazonium salt b (or d) is added to a solution of coupling component compound e (or f), and the pH of the reaction is adjusted to between 3 and 9 with baking soda. The temperature is 0-15°C, and the reaction is carried out for 2-4 hours. The reaction is detected by the ring penetration method, and the disappearance of diazonium salt b (or d) is regarded as the end point. After the reaction is completed, a solution of chromogen g (or h, or I, or k) is obtained.

[0126] The molar ratio of the diazonium salt b (or d) to the coupling component compound e (or f) is 1:0.96 to 1:1.02.

[0127] (2) Condensation reaction of halogenated s-triazine with chromophore

[0128] Cyanuric chloride is slurried, crushed ice, and a small amount of water are added to a beaker and ground with ice for half an hour. A solution of chromophore g (or h, I, or k) is added to the slurry of cyanuric chloride (or cyanuric fluoride is directly added dropwise to the chromophore solution). The pH of the reaction is adjusted between 3 and 7 with baking soda, and the reaction temperature is controlled at 0-10°C. The reaction is maintained under these conditions for 1-3 hours. The end point of the reaction is detected by liquid chromatography, with the disappearance of the chromophore being the end point, to obtain a reaction solution of the monocondensation product l (or m, n, or o) of halogenated s-triazine and chromophore g (or h, I, or k).

[0129] The molar ratio of the compound halogenated s-triazine to the chromophore g (or h, or I, or k) is 1:1 to 1.03:1.

[0130] (3) Condensation reaction with bridging group

[0131] An aromatic amine compound P containing two amino groups is added to the reaction mixture of the condensation product L (or M, N, or O) of a halogenated s-triazine and a chromophore. The reaction temperature is controlled between 30-55°C and the pH is controlled between 5.5-7.5 for 4-12 hours. The reaction endpoint is determined by liquid chromatography detection, with the disappearance of the condensation product of the halogenated s-triazine and the chromophore being the endpoint. After the reaction is completed, the mixture is dried and ground to obtain a solid powder of the reactive dye represented by the final compound (I).

[0132] The molar ratio of the condensation product L (or m, or n, or o) of the halogenated s-triazine and the chromophore to the aromatic amine compound P is 1:0.47 to 1:0.52.

[0133] The specific steps of the second method for preparing the compound of general formula (I) include:

[0134] (1) Preparation of diazonium salt

[0135] Diazotization reaction: Add aniline compound a (or naphthylamine compound c), crushed ice, and a small amount of water to a beaker and grind with ice for 1 hour. Add concentrated hydrochloric acid to the reaction system and stir for 10-60 minutes. Add sodium nitrite solution dropwise to the reaction system. After the addition is complete, continue the reaction for 1-2 hours. The reaction endpoint is detected using Ehrlich reagent (1 g N,N-dimethylbenzoic acid and 5 mL concentrated hydrochloric acid dissolved in 95 mL ethanol). Excess nitrous acid is removed with sulfamic acid to produce a solution of the diazonium salt b (or d) of aniline compound a (or naphthylamine compound c).

[0136] The molar ratio of the compound a (or c) to sodium nitrite is 1:1 to 1:1.02; the molar ratio of the compound a (or c) to hydrochloric acid is 1:0.5 to 1:2.8.

[0137] (2) The first condensation reaction of halogenated s-triazine

[0138] Cyanuric chloride is slurried, crushed ice, and a small amount of water are added to a beaker and ground with ice for half an hour. A solution of coupling component compound e (or f) is added to the slurry of cyanuric chloride (or cyanuric fluoride is directly added dropwise to the solution of coupling component compound e (or f)). The pH of the reaction is adjusted between 3 and 7 with baking soda, and the reaction temperature is controlled at 0-10°C. The reaction is maintained under these conditions for 1-3 hours. The end point of the reaction is determined by liquid chromatography, with the disappearance of coupling component compound e (or f) as the end point, to obtain a reaction solution of the monocondensation product w (or z) of halogenated s-triazine and coupling component compound e (or f).

[0139] The molar ratio of the compound halogenated s-triazine to compound e (or f) is 1:1 to 1.03:1.

[0140] (3) Coupling reaction

[0141] A solution of diazonium salt b (or d) is added to a solution of monocondensation product w (or z) of halogenated s-triazine, and the pH value of the reaction is adjusted to between 3 and 9 with baking soda. The temperature is 0-15°C and the reaction is carried out for 2-4 hours. The reaction is detected by the ring penetration method, and the disappearance of diazonium salt b (or d) is regarded as the end point. After the reaction is completed, a reaction solution of compound l (or m, or n, or o) is prepared.

[0142] The molar ratio of the diazonium salt b (or d) to the condensation product w (or z) of the halogenated s-triazine is 1:0.96 to 1:1.02.

[0143] (4) Condensation reaction with bridging group

[0144] An aromatic amine compound P containing two amino groups is added to the reaction mixture of compound 1 (or m, n, or o). The reaction temperature is controlled between 30-55°C and the pH is controlled between 5.5-7.5 for 4-12 hours. The reaction endpoint is determined by liquid chromatography detection, with the disappearance of the condensation product of the halogenated s-triazine and the chromophore being the endpoint. After the reaction is completed, the mixture is dried and ground to obtain the reactive dye solid powder represented by the final compound (I).

[0145] The molar ratio of the compound product l (or m, or n, or o) to the aromatic amine compound P is 1:0.47 to 1:0.52.

[0146] The specific steps of the third method for preparing the compound of general formula (I) include:

[0147] (1) The first condensation reaction of halogenated s-triazine

[0148] Cyanuric chloride is slurried, crushed ice, and a small amount of water are added to a beaker and ground with ice for half an hour. A solution of coupling component compound e (or f) is added to the slurry of cyanuric chloride (or cyanuric fluoride is directly added dropwise to the solution of coupling component compound e (or f)). The pH of the reaction is adjusted between 3 and 7 with baking soda, and the reaction temperature is controlled at 0-10°C. The reaction is maintained under these conditions for 1-3 hours. The end point of the reaction is determined by liquid chromatography, with the disappearance of coupling component compound e (or f) as the end point, to obtain a reaction solution of the monocondensation product w (or z) of halogenated s-triazine and coupling component compound e (or f).

[0149] The molar ratio of the compound halogenated s-triazine to compound e (or f) is 1:1 to 1.03:1.

[0150] (2) Condensation reaction with bridging group

[0151] An aromatic amine compound P containing two amino groups is added to the reaction solution of compound w (or z). The reaction temperature is controlled between 30-55°C and the pH is controlled between 5.5-7.5. The reaction is allowed to proceed for 4-12 hours. The end point of the reaction is determined by liquid chromatography, with the disappearance of compound w (or z) being the endpoint. This produces a solution of compound r (or s) suitable for coupling reactions.

[0152] The molar ratio of the compound w (or z) to the aromatic amine compound P is 1:0.47 to 1:0.52.

[0153] (3) Preparation of diazonium salt

[0154] Diazotization reaction: Add aniline compound a (or naphthylamine compound c), crushed ice, and a small amount of water to a beaker and grind with ice for 1 hour. Add concentrated hydrochloric acid to the reaction system and stir for 10-60 minutes. Add sodium nitrite solution dropwise to the reaction system. After the addition is complete, continue the reaction for 1-2 hours. The reaction endpoint is detected using Ehrlich reagent (1 g N,N-dimethylbenzoic acid and 5 mL concentrated hydrochloric acid dissolved in 95 mL ethanol). Excess nitrous acid is removed with sulfamic acid to produce a solution of the diazonium salt b (or d) of aniline compound a (or naphthylamine compound c).

[0155] The molar ratio of the compound a (or c) to sodium nitrite is 1:1 to 1:1.02; the molar ratio of the compound a (or c) to hydrochloric acid is 1:0.5 to 1:2.8.

[0156] (4) Coupling reaction

[0157] A solution of diazonium salt b (or d) is added to a solution of compound r (or s), and the pH value of the reaction is adjusted to between 3 and 9 with baking soda. The temperature is 0-15°C, and the reaction is carried out for 2-4 hours. The reaction is detected by the ring penetration method, and the disappearance of diazonium salt b (or d) is taken as the end point. After the reaction is completed, the reaction is dried and ground to obtain the final reactive dye solid powder represented by compound (I).

[0158] The molar ratio of the diazonium salt b (or d) to the compound r (or s) is 1:0.96 to 1:1.02.

[0159] In another aspect, the present invention provides a commercial dye comprising the following raw materials in parts by weight: 5-15 parts of a diffusing agent, 0.1-0.5 parts of a dust suppressant, 5-15 parts of sodium sulfate, and 50-85 parts of the aforementioned reactive dye with ultra-high color fixation and ultra-high color fastness. Preferably, the reactive dye with ultra-high color fixation and ultra-high color fastness comprises 75-85 parts.

[0160] Furthermore, the diffusing agent is a methylnaphthalenesulfonic acid formaldehyde condensate, and the dustproof agent is a water-soluble polymer compound.

[0161] In another aspect, the present invention provides a use of a commercial dye in coloring, printing, pad dyeing, cold pad batch or inkjet printing of cellulose fibers. Preferably, the cellulose fibers are hydroxyl and / or nitrogen-containing cellulose fibers.

[0162] Furthermore, the cellulose fiber is cotton fiber, viscose fiber, linen fiber, and a blended fabric containing two or more of these fibers.

[0163] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: 1. Although the reactive dye in the present invention still uses an aromatic amine compound containing two amino groups as a bridge group to connect two chromophores, the bridge group structure is different from that of the aromatic amine compound containing two amino groups reported in all current patents and literature. The aromatic amine compound containing two amino groups as a bridge group in the present invention has a unique structural feature, that is, it satisfies two conditions at the same time: one is that the ortho positions of the two amino groups must contain a substituent; the other is that the molecular structure of this bridge group contains at least one anionic group.

[0164] 2. The bridge group of the reactive dye in this invention not only serves the traditional role of a bridge group, connecting two chromophores, but the more important technological breakthrough is that when the two amino groups on the bridge group react separately with the chromophore containing a halogenated triazine, the steric hindrance effect of the two substituents ortho to the amino group can cause the two halogenated s-triazine-containing chromophores to undergo spatial structural distortion, making them non-coplanar. This inherently reduces the directness of the dye molecule and its affinity for fiber, making it easier for unreacted dye to fall off the cellulose, and the dye has ultra-high color fastness. In this case, the substituents ortho to the amino group can be either hydrophobic or hydrophilic. When the substituents ortho to the amino group are hydrophobic groups, the bridge group structure also needs to contain anionic groups; when the substituents ortho to the amino group are anionic groups, the bridge group structure does not need additional anionic groups.

[0165] 3. The role of the anionic group on the bridge group of the reactive dye in the present invention is not only the traditional anionic group used to increase the water solubility of the dye molecule. The technical breakthrough lies in that, based on the fact that the dye molecular structure is spatially distorted and not flat, during the application process, the cellulose fiber is negatively charged. At this time, the anionic group on the bridge group is also negatively charged. Like charges repel each other. In addition, the two original chromophores distributed on the left and right sides of the dye molecule also contain multiple sulfonic acid anionic groups, so that the left, middle and right sides of the final dye molecule all contain negative charges, and the repulsion force with the fiber is strong. Therefore, the affinity between the dye and the fiber is further reduced, and ultimately the dye has more outstanding color fastness.

[0166] 4. The reactive dyes of the present invention contain four reactive groups: two halogenated s-triazine reactive groups and a vinyl sulfone sulfate reactive group. Unlike conventional dyes containing multiple reactive groups, although the types and numbers of the reactive groups may be the same, conventional dyes containing multiple reactive groups have high coplanarity and severe molecular association. Therefore, during the reaction between the dye molecules and the fiber, the dye molecules need to first disassociate before reacting with the fiber. However, when reactive dyes are used to color cellulose fibers, water is usually used as the medium. During the heating and disassociation process, the reactive groups undergo hydrolysis side reactions, causing some dye molecules to lose their ability to react with the fiber due to the hydrolysis of the reactive groups. This is also the reason why conventional dyes containing multiple reactive groups do not achieve ultra-high fixation rates. Then, the reactive dye in the present invention, based on the fact that the dye molecular structure is spatially distorted and not flat, the anionic groups on the bridge group make the bridge group and the triazine ring part of the molecular structure of the dye molecular structure carry negative charges, which further increases the charge repulsion between the dye molecules and fundamentally reduces the association between the dye molecules, thereby allowing the dye molecules to react with the fiber more easily and quickly. The synergistic effect of multiple reactive groups results in an increased probability of reaction between the dye and the fiber, ultimately enabling the dye to have an ultra-high fixation rate. DETAILED DESCRIPTION

[0167] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the embodiments. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0168] Example 1

[0169]

[0170] The commercial reactive dye was prepared by mixing the reactive dye I-1 with a diffusing agent (methylnaphthalenesulfonic acid formaldehyde condensate with a condensation degree of 4 and a sulfonation degree of 2), a water-based polymer dust suppressant and sodium sulfate in proportions of 85%, 5%, 0.1% and 9.9% by mass.

[0171] The preparation method of the reactive dye I-1 comprises the following steps:

[0172] (1) Diazotization reaction

[0173] Add 100% para-(β-sulfate ethyl sulfone)aniline (para-ester, 28.1 g), 250 g of ice, and 30 mL of water to a 1000 mL beaker and grind with ice for 1 hour. Add 12.2 g of industrial hydrochloric acid (30%) and continue stirring to react for 50 minutes. Dissolve 100% solid sodium nitrite (7.1 g) in 30 mL of water and slowly add this solution dropwise to the para-ester suspension. During the addition, maintain a slightly blue color on Congo red test paper and a slightly blue color on KI test paper. After the addition is complete, maintain the reaction system temperature below 10°C and continue the reaction for 1 hour. Use Ehrlich reagent to detect the reaction endpoint. After the reaction is completed, remove excess nitrous acid with aminosulfonic acid to obtain a diazonium salt solution of the para-ester.

[0174] (2) First condensation reaction

[0175] 100% cyanuric chloride (19.2g), 250g ice and 30mL water were added to a 1000mL beaker and beaten for 30 minutes under stirring. 100% 1-naphthylamine-8-hydroxy-3,6-disulfonic acid monosodium salt (H acid monosodium salt, 34.1g) and 400mL water were added to a 1000mL beaker and the pH value was adjusted to 5-6 with baking soda until dissolved. This solution was slowly added to the beating liquid of cyanuric chloride, and the reaction conditions were controlled at 0-5°C and pH=3-4. After the addition, the reaction was continued under these conditions for 1.5 hours. The reaction endpoint was detected by liquid phase detection, with the disappearance of H acid as the endpoint. After the reaction was completed, a primary condensation product solution of cyanuric chloride and H acid was obtained.

[0176] (3) Coupling reaction

[0177] The primary condensation product solution of cyanuric chloride and H acid obtained in step (2) is added to the para-ester diazonium salt solution obtained in step (1), and the pH value of the reaction is adjusted to between 5.8 and 6.5 with baking soda, and the temperature is less than 15° C. The reaction is allowed to proceed for 3 hours. The reaction is detected by the ring penetration method, and the disappearance of the para-ester diazonium salt is regarded as the end point. After the reaction is completed, a monoazo red dye solution containing dichloro-s-triazine is obtained.

[0178] (4) Condensation reaction with bridging group

[0179] Add 100% 4,6-diamino-1,3-benzenedisulfonic acid (26.8 g) to the monoazo red dye solution containing dichloro-s-triazine obtained in step (3). Heat to 40-45°C, adjust the pH of the reaction system to between 5.8-6.5 with baking soda, and keep the reaction under this condition for 6 hours. The end point of the reaction is detected by liquid phase detection, and the disappearance of the monoazo red dye product of dichloro-s-triazine is the end point. Dry and grind to obtain the reactive dye solid powder (λ) shown in the final compound (I) max (H2O) = 500 nm).

[0180] Example 2

[0181]

[0182] A commercial red dye was prepared by mixing reactive dye I-2 with a diffusing agent (methylnaphthalenesulfonic acid formaldehyde condensate with a condensation degree of 4 and a sulfonation degree of 2), a water-based polymer dust suppressant, and sodium sulfate in proportions of 85%, 5%, 0.1%, and 9.9% by mass.

[0183] In this embodiment, the preparation method of reactive dye I-2 is the same as that of Example 1, except that 3,5-diamino-2,4,6-trimethylbenzenesulfonic acid is used instead of 4,6-diamino-1,3-benzenedisulfonic acid in step (4) of preparation I-1, and then condensed with monoazo red dye of dichloro-s-triazine to prepare the final reactive red dye (λ max (H2O) = 511 nm).

[0184] Example 3

[0185]

[0186] A commercial red dye was prepared by mixing reactive dye I-3 with a diffusing agent (methylnaphthalenesulfonic acid formaldehyde condensate with a condensation degree of 4 and a sulfonation degree of 2), a water-based polymer dust suppressant, and sodium sulfate in proportions of 85%, 5%, 0.1%, and 9.9% by mass.

[0187] In this embodiment, the preparation method of the reactive dye I-3 is the same as that of Example 1, except that o-methoxy para-ester is used instead of the para-ester in step (1) of preparation I-1 to prepare the corresponding diazonium salt, and 3,5-diamino-2,4,6-trimethylbenzenesulfonic acid is used instead of 4,6-diamino-1,3-benzenedisulfonic acid in step (4) of preparation I-1 to prepare the final reactive red dye (λ max (H2O) = 522 nm).

[0188] Example 4

[0189]

[0190] A commercial red dye was prepared by mixing reactive dye I-4 with a diffusing agent (methylnaphthalenesulfonic acid formaldehyde condensate with a condensation degree of 4 and a sulfonation degree of 2), a water-based polymer dust suppressant, and sodium sulfate in proportions of 85%, 5%, 0.1%, and 9.9% by mass.

[0191] In this embodiment, the preparation method of the reactive dye I-4 is the same as that of Example 1, except that the para-ester in the preparation step (1) of I-1 is replaced by the para-ester of crissidine to prepare the corresponding diazonium salt, and 3,5-diamino-2,4,6-trimethylbenzenesulfonic acid is replaced by 4,6-diamino-1,3-benzenedisulfonic acid in the preparation step (4) of I-1 to prepare the final reactive red dye (λ max (H2O) = 525 nm).

[0192] Example 5

[0193]

[0194] A commercial red dye was prepared by mixing reactive dye I-5 with a diffusing agent (methylnaphthalenesulfonic acid formaldehyde condensate with a condensation degree of 4 and a sulfonation degree of 2), a water-based polymer dust suppressant, and sodium sulfate in proportions of 85%, 5%, 0.1%, and 9.9% by mass.

[0195] In this embodiment, the preparation method of the reactive dye I-5 is the same as that of Example 1, except that 2,5-dimethoxy para-ester is used instead of the para-ester in step (1) of preparation I-1 to prepare the corresponding diazonium salt, and 3,5-diamino-2,4,6-trimethylbenzenesulfonic acid is used instead of 4,6-diamino-1,3-benzenedisulfonic acid in step (4) of preparation I-1 to prepare the final reactive red dye (λ max (H2O) = 536 nm).

[0196] Example 6

[0197]

[0198] A commercial red dye was prepared by mixing reactive dye I-6 with a diffusing agent (methylnaphthalenesulfonic acid formaldehyde condensate with a condensation degree of 4 and a sulfonation degree of 2), a water-based polymer dust suppressant, and sodium sulfate in proportions of 85%, 5%, 0.1%, and 9.9% by mass.

[0199] In this embodiment, the preparation method of the reactive dye I-6 is the same as that of Example 1, except that 2-amino-6-(2-sulfate ethyl sulfone)-1-naphthalenesulfonic acid is used instead of the para-ester in step (1) of preparation I-1 to prepare the corresponding diazonium salt, and 3,5-diamino-2,4,6-trimethylbenzenesulfonic acid is used instead of 4,6-diamino-1,3-benzenedisulfonic acid in step (4) of preparation I-1 to prepare the final reactive red dye (λ max (H2O) = 522 nm).

[0200] Example 7

[0201]

[0202] The commercial reactive dye was prepared by mixing the reactive dye I-7 with a diffusing agent (methylnaphthalenesulfonic acid formaldehyde condensate with a condensation degree of 4 and a sulfonation degree of 2), a water-based polymer dust suppressant and sodium sulfate in proportions of 85%, 5%, 0.1% and 9.9% by mass.

[0203] In this embodiment, the preparation method of reactive dye I-7 is the same as that of Example 1, except that 2-amino-5-naphthol-7-sulfonic acid (J acid) is used instead of 1-naphthylamine-8-hydroxy-3,6-disulfonic acid monosodium salt in step (2) of preparation I-1 to prepare the corresponding primary condensation product solution of cyanuric chloride and J acid before preparing the final reactive orange dye (λ max (H2O) = 482 nm).

[0204] Example 8

[0205]

[0206] The commercial reactive dye I-8 was prepared by mixing a diffusing agent (methylnaphthalenesulfonic acid formaldehyde condensate with a condensation degree of 4 and a sulfonation degree of 2), a water-based polymer dust suppressant and sodium sulfate in proportions of 85%, 5%, 0.1% and 9.9% by mass.

[0207] The preparation method of the reactive dye I-8 comprises the steps:

[0208] (1) First condensation reaction

[0209] Add 100% cyanuric chloride (19.2g), 250g ice, and 30mL water to a 1000mL beaker and slurry for 30 minutes while stirring. Add 100% 2-amino-5-naphthol-7-sulfonic acid (J acid, 23.9g) and 800mL water to a 1000mL beaker and adjust the pH to 6-6.5 with baking soda until dissolved. Slowly add this solution to the slurry of cyanuric chloride, maintaining the reaction conditions at 0-5°C and a pH of 3-4. Continue the reaction under these conditions for 1.5 hours. The end point of the reaction is determined by liquid chromatography, with the disappearance of J acid as the endpoint. After the reaction is completed, a solution of the primary condensation product of cyanuric chloride and J acid is obtained.

[0210] (2) Condensation reaction with bridging group

[0211] Add 100% 3,5-diamino-2,4,6-trimethylbenzenesulfonic acid (23.0 g) to the solution of the primary condensation product of cyanuric chloride and J acid obtained in step (1). Raise the temperature to 40-45°C, adjust the pH of the reaction system to between 5.8 and 6.5 with baking soda, and maintain the reaction under these conditions for 4 hours. The reaction endpoint is determined by liquid chromatography, with the disappearance of the primary condensation product of cyanuric chloride and J acid as the endpoint, to obtain a solution of the secondary condensation product of cyanuric chloride.

[0212] (3) Diazotization reaction

[0213] Add 100% para-(β-sulfate ethyl sulfone)aniline (para-ester, 28.1 g), 250 g of ice, and 30 mL of water to a 1000 mL beaker and grind with ice for 1 hour. Add 12.2 g of industrial hydrochloric acid (30%) and continue stirring to react for 50 minutes. Dissolve 100% solid sodium nitrite (7.1 g) in 30 mL of water and slowly add this solution dropwise to the para-ester suspension. During the addition, maintain a slightly blue color on Congo red test paper and a slightly blue color on KI test paper. After the addition is complete, maintain the reaction system temperature below 10°C and continue the reaction for 1 hour. Use Ehrlich reagent to detect the reaction endpoint. After the reaction is completed, remove excess nitrous acid with aminosulfonic acid to obtain a diazonium salt solution of the para-ester.

[0214] (4) Coupling reaction

[0215] The dicondensation product solution of cyanuric chloride obtained in step (2) is added to the para-ester diazonium salt solution obtained in step (3), and the pH value of the reaction is adjusted to between 5.8 and 6.5 with baking soda, and the temperature is less than 15°C. The reaction is allowed to proceed for 3 hours. The reaction is detected by the ring penetration method, and the disappearance of the para-ester diazonium salt is taken as the end point. After the reaction is completed, the reaction is dried and ground to obtain the final active dye solid powder (λ max (H2O) = 483 nm).

[0216] Example 9

[0217]

[0218] The commercial reactive dye is prepared by mixing the reactive dye I-9 with a diffusing agent (methylnaphthalenesulfonic acid formaldehyde condensate with a condensation degree of 4 and a sulfonation degree of 2), a water-based polymer dust suppressant and sodium sulfate in proportions of 85%, 5%, 0.1% and 9.9% by mass.

[0219] The preparation method of the reactive dye I-9 comprises the steps:

[0220] (1) Diazotization reaction

[0221] 100% 4-β-hydroxyethylsulfonyl sulfate aniline-2-sulfonic acid (sulfonated para-ester, 36.1 g), 250 g of ice, and 30 mL of water were added to a 1000 mL beaker and ground with ice for 1 hour. 12.2 g of 30% industrial hydrochloric acid was added and the reaction was stirred and continued for 50 minutes. 100% solid sodium nitrite (7.1 g) was dissolved in 30 mL of water and the solution was slowly added dropwise to the suspension of the sulfonated para-ester. During the addition, the reaction solution was maintained at a slightly blue color on Congo red test paper and a slightly blue color on KI test paper. After the addition was complete, the reaction system temperature was maintained below 10°C and the reaction was continued for 1 hour. The reaction endpoint was detected using Ehrlich reagent. After the reaction was completed, excess nitrous acid was removed with sulfamic acid to obtain a diazonium salt solution of the sulfonated para-ester.

[0222] (2) Coupling reaction

[0223] 100% 2,4-diaminobenzenesulfonic acid (m-diaminobenzenesulfonic acid, 18.8 g) was added to the diazonium salt solution of the sulfonated para-ester prepared in step (1). The pH of the reaction was adjusted to approximately 3 with baking soda, and the temperature was less than 15°C. The reaction was allowed to proceed for 4 hours. The reaction was monitored by the ring osmosis method, with the disappearance of the diazonium salt of the sulfonated para-ester as the endpoint. After the reaction was completed, a yellow-based solution was obtained.

[0224] (3) Condensation reaction of cyanuric chloride and chromophore

[0225] Add 100% cyanuric chloride (19.2 g), 250 g of ice, and 30 mL of water to a 1000 mL beaker and slurry for 30 minutes while stirring. Slowly add the yellow base solution prepared in step (2) to the slurry of cyanuric chloride, controlling the reaction conditions at 0-5°C and pH = 3-4. After the addition is complete, continue the reaction under these conditions for 2 hours. The end point of the reaction is determined by liquid chromatography detection, and the disappearance of the yellow base is considered the end point. After the reaction is completed, a solution of a condensation product of cyanuric chloride and the yellow base is obtained.

[0226] (4) Condensation reaction with bridging group

[0227] Add 100% 4,6-diamino-1,3-benzenedisulfonic acid (26.8 g) to the condensation product solution of cyanuric chloride and yellow color base obtained in step (3). Heat to 40-45 ° C, adjust the pH of the reaction system to between 5.8-6.5 with baking soda, and keep the reaction under this condition for 6 hours. The end point of the reaction is detected by liquid phase, and the disappearance of the condensation product of cyanuric chloride and yellow color base is the end point. Dry and grind to obtain the final active dye solid powder (λ max (H2O) = 426 nm).

[0228] Example 10

[0229]

[0230] A commercial reactive dye was prepared by mixing reactive dye I-10 with a diffusing agent (methylnaphthalenesulfonic acid formaldehyde condensate with a condensation degree of 4 and a sulfonation degree of 2), a water-based polymer dust suppressant, and sodium sulfate in proportions of 85%, 5%, 0.1%, and 9.9% by mass.

[0231] In this embodiment, the preparation method of reactive dye I-10 is the same as that of Example 9, except that 3,5-diamino-2,4,6-trimethylbenzenesulfonic acid is used instead of 4,6-diamino-1,3-benzenedisulfonic acid in step (4) of preparation of I-9 to prepare the final reactive yellow dye (λ max (H2O) = 423 nm).

[0232] Example 11

[0233]

[0234] The commercial reactive dye was prepared by mixing the reactive dye I-11 with a diffusing agent (methylnaphthalenesulfonic acid formaldehyde condensate with a condensation degree of 4 and a sulfonation degree of 2), a water-based polymer dust suppressant and sodium sulfate in proportions of 85%, 5%, 0.1% and 9.9% by mass.

[0235] In this embodiment, the preparation method of reactive dye I-11 is the same as that of Example 9, except that the intermediate disulfonic acid in step (2) of preparation of I-9 is replaced by meta-acrylate, and the 4,6-diamino-1,3-benzenedisulfonic acid in step (4) of preparation of I-9 is replaced by 3,5-diamino-2,4,6-trimethylbenzenesulfonic acid to prepare the final reactive yellow dye (λ max (H2O) = 435 nm).

[0236] Example 12

[0237]

[0238] The commercial reactive dye was prepared by mixing reactive dye I-12 with a diffusing agent (methylnaphthalenesulfonic acid formaldehyde condensate with a condensation degree of 4 and a sulfonation degree of 2), a water-based polymer dust suppressant and sodium sulfate in proportions of 85%, 5%, 0.1% and 9.9% by mass.

[0239] In this embodiment, the preparation method of reactive dye I-12 is the same as that of Example 9, except that m-aminophenylurea (m-urea) is used instead of m-diaminobenzene in step (2) of I-9 to prepare the corresponding yellow color base, and then the final reactive yellow dye (λ max (H2O) = 422 nm).

[0240] Example 13

[0241]

[0242] The commercial reactive dye was prepared by mixing the reactive dye I-13 with a diffusing agent (methylnaphthalenesulfonic acid formaldehyde condensate with a condensation degree of 4 and a sulfonation degree of 2), a water-based polymer dust suppressant and sodium sulfate in proportions of 85%, 5%, 0.1% and 9.9% by mass.

[0243] In this embodiment, the preparation method of the reactive dye I-13 is the same as that of Example 9, except that the corresponding yellow color base is prepared by replacing the meta-diamino urea (meta-urea) in the preparation step (2) of I-9, and the 4,6-diamino-1,3-benzenedisulfonic acid in the preparation step (4) of I-9 is replaced by 3,5-diamino-2,4,6-trimethylbenzenesulfonic acid, and the final reactive yellow dye (λ max (H2O) = 424 nm).

[0244] Test example:

[0245] The reactive dye printing process was used to test the application performance of reactive dyes I-1 to I-13, and compared them with the currently available bridge structure dyes (comparative dyes 1-6).

[0246]

[0247]

[0248] The product performance test results are shown in Table 1.

[0249] Printing paste recipe: 5g dye, 5g urea, 2.5g baking soda, 60g sodium alginate paste, 1g resist salt, and the rest is water, totaling 100g. Process flow: semi-finished product → active paste printing → drying → steaming (102℃×7min, relative humidity 75%) → washing → soaping → washing → ironing. Test method:

[0250] Determination of color fastness to rubbing and color fixation of dyes:

[0251] The dye fixation rate is determined according to GB / T 2391-2014 “Determination of the fixation rate of reactive dyes”; the color fastness to rubbing of fabrics is determined according to GB / T3920-2008 “Textiles—Tests for color fastness—Color fastness to rubbing”.

[0252] Determination of color fastness of dyes to white ground:

[0253] Seal one side of a fabric (10 cm x 4 cm) steamed from the printing process to a standard cotton patch (10 cm x 4 cm). Place the sewn fabric in 100 mL of soaping solution (containing 5 g / L standard soap flakes and 2 g / L soda ash) and soap at 60°C for 30 minutes. Rinse with water and dry. Use the original standard cotton patch as a reference sample and assess the staining grade of the sample using a gray scale.

[0254] Table 1 Dye solubility, fixation rate and color fastness data

[0255]

[0256] As shown in Table 1, the reactive dyes provided by the present invention exhibit a color fastness to white staining on cotton of grade 4 or 4-5, which is 2-3 grades higher than existing multi-reactive dyes (comparison dyes). The print fixation rate exceeds 91%, which is 20-40% higher than existing multi-reactive dyes (comparison dyes), demonstrating both exceptional color fastness and color fastness to white staining.

Claims

1. Reactive dyes with ultra-high fixation rate and ultra-high staining fastness, characterized in that: The reactive dye is any of the following compounds:

2. A method for preparing the reactive dye with ultra-high fixation rate and ultra-high staining fastness according to claim 1, characterized in that: The preparation method is any one of the following methods: Method 1: First, prepare the chromophore, then carry out a first condensation reaction with a halogenated s-triazine, and then carry out a second condensation reaction with a bridge group; wherein, in a concentrated hydrochloric acid reaction system, an aniline compound a reacts with a sodium nitrite solution to prepare a diazonium salt b of the aniline compound a; The diazonium salt b reacts with the coupling component compound e to obtain the chromophore g; the diazonium salt b reacts with the coupling component compound f to obtain the chromophore i; Chromogen g reacts with cyanuric chloride to obtain a condensation product l of halogenated s-triazine and chromogen g; chromogen I reacts with cyanuric chloride to obtain a condensation product n of halogenated s-triazine and chromogen I; The aromatic amine compound P containing two amino groups is reacted with product 1 and product n respectively to prepare the reactive dye according to claim 1; Method 2: The halogenated s-triazine is first condensed, then reacted with a diazonium salt, and then subjected to a second condensation reaction with a bridging group; wherein, in a concentrated hydrochloric acid reaction system, the aniline compound a reacts with a sodium nitrite solution to prepare the diazonium salt b of the aniline compound a; The coupling component compound e reacts with cyanuric chloride to obtain a condensation product w of the halogenated s-triazine and the coupling component compound e; The coupling component compound f reacts with cyanuric chloride to obtain a condensation product z of the halogenated s-triazine and the coupling component compound f; The diazonium salt b reacts with the product w to obtain compound l; the diazonium salt b reacts with the product z to obtain compound n; The aromatic amine compound P containing two amino groups is reacted with product 1 and product n respectively to prepare the reactive dye according to claim 1; Method 3: The halogenated s-triazine is first subjected to a condensation reaction, then subjected to a second condensation reaction with a bridging group, and then reacted with a diazonium salt; wherein the coupling component compound e reacts with cyanuric chloride to obtain a condensation product w of the halogenated s-triazine and the coupling component compound e; the coupling component compound f reacts with cyanuric chloride to obtain a condensation product z of the halogenated s-triazine and the coupling component compound f; An aromatic amine compound P containing two amino groups reacts with a compound w to prepare a compound r that can be used in a coupling reaction; an aromatic amine compound P containing two amino groups reacts with a compound z to prepare a compound s that can be used in a coupling reaction; In a concentrated hydrochloric acid reaction system, aniline compound a reacts with sodium nitrite solution to prepare diazonium salt b of aniline compound a; The diazonium salt b reacts with the compound r or the compound s respectively to prepare the reactive dye according to claim 1.

3. A commercial dye prepared from the reactive dye with ultra-high fixation rate and ultra-high staining fastness according to claim 1, characterized in that: The raw materials and various raw materials contained in the commercial dye are as follows: 50-85 parts of active dye, 5-15 parts of diffusing agent, 0.1-0.5 parts of dustproof agent and 15-30 parts of sodium sulfate.

4. The commercial dye according to claim 3, wherein The diffusing agent is a methylnaphthalenesulfonic acid formaldehyde condensate; and the dustproof agent is a water-soluble high molecular compound.

5. Use of the commercial dye according to claim 4 in coloring, printing, pad dyeing, cold pad batch or inkjet printing of cellulose fibers.

6. The use according to claim 5, characterized in that The cellulose fibers are cotton fibers, viscose fibers, flax fibers, and blended fabrics containing two or more of these fibers.

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