Reactive disperse dye and supercritical dyeing method using same

Abstract

The invention provides a reactive disperse dye which is shown in the following formula (I): # imgabs0 #, and D, Ra, Rb, Rc, Rd and L are defined in the specification. In addition, the invention also provides a supercritical dyeing method using the reactive disperse dye.

Description

Technical Field

[0001] The present invention relates to a reactive disperse dye and a supercritical dyeing method using the same, and in particular to a reactive disperse dye that can exhibit good dyeing performance or fastness characteristics and a supercritical dyeing method using the same. Background Art

[0002] The supercritical dyeing method uses carbon dioxide to replace water, and uses a specific machine to apply specific temperature and pressure to make the carbon dioxide reach a supercritical state between gas and liquid, allowing the dye to dissolve, diffuse and penetrate into the pores of the fabric fibers.

[0003] In the current supercritical dyeing market, the use of disperse dyes to dye polyester fibers has reached mass production specifications. However, there are currently no commercial dyes for nylon that can be used in supercritical dyeing.

[0004] Nylon fiber is a strong, wear-resistant, light-weight, and non-deformable man-made fiber. It is suitable for mixing with other fibers to make high-quality and durable clothing. Nylon fiber fabrics are more durable, strong, and ductile than polyester fibers. Nylon fibers are dyed with traditional acid dyes in a water bath. After dyeing, they are washed with soft water. The traditional water bath dyeing process will produce wastewater and other problems.

[0005] Reference 1 points out that traditional acid dyes are insoluble in supercritical carbon dioxide fluid and traditional acid dyes have their own limitations in supercritical dyeing.

[0006] Reference Patent 1 uses supercritical carbon dioxide disperse dyes to dye hydrophobic textile materials but has not been applied to nylon fibers. Reference 1 points out that supercritical dyeing with CI Disperse Red 60 and CI Disperse Yellow 3 dyes to dye nylon fibers has the problem of low water fastness.

[0007] The reactive disperse dyes of references 1 and 2 were used to dye nylon fibers using supercritical dyeing. The ATR spectrum of the dyed fabric proved that there was a covalent bond between the amino group of the nylon fiber and the dye vinyl sulfone, but the dye uptake and color gamut range are also issues to be developed.

[0008] The reactive disperse dye structure of reference patent 2 contains a reactive group diazo component, and the color gamut range is limited by its reactive group.

[0009] In view of this, in order to improve the color gamut of reactive disperse dyes in supercritical dyeing systems, it is urgently needed to develop a novel reactive disperse dye for use in supercritical dyeing, thereby improving the dye uptake, fixation, supercritical carbon dioxide solubility and water fastness of the dye.

[0010] References

[0011] Reference 1: SK Liao, Dyeing of nylon 66 with a disperse-reactive dye using supercritical carbondioxide as the transport medium, 2000, JSDC, 116, 403-407

[0012] Reference 2: SKLiao, Dyeing Nylon-6, 6 with Some Hydrophobic ReactiveDyes by Supercritical Processing, 2004, Journal of Polymer Research, 11, pages 285-291

[0013] Reference Patent

[0014] Reference Patent 1: US5199956

[0015] Reference Patent 2: IN405966 Summary of the invention

[0016] In view of this, the present invention provides a reactive disperse dye and a supercritical dyeing method using the same, in order to at least partially solve the above technical problems. In this regard, the technical solution provided by the present invention is as follows.

[0017] The main purpose of the present invention is to provide a reactive disperse dye, in particular to a reactive disperse dye for use in a supercritical carbon dioxide fluid dyeing method, so as to be applied to supercritical dyeing.

[0018] The reactive disperse dye of the present invention is shown in the following formula (I):

[0019]

[0020] Wherein, D is an aryl or heteroaryl group that does not contain a water-soluble group;

[0021] Ra is H, R or OR;

[0022] Rb is unsubstituted C 3-5 Alkylene;

[0023] Rc and Rd are each independently H; unsubstituted C 1-4 Alkyl; or substituted C 1-4 Alkyl, the substituent is at least one selected from OH, OR, CN, COOR, OC(=O)R, halogen and C 2-4 A combination consisting of alkenyl, and Rc and Rd are not H at the same time;

[0024] L is CH=CH 2 or CH 2 CH 2 Cl; and

[0025] Each R is independently an unsubstituted C1-4 alkyl group; or a substituted C1-4 alkyl group, wherein the substituent is at least one selected from the group consisting of OH, CN and halogen.

[0026] The supercritical dyeing temperature in the method of the present invention depends substantially on the textile fiber to be dyed. Usually the range is 90° C. to 200° C., preferably from 100° C. to 150° C. The pressure must be at least large enough to make the carbon dioxide in a supercritical state. The pressure is preferably 73 to 400 bar, preferably from 150 to 250 bar.

[0027] Generally speaking, the higher the pressure, the greater the solubility of the dye in supercritical carbon dioxide, but the more complex the equipment required.

[0028] Bath ratio (fabric fiber weight: CO 2 Weight) will depend on the product to be dyed and its appearance. Usually the bath ratio is 1:2 to 1:100, preferably about 1:5 to 1:75.

[0029] The temperature and pressure are kept constant for a period of time, generally from 0.5 to 90 minutes, while complete penetration of the supercritical carbon dioxide into the textile material is ensured by suitable measures, usually by stirring or shaking, or preferably by circulating the dye liquor.

[0030] The pressure is then reduced, most simply by opening a valve and releasing the CO2 overpressure. After the valve is opened, the dyed textile material is left dry.

[0031] The reactive disperse dye provided by the present invention has a reactive group; when the reactive disperse dye provided by the present invention is applied to supercritical dyeing, good dyeing behavior can be exhibited. In addition, the alkylene vinyl sulfone reactive group of the reactive disperse dye of the present invention can form a covalent bond with a textile fiber (e.g., nylon fiber) to improve the dyeing properties and the solubility of the dye in supercritical carbon dioxide. Furthermore, the present invention provides a novel reactive disperse dye to improve the color gamut range of the reactive disperse dye in the supercritical dyeing system.

[0032] In the present invention, Ra of formula (I) is H, R or OR, wherein R is an unsubstituted C 1-4 Alkyl; or substituted C 1-4 alkyl, the substituent is at least one selected from the group consisting of OH, CN and halogen. In one embodiment of the present invention, Ra may be H or OR, and R may be an unsubstituted C 1-4In one embodiment of the present invention, Ra may be H or OR, and R may be an unsubstituted C 1-2 In one embodiment of the present invention, Ra may be H or methoxy.

[0033] In the present invention, Rb of formula (I) is an unsubstituted C 3-5 In one embodiment of the present invention, Rb may be an unsubstituted straight chain C 3-5 In one embodiment of the present invention, Rb may be a n-propylene group.

[0034] In the present invention, Rc and Rd in formula (I) are each independently H; unsubstituted C 1-4 Alkyl; or substituted C 1-4 Alkyl, the substituent is at least one selected from OH, OR, CN, COOR, OC(=O)R, halogen and C 2-4 Rc and Rd are not H at the same time; each R is independently an unsubstituted C 1-4 Alkyl; or substituted C 1-4 alkyl, the substituent is at least one selected from the group consisting of OH, CN and halogen. In one embodiment of the present invention, Rc and Rd can each independently be an unsubstituted C 1-4 Alkyl; or substituted C 1-4 Alkyl, the substituent is at least one selected from OR, CN, OC(=O)R and C 2-4 a combination of alkenyl, and R is an unsubstituted C 1-4 In one embodiment of the present invention, Rc and Rd can each independently be an unsubstituted C 1-2 Alkyl; or substituted C 1-2 Alkyl, the substituent is at least one selected from the group consisting of OR, CN, OC(=O)R and vinyl, and R is an unsubstituted C 1-2 In one embodiment of the present invention, Rc and Rd can each independently be an unsubstituted C 1-4 In one embodiment of the present invention, Rc and Rd can each independently be an unsubstituted C 1-2 alkyl.

[0035] In the present invention, Rc and Rd of formula (I) may be the same or different from each other. In one embodiment of the present invention, Rc and Rd may be the same. In one embodiment of the present invention, Rc and Rd may be the same unsubstituted C 1-4 In one embodiment of the present invention, Rc and Rd may be the same unsubstituted C 1-2 In one embodiment of the present invention, Rc and Rd may be the same unsubstituted ethyl group.

[0036] In the present invention, D is an aryl or heteroaryl group that does not contain a water-soluble group; more specifically, D is an aryl or heteroaryl group derived from a diazo component that does not contain a water-soluble group. In one embodiment of the present invention, D may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzothiazolyl group, a substituted or unsubstituted thienyl group, or a substituted or unsubstituted thiazolyl group.

[0037] In one embodiment of the present invention, D may be Among them, each R 1 can be independently chlorine, bromine, nitro, cyano, C 1-4 Alkyl, C 1-4 Alkoxy, C 1-4 Alkoxycarbonyl, C 1-4 Alkylsulfonyl, -SO 2 -C 2-4 Alkenyl or -NHC(=O)-C 1-4 Alkyl; R 2 , R 3 and R 4 can be independently hydrogen, chlorine, bromine, nitro or C 1-4 Alkoxy; each R 5 Can be independently nitro, cyano, C 1-4 Alkyl, C 1-4 Alkylcarbonyl, C 1-4 Alkoxycarbonyl or phenylazo; R 6 can be hydrogen or nitro; n can be 0, 1, 2, 3, 4 or 5; and m can be 0, 1, 2 or 3.

[0038] In one embodiment of the present invention, D may be

[0039] Among them, each R 1 Can be independently chlorine, bromine, nitro, C 1-4 Alkyl, C 1-4 Alkoxy, -SO 2 -C 2-4 Alkenyl or -NHC(=O)-C 1-4 Alkyl; R 2 Can be hydrogen or C 1-4 Alkoxy; R 4 Can be nitro; each R 5 can be independently nitro, cyano or C 1-4 Alkyl; and R 6 It may be nitro.

[0040] In one embodiment of the present invention, specific examples of D include, but are not limited to,

[0041] In one embodiment of the present invention, D may be

[0042] In the present invention, "*" on a functional group or a substituent represents its bonding position.

[0043] The so-called "(ene)alkyl" includes a straight chain or branched carbon-hydrogen substituent, including 1-5 (e.g., 1-4, 1-3 or 1-2) carbon atoms. Examples of (ene)alkyl include (methylene), (ethylene), (n-propylene), (isopropylene), (n-butyl), (isobutyl), (tert-butyl.

[0044] The term "alkoxy" refers to an -O-alkyl group. Examples of alkoxy include methoxy, ethoxy, propoxy, and isopropoxy.

[0045] The term "halogen" includes free radicals of fluorine, chlorine, bromine, or iodine.

[0046] The term "aryl" includes 6-carbon monocyclic, 10-carbon bicyclic, and 14-carbon tricyclic aromatic ring systems. Examples of aryl include phenyl, naphthyl, and anthracenyl.

[0047] By "heteroaryl" is meant a 5-8 membered monocyclic, 8-12 membered bicyclic, or 11-14 membered tricyclic ring system having one or more heteroatoms (e.g., O, N, P, and S). Examples of heteroaryl include triazolyl, oxazolyl, thiadiazolyl, tetrazolyl, pyrazolyl, pyridyl, furyl, imidazolyl, benzimidazolyl, pyrimidinyl, thienyl, quinolinyl, indolyl, thiazolyl, and benzothiazolyl.

[0048] In one embodiment of the present invention, specific examples of the reactive disperse dyes of formula (I) include, but are not limited to, the reactive dyes represented by the following formulas (1) to (6):

[0049]

[0050]

[0051] The present invention also provides the use of the reactive disperse dyes for supercritical dyeing. In one embodiment of the present invention, the reactive disperse dyes can be used to dye a fabric using a supercritical dyeing method. In one embodiment of the present invention, the fabric can be nylon fabric.

[0052] The present invention also provides a supercritical dyeing method using the reactive disperse dye, comprising the following steps: dyeing a fabric with supercritical carbon dioxide fluid and the reactive disperse dye.

[0053] In one embodiment of the present invention, the fabric may be nylon fabric. In one embodiment of the present invention, the amount of dye is 0.1wt% to 5wt% of the weight of the fabric. In one embodiment of the present invention, the amount of dye is about 1wt% of the weight of the fabric.

[0054] The reactive disperse dye of the present invention has a reactive group. When the reactive disperse dye of the present invention is used for supercritical dyeing, the reactive group can form a covalent bond with a fabric (eg, nylon fiber), thereby exhibiting good dyeing performance and fastness characteristics. DETAILED DESCRIPTION

[0055] The following is an explanation of the implementation of the present invention through specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and the details in this specification can also be modified and changed in various ways for different viewpoints and applications without departing from the spirit of the present invention.

[0056] As used in the specification and claims, the singular forms "a," "an," and "the" include one or plural individuals unless the context dictates otherwise.

[0057] Unless otherwise specified herein, the term "or" used in the specification and the appended patent claims generally includes the meaning of "and / or".

[0058] In addition, in this article, the term "about" generally means within 20%, or within 10%, or within 5%, or within 3%, or within 2%, or within 1%, or within 0.5% of a given value or range. The number given here is an approximate number, that is, in the absence of a specific description of "about", the meaning of "about" can still be implied. In addition, the term "range is from a first value to a second value" or "range is between a first value and a second value" means that the range includes the first value, the second value and other values ​​between them.

[0059] The present invention will be described in more detail by way of examples, but these examples are not intended to limit the scope of protection of the present invention. Unless otherwise specified, in the following examples and comparative examples, temperatures are in degrees Celsius, and parts and percentages are by weight. The relationship between parts by weight and parts by volume is like the relationship between kilograms and liters.

[0060] Example 1

[0061] Take 16.4 g of 3-N, N-dimethylaminoaniline and dissolve it in glacial acid aqueous solution, slowly add 23.8 g of 4-(2-chloroethylsulfonyl)butyryl chloride, control the temperature at 5-10°C, and slowly adjust the reaction pH to 4.0-6.0 with sodium carbonate aqueous solution. React for 1 hour, filter the precipitated solid, and vacuum dry to obtain compound 1, 30 g (yield 83%).

[0062]

[0063] Example 2

[0064] Compound 1 (30 g) was dissolved in acetone solution and slowly added into a diluted aqueous solution of glacial sodium hydroxide. The temperature was controlled at 0-5°C and the pH value was maintained at greater than 12. The reaction was carried out for 30 minutes and the reaction pH value was slowly adjusted to 5.0-6.0 to obtain compound 2 (yield 89%).

[0065]

[0066] Example 3

[0067] Take 19.43 g of 3-(N,N-diethyl)amino-4-methoxyaniline and dissolve it in glacial acid aqueous solution, slowly add 23.8 g of 4-(2-chloroethylsulfonyl)butyryl chloride, control the temperature at 5-10°C, and slowly adjust the reaction pH to 4.0-6.0 with sodium carbonate aqueous solution. React for 1 hour, filter the precipitated solid, and vacuum dry to obtain compound 3, 34.4 g (yield 88%).

[0068]

[0069] Example 4

[0070] Take 18.92 g of 3-amino-N-ethyl-N-cyanoethylaniline and dissolve it in glacial acid aqueous solution, slowly add 23.8 g of 4-(2-chloroethylsulfonyl)butyryl chloride, control the temperature at 5-10°C, and slowly adjust the reaction pH to 4.0-6.0 with sodium carbonate aqueous solution. React for 1 hour, filter the precipitated solid, and vacuum dry to obtain compound 4, 31.6 g (yield 82%).

[0071]

[0072] Example 5 to Example 30

[0073] The following Examples 5 to 30 were prepared in a similar manner to the above Examples 1 to 4. The structures of the compounds of Examples 5 to 30 are shown in Table 1 below.

[0074] Table 1

[0075]

[0076]

[0077] Embodiment 31

[0078] Step (a): 11.7 parts of 4-nitroaniline were added to 250 parts of water and mixed thoroughly, 25 mL of 32% HCl was added to adjust the pH to 1.0, and 6.05 parts of sodium nitrite were slowly added under stirring within 20 minutes, stirred for one hour, and excess nitrite was destroyed by adding 0.5 parts of ammonium sulfite.

[0079] Step (b): Compound 1 is added to 100 parts of water and the diazonium salt component obtained in step (a) is slowly added under stirring. The temperature is controlled at 10-15°C and Na 2 CO 3 The reaction solution was stirred for two hours while maintaining a pH value of 2-4, and the precipitated solid was filtered and vacuum dried to obtain the red dye compound 31. max =512nm, MS: m / z 510.16(M+H) + .

[0080]

[0081] Embodiment 32

[0082] Step (a): 10.41 g of 4-nitroaniline was added to 250 g of water and mixed thoroughly, 25 mL of 32% HCl was added to adjust the pH to 1.0, and 5.4 g of sodium nitrite was slowly added under stirring within 20 minutes, stirred for one hour, and excess nitrite was destroyed by adding 0.5 g of ammonium sulfite.

[0083] Step (b): Compound 2 is slowly added to the diazonium salt component obtained in step (a) under stirring, the temperature is controlled at 10-15°C, and Na 2 CO 3 The reaction solution was stirred for two hours while maintaining a pH value of 2-4, and the precipitated solid was filtered and vacuum dried to obtain the red dye compound 32. max =512nm, MS: m / z 474.23(M+H) + .

[0084]

[0085] Embodiment 33

[0086] Step (a): 21.82 g of 2-[(4-aminophenyl)sulfonyl]ethanol hydrogen sulfate is added to 150 g of water and mixed thoroughly, and then slowly added to a diluted glacial sodium hydroxide aqueous solution, the temperature is controlled at 0-5° C., the pH value is maintained at greater than 12, and the reaction is carried out for 30 minutes. 35 mL of 32% HCl is added to adjust the pH value to 1.0, the temperature is controlled at 0-5° C., and 5.51 g of sodium nitrite is slowly added under stirring within 20 minutes, stirred for one hour, and excess nitrite is destroyed by adding 0.5 g of ammonium sulfite.

[0087] Step (b): Compound 2 is slowly added to the diazonium salt component obtained in step (a) under stirring, the temperature is controlled at 10-15°C, and Na 2 CO 3 The reaction solution was stirred for two hours while maintaining a pH value of 2-4, and the precipitated solid was filtered and vacuum dried to obtain the orange dye compound 33. max =486nm, MS: m / z 519.19(M+H) + .

[0088]

[0089] Embodiment 34

[0090] Step (a): 98% concentrated sulfuric acid solution, the temperature is controlled at 0-5°C, 5.15g of sodium nitrite is slowly added under stirring, and the reaction is stirred at low temperature for 10-15 minutes, and then the temperature is controlled at 60-75°C and stirred until the sodium nitrite is completely dissolved to obtain a nitrosyl sulfuric acid solution. The solution is placed in a low temperature environment of 0-5°C again, 19.36g of 2-bromo-4,6-dinitroaniline is added in batches, and the reaction is kept at a constant temperature and stirred for 2-3 hours to obtain an aromatic amine diazonium salt.

[0091] Step (b): Compound 2 is slowly added to the diazonium salt component obtained in step (a) under stirring, the temperature is controlled at 10-15°C, and Na 2 CO 3 The reaction solution was stirred for two hours while maintaining a pH value of 2-4, and the precipitated solid was filtered and vacuum dried to obtain the blue-violet dye compound 34. max =558nm, MS: m / z 597.08(M+H) + .

[0092]

[0093] Embodiment 35

[0094] Step (a): 98% concentrated sulfuric acid solution, the temperature is controlled at 0-5°C, 5.15g of sodium nitrite is slowly added under stirring, and the reaction is stirred at low temperature for 10-15 minutes, and then the temperature is controlled at 60-75°C and stirred until the sodium nitrite is completely dissolved to obtain a nitrosyl sulfuric acid solution. The solution is placed in a low temperature environment of 0-5°C again, 19.36g of 2-bromo-4,6-dinitroaniline is added in batches, and the reaction is kept at a constant temperature and stirred for 2-3 hours to obtain an aromatic amine diazonium salt.

[0095] Step (b): Compound 13 is slowly added to the diazonium salt component obtained in step (a) under stirring, the temperature is controlled at 10-15°C, and Na 2 CO 3 The reaction solution was stirred for two hours while maintaining the pH value of 2-4, and the precipitated solid was filtered and dried in vacuo to obtain a blue dye compound (35). λmax=580nm, MS: m / z 627.09 (M+H)+.

[0096]

[0097] Embodiment 36

[0098] Step (a): 98% concentrated sulfuric acid solution, the temperature is controlled at 0-5°C, 5.15g of sodium nitrite is slowly added under stirring, and the reaction is stirred at low temperature for 10-15 minutes, and then the temperature is controlled at 60-75°C and stirred until the sodium nitrite is completely dissolved to obtain a nitrosyl sulfuric acid solution. The solution is placed in a low temperature environment of 0-5°C again, 12.06g of 5-amino-3-methyl-2,4-thiophene dicarbonitrile is added in batches, and the reaction is kept at a constant temperature and stirred for 2-3 hours to obtain an aromatic amine diazonium salt.

[0099] Step (b): Compound 2 is slowly added to the diazonium salt component obtained in step (a) under stirring, the temperature is controlled at 5-10°C, and Na 2 CO 3 The reaction solution was stirred for two hours while maintaining the pH value of 2-4, and the precipitated solid was filtered and dried in vacuo to obtain the blue-violet dye compound 36. λmax=591nm, MS: m / z 499.16 (M+H)+.

[0100]

[0101] Example 37 to Example 44

[0102] The following Examples 37 to 44 were prepared in a similar manner to the above Examples 31 to 36. The structures of the compounds of Examples 37 to 44 are shown in Table 2 below.

[0103] Table 2

[0104]

[0105]

[0106] Supercritical dyeing method

[0107] The supercritical carbon dioxide dyeing equipment used in the present invention is manufactured by DyeCoo. The nylon fiber is laboratory dyed with supercritical carbon dioxide fluid, and the dye (accounting for 1% of the weight of the nylon fiber) and 10 grams of nylon fiber are placed in a dyeing pot. The dyeing pot is tightly covered, and the required amount of liquid carbon dioxide is poured into the tightly closed dyeing pot, with a carbon dioxide bath ratio of 1:15; it is subjected to a dyeing cycle at 120°C and 250 bar pressure for 60 minutes. After appropriate washing and drying, the dyed material is evaluated for K / S. The test results are shown in Table 3 below.

[0108] Table 3

[0109] dye K / S <![CDATA[λ max ]]> Compound 33 of Example 33 29.5 486nm Compound 32 of Example 32 26.8 512nm Compound 34 of Example 34 26.4 558nm

[0110] As shown in the results of Table 3, the reactive disperse dyes provided by the present invention can exhibit good dyeing performance and fastness characteristics.

[0111] Covalent bond confirmation method

[0112] The red reactive disperse dye of compound 32 of Example 32 was compared with the compound of the following formula (a); and the orange reactive disperse dye of compound 33 of Example 33 was compared with the compound of the following formula (b). The comparison method is as follows.

[0113]

[0114] After the supercritical carbon dioxide dyeing is completed, 1 g of the dyed fabric sample (nylon fiber) is taken out, placed in 85°C x 50 g DMSO and stirred for 30 minutes each, and then the fabric sample is taken out and washed with 60°C x 50 g water for 5 minutes each and subjected to conventional drying procedures.

[0115] The test results show that when the red reactive disperse dye of compound 32 of Example 32 and the orange reactive disperse dye of compound 33 of Example 33 were used for dyeing, and the dyed nylon fibers were treated with DMSO, almost no DMSO was removed during the washing process. However, the compounds of formula (a) and (b) without reactive groups were observed to fade significantly.

[0116] Washing fastness test

[0117] Using the aforementioned supercritical dyeing method, nylon fabric and cotton fabric were dyed with the orange reactive disperse dye of compound 33 of Example 33. Here, the dyeing and finishing AATCC 2A test method was used, which is a method for testing the color fastness of dyed and finished fabrics after home washing. The operation process of dyeing and finishing AATCC 2A is as follows.

[0118] Prepare WOB detergent and six-fiber strips, as well as special spring steel bottles and steel balls. There are six different fibers on the six-fiber strips, namely acetate, cotton, nylon, polyester, acrylic and wool. Dissolve 1.5 grams of WOB detergent in 200 ml of warm distilled water, and then add cold distilled water to 1 liter to make detergent. Cut the test color cloth into 15 cm x 5 cm sizes, and cut the six-fiber strips into 5 cm x 5 cm sizes. Put the wool strip of the six-fiber strip on the right side, and then put the six-fiber strip on the upper half of the color cloth, and sew along the 5 cm edge with thread or nails to form a synthetic sample. Pour 150 ml of detergent into the spring steel bottle and add 50 steel balls. Put the synthetic sample into the spring steel bottle and close the bottle mouth. Put the spring steel bottle into the cylinder of the washing fastness machine preheated to 49 degrees and wash it for 45 minutes. Take the sample out of the spring steel bottle, rinse it with tap water, dehydrate it, and dry it at a temperature below 60 degrees.

[0119] The test results are shown in Table 4 below.

[0120] Table 4

[0121]

[0122] The test results show that the orange reactive disperse dye of compound 33 of Example 33 exhibits excellent washing fastness on both cotton fabric and nylon fabric.

[0123] In summary, the novel reactive disperse dyes provided by the present invention can exhibit good dyeing performance and fastness properties on fabrics (eg, nylon fibers) through supercritical dyeing, and can be applied to supercritical dyeing.

[0124] The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A reactive disperse dye for use in a supercritical carbon dioxide fluid dyeing method, as shown in the following formula (I): in, D is an aryl or heteroaryl group that does not contain a water-soluble group; Ra is H, R or OR; Rb is unsubstituted C 3-5 Alkylene; Rc and Rd are each independently H; unsubstituted C 1-4 Alkyl; or substituted C 1-4 Alkyl, the substituent is at least one selected from OH, OR, CN, COOR, OC(=O)R, halogen and C 2-4 A combination consisting of alkenyl, and Rc and Rd are not H at the same time; L is CH=CH2 or CH2CH2C1 and Each R is independently unsubstituted C 1-4 Alkyl; or substituted C 1-4 The alkyl group, the substituent is at least one selected from the group consisting of OH, CN and halogen.

2. The reactive disperse dye according to claim 1, wherein Ra is H or OR, and R is unsubstituted C 1-4 alkyl.

3. The reactive disperse dye according to claim 1, wherein Rc and Rd are each independently unsubstituted C 1-4 Alkyl; or substituted C 1-4 Alkyl, the substituent is at least one selected from OR, CN, OC(=O)R and C 2-4 a combination of alkenyl, and R is an unsubstituted C 1-4 alkyl.

4. The reactive disperse dye according to claim 3, wherein Rc and Rd are each independently unsubstituted C 1-4 alkyl.

5. The reactive disperse dye according to claim 1, wherein Rc and Rd are the same.

6. The reactive disperse dye according to claim 1, wherein D is substituted or unsubstituted phenyl, substituted or unsubstituted benzothiazolyl, substituted or unsubstituted thienyl or substituted or unsubstituted thiazolyl.

7. The reactive disperse dye according to claim 1, wherein D is wherein each R1 is independently chlorine, bromine, nitro, cyano, C 1-4 Alkyl, C 1-4 Alkoxy, C 1-4 Alkoxycarbonyl, C 1-4 Alkylsulfonyl, -SO2-C 2-4 Alkenyl or -NHC(=O)-C 1-4 alkyl; R2, R3 and R4 are each independently hydrogen, chlorine, bromine, nitro or C 1-4 Alkoxy; Each R5 is independently nitro, cyano, C 1-4 Alkyl, C 1-4 Alkylcarbonyl, C 1-4 Alkoxycarbonyl or phenylazo; R6 is hydrogen or nitro; n is 0, 1, 2, 3, 4 or 5; and m is 0, 1, 2 or 3.

8. The reactive disperse dye according to claim 7, wherein D is wherein each R1 is independently chlorine, bromine, nitro, C 1-4 Alkyl, C 1-4 Alkoxy, -SO2-C 2-4 Alkenyl or -NHC(=O)-C 1-4 alkyl; R2 is hydrogen or C 1-4 Alkoxy; R4 is nitro; Each R5 is independently nitro, cyano or C 1-4 Alkyl; and R6 is nitro.

9. The reactive disperse dye according to claim 8, wherein D is 10. The reactive disperse dye according to claim 9, wherein D is 11. The reactive disperse dye according to claim 1, which is any reactive dye represented by the following formulas (1) to (6):

12. A supercritical dyeing method comprising the following steps: A fabric is dyed with supercritical carbon dioxide fluid and the reactive disperse dye according to any one of claims 1 to 11.

13. The dyeing method according to claim 12, wherein The fabric is nylon fabric.

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