Dicarboximide monoazo disperse dye as well as preparation method and application thereof

Abstract

The invention discloses a dicarboximide monoazo disperse dye as well as a preparation method and application thereof, and relates to the technical field of azo disperse dyes, the structural general formula of the dicarboximide monoazo disperse dye is as shown in a formula 1 or a formula 2: # imgabs0. The dicarboximide monoazo disperse dye synthesized by the invention is applied to hydrophobic fiber dyeing, especially polyester fibers, and the dye has a good application prospect. The light-resistant, heat-migration-resistant, water-soaking-resistant, perspiration-resistant, color-fastness to washing and good fastness to rubbing are shown by the light-resistant, heat-migration-resistant, water-soaking-resistant, sweat-resistant, color-fastness to washing and good fastness to rubbing.

Description

Technical Field

[0001] The present invention relates to an azo disperse dye, and in particular to a dicarboximide monoazo disperse dye and a preparation method and application thereof. Background Art

[0002] Polyester fabric is the most widely used textile fiber in the market. Polyester fiber has excellent properties, such as high breaking strength and elastic modulus, good heat resistance and light resistance, good corrosion resistance and washability, making it one of the fastest growing and highest-yielding varieties of polyester fiber. Polyester is a polymer obtained by polycondensation of dibasic acid and diol. The basic chain segments are connected by ester groups. There are no hydrophilic groups on the molecular chain and there are no active groups that can bind to dyes. It can only be dyed with disperse dyes.

[0003] Disperse dyes are special dyes for polyester fabrics. They have a simple structure and diffuse into the fiber interior and gaps in a molecular state during dyeing. They are fixed on polyester under the action of van der Waals force, hydrogen bond and dipole force. For conventional azo disperse dyes, their structure can be mainly divided into two parts: diazo component and coupling component. The diazo component mainly affects the hue of the dye, and the coupling component affects the dyeing application performance of the dye. A small structural change on the coupling component may cause a huge change in the dyeing performance, diffusion mechanism, adhesion ability, etc. of the entire dye, thereby greatly affecting the process control and waste liquid treatment in the polyester dyeing process. In addition, the performance of disperse dyes with new structures also provides a theoretical basis and practical experience for future research on the structure-activity relationship of dyes. Therefore, it is very meaningful to discover and study disperse dyes with coupling components with new structures. Summary of the invention

[0004] The first aspect of the present invention is to provide a dicarboximide monoazo disperse dye, the general structural formula of which is shown in Formula 1 or Formula 2:

[0005]

[0006]

[0007] Where:

[0008] Ar is a dye diazo component, including but not limited to any one of formula (a)-(l):

[0009]

[0010] R0 is a C1-C4 alkyl group or a derivative thereof;

[0011] R1 is H, a halogen atom, a C1-C4 alkyl or alkoxy group;

[0012] R2 is H, a halogen atom, a C1-C4 alkyl group or -NHCOR8 (wherein R8 is a C1-C4 alkyl group or alkoxy group, aryl group, hydroxyl group, amino group or halogen atom which is unsubstituted or substituted by one or more than one substituted group), an aromatic group which is unsubstituted or substituted by one or more than one substituted group (the substituent of the aromatic group may be a C1-C4 alkoxy group, hydroxyl group, amino group or halogen atom).

[0013] R3 is unsubstituted or substituted with one or more C1-C4 alkane, hydroxyl, amino, -COOR8, -OCOR8 (wherein R8 is unsubstituted or substituted with one or more C1-C4 alkyl or alkoxy, aryl, hydroxyl, amino or halogen atom);

[0014] R4 is H or a C1-C4 alkane;

[0015] X is O or S;

[0016] n is 0 or 1;

[0017] m is 1-5;

[0018] When n=0, m=1, R2 is not O or methyl;

[0019] R5, R6 and R7 are independently H at any substitution position of the benzene ring, C1-C4 alkyl or alkoxy, -CN, -NO2, OH, CF3, -COOR9 or -CONHR9 (wherein R9 is C1-C4 alkane or aryl), or a heterocyclic substituent; the heterocyclic substituent preferably contains 4 or 5 carbon atoms and 1 or 2 heteroatoms from O, S and N groups, for example, pyrrolyl, furanyl, thienyl, oxazolyl, thiazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridyl, indolyl, purinyl or quinolyl.

[0020] R 10 It is a C1-C4 alkane, a C1-C4 alkoxy group or a C1-C4 cyanoalkyl group.

[0021] M1, M2 and M3 are independently H, Br, Cl, CN, OH, NO2, CF3 or C1-C4 alkane.

[0022] M4 and M5 are independently H, Br, Cl, cyano, hydroxyl, nitro or trifluoromethyl.

[0023] M6 is cyano, nitro or C1-C4 alkane.

[0024] M7 is H, Br, Cl, C1-C4 alkoxy, 5-30 C aromatic ring group or 6-30 C aralkyl group.

[0025] M8 is H, cyano, nitro or -COR4 (R4 is H or C1-C4 alkane).

[0026] Further:

[0027] When the aforementioned substituent is an aryl group, it preferably has 5 to 24 carbon atoms, and particularly has 6 to 14 carbon atoms. It is preferably any one of the following substituents: phenyl, formylphenyl, methoxyphenyl, ethoxyphenyl, 2-hydroxyphenyl, 4-hydroxyphenyl, 2-chlorophenyl, 4-chlorophenyl, 2,6-dichlorophenyl, 2-aminophenyl, 3-aminophenyl, 4-aminophenyl, 4-methoxyphenyl, 4-ethoxyphenyl, naphthyl and phenol.

[0028] When the aforementioned substituent is an alkyl group, it may be a straight chain or branched alkyl group, and preferably any one of the following substituents: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, n-decyl and n-dodecyl.

[0029] When the aforementioned substituent is a substituted alkyl group, it is preferably any one of the following substituents: 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybutyl, 2-aminoethyl, 2-aminopropyl, 4-aminobutyl, cyanoethyl, 2-cyanoethyl, 2-chloroethyl, 2-bromoethyl and 4-chlorobutyl.

[0030] When the aforementioned substituent is an alkoxy group, it is preferably any one of the following substituents: methoxy, ethoxy, n-propyl, isopropyl, n-butoxy, isobutoxy, n-butoxy, tert-butoxy, pentyloxy, neopentyloxy, n-hexyl, n-heptyl, n-octyl, isooctyl, n-decyl, and n-dodecyl.

[0031] Halogen is preferably F, Cl or Br, in particular Cl or Br.

[0032] The second aspect of the present invention is to provide a method for preparing a dicarboximide monoazo disperse dye, characterized in that it comprises the following steps:

[0033] (1) Using dianhydride and amino compound as raw materials, generating coupling component (Formula 3 or Formula 4) through coupling reaction;

[0034]

[0035] (2) Using the diazonium salt and the coupling component synthesized in step (1) as raw materials, a novel dicarboximide monoazo disperse dye is synthesized through a coupling reaction.

[0036] Further settings are as follows:

[0037] In step (1):

[0038] The dianhydride is selected from one of the compounds shown in Formula 6 or Formula 7; the amino compound is selected from one of the compounds shown in Formula 5:

[0039]

[0040] In step (2):

[0041] The diazonium salt can be a commercial product or can be synthesized by a known diazotization reaction, for example, sodium nitrite in an aqueous medium containing hydrochloric acid or sulfuric acid. In addition, the diazotization can also be carried out using other diazotization agents, for example, nitrosylsulfuric acid. In the diazotization, an additional acid can be present in the reaction medium, for example, phosphoric acid, sulfuric acid, acetic acid, propionic acid or hydrochloric acid or a mixture of these acids, for example a mixture of propionic acid and acetic acid. The diazotization is advantageously carried out at a temperature of -10 to 30°C.

[0042] In step (2), the diazonium salt undergoes a coupling reaction with the coupling components of formula (3) and (4), and the coupling reaction is preferably carried out in an acidic or organic aqueous medium, and the acid used is selected from any one of hydrochloric acid, acetic acid, propionic acid, sulfuric acid and phosphoric acid; the reaction temperature is preferably -10 to 30°C.

[0043]

[0044] After the reaction of the coupling component and the diazonium salt is completed, the pH of the solution needs to be adjusted to 7-8 by adding alkaline substances, such as adding Na2CO3 or NaOH, to hydrolyze the excess unreacted acid anhydride.

[0045] After the above steps are completed, the new disperse dye pure product is obtained through conventional post-treatment, and the post-treatment includes: filtration, drying, and recrystallization.

[0046] The third aspect of the present invention is to provide a use of the dicarboximide monoazo disperse dye in dyeing hydrophobic fibers.

[0047] According to the dye characteristics of the present invention, it can be applied to dyeing, printing, color matching, etc. of common hydrophobic fibers, including but not limited to: polyester, polyester-cotton blended fibers, acetate fibers. The hydrophobic fibers can have a variety of processing forms, such as: fibers, yarn rolls, non-woven fabrics, or knitted and woven fabrics.

[0048] The dyeing process follows the common disperse dyeing process, for example, dyeing is carried out at a temperature of 80-140° C. in the presence of a dispersant or a carrier. Applicable dyeing methods include but are not limited to: hot melt dyeing, high temperature and high pressure dyeing, carrier dyeing, printing dyeing, and supercritical CO2 dyeing.

[0049] The dye master liquor is prepared in a common manner, for example, the dye and the dispersant are evenly ground in a ratio of 1:1 to prepare a 2 g / L dye master liquor.

[0050] For printing, common thickeners are used, such as modified or unmodified natural products, or synthetic products.

[0051] The beneficial effects of the present invention are as follows:

[0052] The invention synthesizes a novel dicarboximide monoazo disperse dye. According to the dye structure and dye characteristics of the invention, the dye has very good use fastness when applied to dyeing hydrophobic fibers, especially polyester fibers, and exhibits good light fastness, heat migration resistance, blister resistance, sweat resistance, color fastness to washing, and good rubbing fastness.

[0053] The present invention is further described below in conjunction with the accompanying drawings and specific embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] Figure 1 This is the NMR spectrum of the new dye 1.

[0055] Figure 2 This is the infrared spectrum of the new dye 1.

[0056] Figure 3 This is the absorption spectrum curve of the new dye 1.

[0057] Figure 4 It improves the dyeing ability of the new dye 1.

[0058] Figure 5 is the dyeing rate of the new dye 1.

[0059] Figure 6 This is the NMR spectrum of the new dye 2.

[0060] Figure 7 This is the infrared spectrum of the new dye 2.

[0061] Figure 8 This is the absorption spectrum curve of the new dye 2.

[0062] Fig. 9 Improves the dyeing ability of new dye 2.

[0063] Fig.10 is the dyeing rate of new dye 2.

[0064] Fig.11 This is the NMR spectrum of the new dye 3.

[0065] Fig.12 This is the infrared spectrum of the new dye 3.

[0066] Fig.13This is the absorption spectrum curve of the new dye 3.

[0067] Fig.14 Improves the dyeing ability of new dye 3.

[0068] Fig.15 is the dyeing rate of new dye 3.

[0069] Fig.16 This is the NMR spectrum of the new dye 4.

[0070] Fig.17 This is the infrared spectrum of the new dye 4.

[0071] Fig.18 This is the absorption spectrum curve of the new dye 4.

[0072] Fig.19 Improves the dyeing ability of new dye 4.

[0073] Fig. 20 is the dyeing rate of new dye 4. DETAILED DESCRIPTION

[0074] Example 1

[0075] Add 20mL of acetic acid as solvent to a 100mL three-necked flask, add 10mmol of N-(3-aminopropyl)-N-methylaniline, heat and stir to dissolve, after complete dissolution, add 11mmol of phthalic anhydride at 60℃, heat and reflux to react, and track the reaction by thin layer chromatography. After the reaction is complete, transfer all the liquid to a 1L three-necked flask, add 100mL of distilled water, and a few drops of concentrated sulfuric acid to promote dissolution, stir until the liquid is clear, and cool to 0℃ for use.

[0076] Add 20mL of distilled water, 6mL of hydrochloric acid, and 10mmol of p-nitroaniline to a three-necked flask, heat to 80℃, stir and dissolve, then cool to 0℃, add 11mmol of sodium nitrite solution, and react for 1h. Then slowly add the diazonium salt dropwise to the coupling component prepared in the previous step, keep the reaction at 0℃, use H acid to check the end point of the reaction, adjust the pH of the solution to 7 with Na2CO3 after the reaction, continue stirring for 2h, and remove the excess anhydride. Filter and wash to obtain a crude product with a yield of 94%. The crude product is recrystallized from ethanol to obtain a pure disperse dye, marked as dye 1.

[0077] The reaction equations involved are as follows:

[0078]

[0079] Product Confirmation:

[0080] (1) Dye molecular structure

[0081]

[0082] (2) Molecular structure characterization

[0083] like Figure 1 Shown is the nuclear magnetic resonance spectrum of the new dye 1.

[0084] NMR analysis: 1 H-NMR (500MHz, DMSO-d6, δ H ,ppm):8.36-8.37(d,2H,Ar-H),7.93-7.95(d,2H,Ar-H),7.82-7.88(m,6H,Ar-H),6.89-6.91(d,2 H,Ar-H),3.65-3.68(t,2H,CH2),3.57-3.60(t,2H,CH2),3.09(s,3H,CH3),1.90-1.96(m,2H,CH2).

[0085] like Figure 2 Shown is the infrared spectrum of the new dye 1.

[0086] Infrared analysis: 3090cm -1 It is the CH stretching vibration peak of the benzene ring, 2936cm -1 , 2886cm -1 It is the CH stretching vibration peak of saturated hydrocarbons, 1709cm -1 C=O stretching vibration peak, 1597cm -1 The peak of the skeleton vibration of the benzene ring is 1506 cm -1 The nitro group has the N=O asymmetric stretching vibration peak, 1377 cm -1 The CH bending vibration peak of the methyl group is 1331 cm -1 The N=O symmetrical stretching vibration peak of the nitro group is 1157 cm -1 , 1142cm -1 , 1097cm -1 The CN bending vibration peak of amide, 860 cm -1 , 822cm -1 They correspond to the out-of-plane swing peaks of the para-substituted CH of the two benzene rings.

[0087] (3) Spectral absorption performance

[0088] Weigh 0.01 g of the new dye 1, dissolve it in 100 mL of N,N-dimethylformamide, dilute it 5 times to a concentration of 0.02 g / L, and use a UV-2450 ultraviolet-visible spectrophotometer (Shimadzu Corporation, Japan) to measure the absorption spectrum curve. Figure 3 shown.

[0089] The maximum absorption wavelength of the new dye 1 is 494nm, and the molar extinction coefficient ε=28603.17L·mol -1 cm -1 .

[0090] (4) Dye solution and dyeing properties

[0091] Accurately weigh 2 g of dye 1 and put it into a mortar. Add a little water, grind and transfer to a 1000 mL volumetric flask to make a 2 g / L mother solution.

[0092] This mother liquor was taken to prepare dye liquor of different concentrations. The cut 1g polyester fabric sample was wetted and then thrown into the dye bath (pH=5, bath ratio 1:20). Then the sealed dye cylinder was installed in the high temperature and high pressure dyeing machine. The dye bath temperature was raised from 50℃ to 130℃ at a heating rate of 2℃ / min, kept warm for 60min, and then quickly cooled to room temperature. After rinsing the fabric sample with cold water, the dyed polyester fabric was reduced and cleaned at 85℃ for 15min with the prepared reduction cleaning solution (2g / L sodium carbonate, 2g / L hydrosulfite, bath ratio 1:50) and then dried. The dyeing results are as follows: Figure 4 The saturation concentration of the new dye 1 is about 3%, and the K / S value can reach more than 16 when the dosage is 2%.

[0093] The mother liquor was taken out to prepare a 1% (owf) dye solution. The cut 1g polyester fabric sample was wetted and then thrown into the dye solution (pH=5, bath ratio 1:20). Then the sealed dye cup was installed in the high temperature and high pressure dyeing machine. The dye solution temperature was raised from 50°C to 130°C at a heating rate of 2°C / min, kept warm for 60 minutes, and then quickly cooled to room temperature. A dye cup was taken out every 10 minutes during the heating stage and every 15 minutes during the insulation stage. After rinsing the fabric sample with cold water, the dyed polyester fabric was reduced and cleaned at 85°C for 15 minutes using the prepared reduction cleaning solution (2g / L sodium carbonate, 2g / L insurance powder, bath ratio 1:50) and then dried. The dyeing results are as follows: Figure 5 The dye reaches saturation concentration around 55 minutes, and then the dye can only be adsorbed in the shallow surface layer, which is greatly affected by the physical properties of the fiber.

[0094] (5) Color fastness performance

[0095] According to ISO 105-C04 (2010) "Textiles - Tests for Color Fastness to Washing", the color fastness to washing of dyed fabrics with a dye concentration of 1% (owf) is tested. According to ISO 105 / P01 (1993) "Textiles - Tests for Color Fastness to Dry Heat (Except Hot Pressing)", the color fastness to sublimation of dyed fabrics with a dye concentration of 1% (owf) is tested. According to ISO 105-X12 (2016) "Textiles - Tests for Color Fastness to Rubbing", the dry / wet rubbing fastness of polyester dyed fabrics with a dye dosage of 1% (owf) is tested, as shown in the following table:

[0096]

[0097] From the data in the table, we can see that the fastness of the new dye 1 is above level 4-5, the light fastness is level 6, and it has good color fastness.

[0098] Example 2

[0099] Add 20mL of acetic acid as solvent to a 100mL three-necked flask, add 10mmol of N-(3-aminopropyl)-N-methylaniline, heat and stir to dissolve, after complete dissolution, add 11mmol of succinic anhydride at 60℃, heat and reflux to react, and track the reaction by thin layer chromatography. After the reaction is complete, transfer all the liquid to a 1L three-necked flask, add 100mL of distilled water, stir until the liquid is clear, and cool to 0℃ for use.

[0100] Add 20mL of distilled water, 6mL of hydrochloric acid, and 10mmol of p-nitroaniline to a three-necked flask, heat to 80℃, stir and dissolve, then cool to 0℃, drop 11mmol of sodium nitrite solution, and react for 1h. Then slowly drop the diazonium salt into the coupling component prepared in the previous step, keep the reaction at 0℃, use H acid to check the end point of the reaction, adjust the solution pH to 7 with Na2CO3 after the end, continue stirring for 2h, and remove excess anhydride. Filter and wash to obtain a crude product with a yield of 92%. The crude product is recrystallized from ethanol to obtain a pure disperse dye, marked as dye 2.

[0101] The reaction equations involved are as follows:

[0102]

[0103] Product Confirmation:

[0104] (1) Dye molecular structure

[0105]

[0106] (2) Molecular structure characterization

[0107] like Figure 6Shown is the NMR spectrum of the new dye 2.

[0108] NMR analysis: 1 H-NMR (500MHz, DMSO-d6, δ H ,ppm):8.36-8.37(d,2H,Ar-H),7.93-7.95(d,2H),7.84-7.86(d,2H,Ar-H),6.87-6.89(d,2H,Ar-H),3. 50-3.53(t,2H,CH2),3.42-3.45(t,2H,CH2),3.07(s,3H,CH3),2.63(s,4H,CH2-CH2),1.76-1.82(m,2H).

[0109] like Figure 7 Shown is the infrared spectrum of the new dye 2.

[0110] Infrared analysis: 3098cm -1 , 3075cm -1 is the CH stretching vibration of the benzene ring, 2951 cm -1 and 2830cm -1 Corresponding to the stretching vibration peak of saturated hydrocarbon CH, 1692 cm -1 is the C=O stretching vibration peak of the anhydride, 1605cm -1 , 1587cm -1 , 1447cm -1 , is the skeleton stretching vibration peak of the benzene ring, 1510cm -1 It is the asymmetric stretching vibration of nitro N=O, 1410cm -1 The CN stretching vibration peak on the amide, 1385 cm -1 The bending vibration peak of methyl group is 1335cm -1 The N=O symmetrical stretching vibration peak of the nitro group is 1211 cm -1 , 1159cm -1 , 1142cm -1 , is the CN bending vibration on the amide, 858cm -1 , 827cm -1 They correspond to the out-of-plane swing peaks of the CH substituents on the two benzene rings.

[0111] (3) Spectral absorption performance

[0112] Weigh 0.01 g of new dye 2, dissolve it in 100 mL of N,N-dimethylformamide, dilute it 5 times to a concentration of 0.02 g / L, and use a UV-2450 ultraviolet-visible spectrophotometer (Shimadzu Corporation, Japan) to measure the absorption spectrum curve. Figure 8 shown.

[0113] The maximum absorption wavelength of the new dye 2 is 492nm, and the molar extinction coefficient ε=41453.20L·mol -1 cm -1 .

[0114] (4) Dye solution and dyeing properties

[0115] Accurately weigh 2 g of dye 2 and put it into a mortar. Add a little water, grind and transfer to a 1000 mL volumetric flask to make a 2 g / L mother solution.

[0116] This mother liquor was taken to prepare dye liquor of different concentrations. The cut 1g polyester fabric sample was wetted and then thrown into the dye bath (pH=5, bath ratio 1:20). Then the sealed dye cylinder was installed in the high temperature and high pressure dyeing machine. The dye bath temperature was raised from 50℃ to 130℃ at a heating rate of 2℃ / min, kept warm for 60min, and then quickly cooled to room temperature. After rinsing the fabric sample with cold water, the dyed polyester fabric was reduced and cleaned at 85℃ for 15min with the prepared reduction cleaning solution (2g / L sodium carbonate, 2g / L hydrosulfite, bath ratio 1:50) and then dried. The dyeing results are as follows: Fig. 9 When the dosage of the new dye 2 is 0.25%, the K / S can reach 9, when the concentration is 1%, the K / S exceeds 16, and when the concentration is 2%, the equilibrium is reached, and the K / S reaches more than 18.

[0117] The mother liquor was taken out to prepare a 1% (owf) dye solution. The cut 1g polyester fabric sample was wetted and then thrown into the dye solution (pH=5, bath ratio 1:20). Then the sealed dye cup was installed in the high temperature and high pressure dyeing machine. The dye solution temperature was raised from 50°C to 130°C at a heating rate of 2°C / min, kept warm for 60 minutes, and then quickly cooled to room temperature. A dye cup was taken out every 10 minutes during the heating stage and every 15 minutes during the insulation stage. After rinsing the fabric sample with cold water, the dyed polyester fabric was reduced and cleaned at 85°C for 15 minutes using the prepared reduction cleaning solution (2g / L sodium carbonate, 2g / L insurance powder, bath ratio 1:50) and then dried. The dyeing results are as follows: Fig.10 As shown in Figure 2, the new dye 2 basically reached saturation after 55 minutes of dyeing.

[0118] (5) Color fastness performance

[0119] According to ISO 105-C04 (2010) "Textiles - Tests for Color Fastness to Washing" standard, the color fastness to washing of dyed fabrics with a dye concentration of 1% (owf) is tested. According to ISO 105 / P01 (1993) "Textiles - Tests for Color Fastness to Dry Heat (Except Hot Pressing)" standard, the color fastness to sublimation of dyed fabrics with a dye concentration of 1% (owf) is tested. According to ISO 105-X12 (2016) "Textiles - Tests for Color Fastness to Rubbing" standard, the dry / wet rubbing fastness of polyester dyed fabrics with a dye dosage of 1% (owf) is tested. The test results are shown in the following table:

[0120]

[0121] It can be seen from the above table that the fastness of the new dye 2 is above level 4-5, and the light fastness is level 6, showing excellent color fastness performance.

[0122] Example 3

[0123] Add 20mL of acetic acid as solvent to a 100mL three-necked flask, add 10mmol of N-(3-aminopropyl)-N-methylaniline, heat and stir to dissolve, after complete dissolution, add 11mmol of phthalic anhydride at 60℃, heat and reflux to react, and track the reaction by thin layer chromatography. After the reaction is complete, transfer all the liquid to a 1L three-necked flask, add 100mL of distilled water, stir until the liquid is clear, and cool to 5℃ for use.

[0124] Add 10mL of concentrated sulfuric acid and 10mmol of 3-amino-5-nitrobenzisothiazole to a three-necked flask. After stirring and dissolving completely, slowly add 11mmol of nitrosyl sulfuric acid solution and react for 2h. Then slowly add the diazonium salt to the coupling component prepared in the previous step, keep the reaction at 5℃, use H acid to check the end point of the reaction, adjust the pH of the solution to 8 with Na2CO3 after the reaction, continue stirring for 2h, and remove the excess anhydride. Filter and wash to obtain a crude product with a yield of 95%. The crude product is recrystallized from ethanol to obtain a pure disperse dye, marked as dye 3.

[0125] The reaction equations involved are as follows:

[0126]

[0127] Product Confirmation:

[0128] (1) Dye molecular structure

[0129]

[0130] (2) Molecular structure characterization

[0131] like Fig.11 Shown is the NMR spectrum of the new dye 3

[0132] NMR analysis: 1 H-NMR (500MHz, DMSO-d6, δ H ,ppm):8.20-8.21(dd,1H,Ar-H),7.95-7.96(d,2H),7.87-7.89(d,2H),7.83-7.85(m,4H),6.95-6. 98(d,2H),3.71-3.73(t,2H,CH2),3.66-3.69(t,2H,CH2),3.19(s,3H,CH3),1.94-1.97(m,2H,CH2).

[0133] like Fig.12 Shown is the infrared spectrum of the new dye 3.

[0134] Infrared analysis: 3091cm -1 is the CH stretching vibration of the benzene ring, 2939cm -1 Corresponding to the stretching vibration peak of saturated hydrocarbon CH, 1709cm -1 is the C=O stretching vibration peak of the anhydride, 1597 cm -1 The peak of the skeleton stretching vibration of the benzene ring is 1521 cm -1 and 1500cm -1 It is the asymmetric stretching vibration of nitro N=O, 1396cm -1 The CN stretching vibration peak on the amide, 1320 cm -1 The N=O symmetrical stretching vibration peak of the nitro group is 1208 cm -1 , 1186cm -1 , 1157cm -1 , 1140cm -1 , is the CN bending vibration on the amide, 825cm -1 The out-of-plane swing peak of the CH substituent on the benzene ring is 751 cm -1 It is the out-of-plane swing peak of CH substituted at the ortho position of benzene ring.

[0135] (3) Spectral absorption performance

[0136] Weigh 0.01 g of the new dye 3, dissolve it in 100 mL of N,N-dimethylformamide, dilute it 5 times to a concentration of 0.02 g / L, and measure the absorption spectrum curve using a UV-2450 ultraviolet-visible spectrophotometer (Shimadzu Corporation, Japan). Fig.13 shown.

[0137] The maximum absorption wavelength of the new dye 3 was determined to be 608 nm, and the molar extinction coefficient ε = 29531.27 L·mol-1 cm -1 .

[0138] (4) Dye solution and dyeing properties

[0139] Accurately weigh 2 g of dye 3 and put it into a mortar. Add a little water, grind and transfer to a 1000 mL volumetric flask to make a 2 g / L mother solution.

[0140] This mother liquor was taken to prepare dye liquor of different concentrations. The cut 1g polyester fabric sample was wetted and then thrown into the dye bath (pH=5, bath ratio 1:20). Then the sealed dye cylinder was installed in the high temperature and high pressure dyeing machine. The dye bath temperature was raised from 50℃ to 130℃ at a heating rate of 2℃ / min, kept warm for 60min, and then quickly cooled to room temperature. After rinsing the fabric sample with cold water, the dyed polyester fabric was reduced and cleaned at 85℃ for 15min with the prepared reduction cleaning solution (2g / L sodium carbonate, 2g / L hydrosulfite, bath ratio 1:50) and then dried. The dyeing results are as follows: Fig.14 When the dosage of the new dye 3 is 0.5%, the K / S can reach 9, when the concentration is 1%, the K / S exceeds 14, and when the concentration is 2%, it basically reaches a balance, and the K / S value is close to 18.

[0141] The mother liquor was taken out to prepare a 1% (owf) dye solution. The cut 1g polyester fabric sample was wetted and then thrown into the dye solution (pH=5, bath ratio 1:20). Then the sealed dye cup was installed in the high temperature and high pressure dyeing machine. The dye solution temperature was raised from 50°C to 130°C at a heating rate of 2°C / min, kept warm for 60 minutes, and then quickly cooled to room temperature. A dye cup was taken out every 10 minutes during the heating stage and every 15 minutes during the insulation stage. After rinsing the fabric sample with cold water, the dyed polyester fabric was reduced and cleaned at 85°C for 15 minutes using the prepared reduction cleaning solution (2g / L sodium carbonate, 2g / L insurance powder, bath ratio 1:50) and then dried. The dyeing results are as follows: Fig.15 As shown in the figure, the new dye 3 dyed faster around 40 minutes, but dyed more slowly after 60 minutes, and basically reached saturation at 100 minutes of dyeing.

[0142] (5) Color fastness performance

[0143] According to ISO 105-C04 (2010) "Textiles - Tests for Color Fastness to Washing" standard, the color fastness to washing of dyed fabrics with a dye concentration of 1% (owf) is tested. According to ISO 105 / P01 (1993) "Textiles - Tests for Color Fastness to Dry Heat (Except Hot Pressing)" standard, the color fastness to sublimation of dyed fabrics with a dye concentration of 1% (owf) is tested. According to ISO 105-X12 (2016) "Textiles - Tests for Color Fastness to Rubbing" standard, the dry / wet rubbing fastness of polyester dyed fabrics with a dye dosage of 1% (owf) is tested. The test results are shown in the following table:

[0144]

[0145] It can be seen from the above table that the fastness of the new dye 3 is above level 4-5, the light fastness is level 5, and all color fastnesses are excellent.

[0146] Example 4

[0147] Add 20mL of acetic acid as solvent to a 100mL three-necked flask, add 10mmol of N-(3-aminopropyl)-N-methylaniline, heat and stir to dissolve, after complete dissolution, add 11mmol of succinic anhydride at 60℃, heat and reflux to react, and track the reaction by thin layer chromatography. After the reaction is complete, transfer all the liquid to a 1L three-necked flask, add 100mL of distilled water, stir until the liquid is clear, and cool to 5℃ for use.

[0148] Add 10mL of concentrated sulfuric acid and 10mmol of 3-amino-5-nitrobenzisothiazole to a three-necked flask. After stirring and dissolving completely, slowly add 11mmol of nitrosyl sulfuric acid solution and react for 2h. Then slowly add the diazonium salt to the coupling component prepared in the previous step, keep the reaction at 5℃, use H acid to check the end point of the reaction, adjust the pH of the solution to 8 with Na2CO3 after the reaction, continue stirring for 2h, and remove the excess anhydride. Filter and wash to obtain a crude product with a yield of 91%. The crude product is recrystallized from ethanol to obtain a pure disperse dye, marked as dye 4.

[0149] The reaction equations involved are as follows:

[0150]

[0151] Product Confirmation:

[0152] (1) Dye molecular structure

[0153]

[0154] (2) Molecular structure characterization

[0155] like Fig.16Shown is the NMR spectrum of the new dye 4.

[0156] NMR analysis: 1 H-NMR (500MHz, DMSO-d6, δ H ,ppm):9.03-9.04(d,1H,Ar-H),8.18-8.20(dd,1H,Ar-H),7.95-7.97(d,2H,Ar-H),7.83-7.85(d,1H,Ar-H),6.95-6.97(d, 2H,Ar-H),3.58-3.61(t,2H,CH2),3.45-3.48(t,2H,CH2),3.17(s,3H,CH3),2.64(s,4H,CH2-CH2),1.80-1.86(m,2H,CH2).

[0157] like Fig.17 Shown is the infrared spectrum of the new dye 4.

[0158] Infrared analysis: 3088cm -1 is the CH stretching vibration of the benzene ring, 2936cm -1 , 2839cm -1 Corresponding to the stretching vibration peak of saturated hydrocarbon CH, 1701cm -1 is the C=O stretching vibration peak of the anhydride, 1599cm -1 The peak of the skeleton stretching vibration of the benzene ring is 1520 cm -1 and 1499cm -1 It is the asymmetric stretching vibration of nitro N=O, 1398cm -1 The CN stretching vibration peak on the amide, 1325 cm -1 The N=O symmetrical stretching vibration peak of the nitro group is 1142 cm -1 , 1123cm -1 , is the CN bending vibration of the amide, 808cm -1 The out-of-plane swing peak of CH substituted at the para position of benzene ring is 735 cm -1 It is the out-of-plane swing peak of CH substituted at the ortho position of benzene ring.

[0159] (3) Spectral absorption performance

[0160] Weigh 0.01 g of new dye 4, dissolve it in 100 mL of N,N-dimethylformamide, dilute it 5 times to a concentration of 0.02 g / L, and measure the absorption spectrum curve using a UV-2450 ultraviolet-visible spectrophotometer (Shimadzu Corporation, Japan). Fig.18 shown.

[0161] The maximum absorption wavelength of the new dye 4 is 608 nm, and the molar extinction coefficient ε is 35595.88 L·mol -1 cm -1 .

[0162] (4) Dye solution and dyeing properties

[0163] Accurately weigh 2 g of dye 4 and put it into a mortar. Add a little water, grind and transfer to a 1000 mL volumetric flask to make a 2 g / L mother solution.

[0164] This mother liquor was taken to prepare dye liquor of different concentrations. The cut 1g polyester fabric sample was wetted and then thrown into the dye bath (pH=5, bath ratio 1:20). Then the sealed dye cylinder was installed in the high temperature and high pressure dyeing machine. The dye bath temperature was raised from 50℃ to 130℃ at a heating rate of 2℃ / min, kept warm for 60min, and then quickly cooled to room temperature. After rinsing the fabric sample with cold water, the dyed polyester fabric was reduced and cleaned at 85℃ for 15min with the prepared reduction cleaning solution (2g / L sodium carbonate, 2g / L hydrosulfite, bath ratio 1:50) and then dried. The dyeing results are as follows: Fig.19 When the dosage of the new dye 4 is 0.5%, the K / S can reach 15, and when the concentration is 1%, the K / S exceeds 18, and then slowly increases with the concentration.

[0165] The mother liquor was taken out to prepare a 1% (owf) dye solution. The cut 1g polyester fabric sample was wetted and then thrown into the dye solution (pH=5, bath ratio 1:20). Then the sealed dye cup was installed in the high temperature and high pressure dyeing machine. The dye solution temperature was raised from 50°C to 130°C at a heating rate of 2°C / min, kept warm for 60 minutes, and then quickly cooled to room temperature. A dye cup was taken out every 10 minutes during the heating stage and every 15 minutes during the insulation stage. After rinsing the fabric sample with cold water, the dyed polyester fabric was reduced and cleaned at 85°C for 15 minutes using the prepared reduction cleaning solution (2g / L sodium carbonate, 2g / L insurance powder, bath ratio 1:50) and then dried. The dyeing results are as follows: Fig. 20 As shown in the figure, the new dye 4 dyed faster around 30 minutes and reached saturation at 60 minutes.

[0166] (5) Color fastness performance

[0167] According to ISO 105-C04 (2010) "Textiles - Tests for Color Fastness to Washing" standard, the color fastness to washing of dyed fabrics with a dye concentration of 1% (owf) is tested. According to ISO 105 / P01 (1993) "Textiles - Tests for Color Fastness to Dry Heat (Except Hot Pressing)" standard, the color fastness to sublimation of dyed fabrics with a dye concentration of 1% (owf) is tested. According to ISO 105-X12 (2016) "Textiles - Tests for Color Fastness to Rubbing" standard, the dry / wet rubbing fastness of polyester dyed fabrics with a dye dosage of 1% (owf) is tested. The test results are shown in the following table:

[0168]

[0169] It can be seen from the above table that the fastness of each item of the new dye 4 is above level 4-5, the light fastness is level 5, and the light fastness reaches level 5.

Claims

1. A dicarboximide monoazo disperse dye, the general structural formula of which is shown in Formula 1 or Formula 2: Where: Ar is a dye diazo component, including but not limited to any one of formula (a)-(l): R0 is a C1-C4 alkyl group or a derivative thereof; R1 is H, a halogen atom, a C1-C4 alkyl or alkoxy group; R2 is H, a halogen atom, a C1-C4 alkyl group or -NHCOR8, wherein R8 is an unsubstituted or one or more substituted C1-C4 alkyl group or alkoxy group, aryl group, hydroxyl group, amino group or a halogen atom, an unsubstituted or one or more substituted aromatic group, wherein the substituent of the aromatic group may be a C1-C4 alkoxy group, hydroxyl group, amino group or a halogen atom; R3 is unsubstituted or substituted by one or more C1-C4 alkane, hydroxyl, amino, -COOR8 or -OCOR8, wherein R8 is unsubstituted or substituted by one or more C1-C4 alkyl or alkoxy, aryl, hydroxyl, amino or halogen atom; R4 is H or a C1-C4 alkane; X is O or S; n is 0 or 1; m is 1-5; When n=0, m=1, R2 is not O or methyl; R5, R6 and R7 are independently H, C1-C4 alkyl or alkoxy, -CN, -NO2, OH, CF3, -COOR9, -CONHR9 or heterocyclic substituents at any substitution position of the benzene ring, wherein R9 is C1-C4 alkane or aryl, and the heterocyclic substituent is selected from a group containing 4 or 5 carbon atoms and 1 or 2 heteroatoms from O, S and N groups; R 10 is a C1-C4 alkane, a C1-C4 alkoxy group or a C1-C4 cyanoalkyl group; M1, M2 and M3 are independently H, Br, Cl, CN, OH, NO2, CF3 or C1-C4 alkane; M4 and M5 are independently H, Br, Cl, cyano, hydroxyl, nitro or trifluoromethyl; M6 is cyano, nitro or C1-C4 alkane; M7 is H, Br, Cl, C1-C4 alkoxy, an aromatic ring group containing 5-30 carbon atoms, or an aralkyl group containing 6-30 carbon atoms. M8 is H, cyano, nitro or -COR4, wherein R4 is H or a C1-C4 alkane.

2. A dicarboximide monoazo disperse dye according to claim 1, characterized in that: When the aforementioned substituent is an aryl group, the aryl group has 6 to 14 carbon atoms.

3. A dicarboximide monoazo disperse dye according to claim 2, characterized in that: When the aforementioned substituent is an aryl group, it is any one selected from the following substituents: phenyl, formylphenyl, methoxyphenyl, ethoxyphenyl, 2-hydroxyphenyl, 4-hydroxyphenyl, 2-chlorophenyl, 4-chlorophenyl, 2,6-dichlorophenyl, 2-aminophenyl, 3-aminophenyl, 4-aminophenyl, 4-methoxyphenyl, 4-ethoxyphenyl, naphthyl and phenol.

4. A dicarboximide monoazo disperse dye according to claim 1, characterized in that: When the aforementioned substituent is an alkyl group, it may be a linear or branched alkyl group.

5. A dicarboximide monoazo disperse dye according to claim 4, characterized in that: When the aforementioned substituent is an alkyl group, it is selected from any one of the following substituents: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, n-decyl and n-dodecyl.

6. A dicarboximide monoazo disperse dye according to claim 1, characterized in that: When the aforementioned substituent is a substituted alkyl, it is selected from any one of the following substituents: 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybutyl, 2-aminoethyl, 2-aminopropyl, 4-aminobutyl, cyanoethyl, 2-cyanoethyl, 2-chloroethyl, 2-bromoethyl and 4-chlorobutyl.

7. A dicarboximide monoazo disperse dye according to claim 1, characterized in that: When the aforementioned substituent is an alkoxy group, it is selected from any one of the following substituents: methoxy, ethoxy, n-propyl, isopropyl, n-butoxy, isobutoxy, n-butoxy, tert-butoxy, pentyloxy, neopentyloxy, n-hexyl, n-heptyl, n-octyl, isooctyl, n-decyl, and n-dodecyl.

8. A method for synthesizing dicarboximide monoazo disperse dyes, characterized in that: The following steps are involved: (1) using dianhydride and amino compound as raw materials, and generating a coupling component shown in Formula 3 or Formula 4 through coupling reaction; (2) using the diazonium salt and the coupling component synthesized in step (1) as raw materials, synthesizing a dicarboximide monoazo disperse dye through a coupling reaction.

9. The method for synthesizing a dicarboximide monoazo disperse dye according to claim 8, characterized in that: In step (1), the dianhydride is selected from one of the compounds represented by Formula 6 or Formula 7; and the amino compound is selected from one of the compounds represented by Formula 5: In step (2): The diazonium salt undergoes a coupling reaction with the coupling components of formula (3) and (4), and the coupling reaction is carried out in an acidic or organic aqueous medium, and the acid used is selected from any one of hydrochloric acid, acetic acid, propionic acid, sulfuric acid and phosphoric acid; the reaction temperature is -10 to 30°C.

10. Use of the dicarboximide monoazo disperse dye according to claim 1 in dyeing hydrophobic fibers.

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