CN115637057A - Synthesis method of double-crosslinking azo disperse dye - Google Patents
Synthesis method of double-crosslinking azo disperse dye Download PDFInfo
- Publication number
- CN115637057A CN115637057A CN202211331358.3A CN202211331358A CN115637057A CN 115637057 A CN115637057 A CN 115637057A CN 202211331358 A CN202211331358 A CN 202211331358A CN 115637057 A CN115637057 A CN 115637057A
- Authority
- CN
- China
- Prior art keywords
- double
- crosslinking
- dye
- disperse dye
- azo disperse
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Coloring (AREA)
Abstract
The invention discloses a synthesis method of a dye, in particular to a synthesis method of a double-crosslinking azo disperse dye, which is characterized by comprising the following steps: selecting aniline derivatives with a reaction group, firstly carrying out cross-linking reaction through a cross-linking agent to obtain a double cross-linking type coupling component, and then carrying out bilateral coupling on the double cross-linking type coupling component and diazonium salt to obtain a double cross-linking type azo disperse dye; according to the invention, a series of double-crosslinking disperse dyes with different structures can be obtained by changing the structures of aniline derivatives and diazonium salts, and the color spectrum of the dye product is complete; the synthetic route of the invention has mild conditions, simple and convenient operation and high yield, and is very suitable for large-scale industrial popularization.
Description
The technical field is as follows:
the invention relates to synthesis of a disperse dye, in particular to a synthesis method of a double-crosslinking azo disperse dye.
Background art:
disperse dyes were used for the earliest time for the dyeing of acetate fibers, and were then rapidly developed as polyester fibers (dacron) are developed. Because the terylene structure is compact, the molecular structure of the disperse dye is simple, and the molecular weight of the disperse dye is generally 300-400. In practical applications, the lower the molecular weight, the lower the sublimation fastness of the dye, and vice versa. According to the sublimation fastness, the disperse dyes can be divided into three types, namely a low-temperature type (small molecular weight), a medium-temperature type (medium molecular weight) and a high-temperature type (large molecular weight). The low temperature is suitable for low temperature dyeing, the medium temperature type is generally suitable for a high temperature and high pressure dyeing method, and the high temperature type is suitable for a high temperature dip dyeing process and is also suitable for hot melt dyeing.
With the increasing requirements of people on the performance of dye products and the continuous emergence of novel hydrophobic fibers, the heat migration resistance of disperse dyes becomes a problem which is generally concerned by the people in the industry. The conventional disperse dye has the defects that the molecules are generally simpler (the general molecular weight is 300-400), the acting force with fibers is relatively weaker, and the dye adsorbed on the fibers can be desorbed again when the fibers are heated, so that the dye is migrated from inside to outside, the color fastness performance of a dyeing product is reduced, and meanwhile, the phenomenon of unstable color light is caused.
In order to increase the heat migration resistance of the dye, the development of the double-crosslinking disperse dye is one of the methods and ways for fundamentally solving the heat migration resistance of the dye. Through the reaction of a cross-linking agent (generally a compound with two reactive functional groups), two independent color bodies are linked together finally, the molecular weight is effectively improved and can reach 700-900. The intermolecular force between dye molecules and fibers is increased, so that the affinity between the dye and the fibers is greatly increased, and the dye is not easy to desorb and is firmly fixed in the fibers when being heated.
The present inventors have invented a method for synthesizing a disperse Dye by cross-linking modification (CN 201410175095.0, cn201510103344. X), and first synthesized a conventional disperse Dye (Dye-OH or Dye-NH) containing a reactive group 2 ) The two disperse dyes are then crosslinked together by means of a crosslinking agent, generally a diisocyanate compound or a diformylchloride compound. The reaction formula is shown as formula 1:
in the formula: dye-OH and Dye-NH 2 Represents a conventional disperse dye having one hydroxyl or amino group, and R is a hydrocarbon group.
In the aforementioned synthesis methods, there are major problems: the reaction yields of the synthesis are generally low and may be analyzed for reasons: because the solubility of the conventional disperse dye in a solvent is limited and the solubilities of azo disperse dyes with different structures are different, the reaction yield is influenced, and more byproducts are brought.
The invention content is as follows:
the invention aims to provide a synthetic method of a double-cross-linked azo disperse dye with high synthetic yield and excellent dyeing performance.
The technical scheme adopted by the invention is as follows:
a synthetic method of a double-crosslinking azo disperse dye is characterized by comprising the following steps: selecting aniline derivatives with a reaction group, firstly carrying out crosslinking reaction through a crosslinking agent to obtain a double-crosslinking coupling component, and then carrying out bilateral coupling on the double-crosslinking coupling component and diazonium salt to obtain the double-crosslinking azo disperse dye.
Further:
a synthetic method of a double-crosslinking azo disperse dye is characterized by comprising the following steps:
(1) Preparation of a double-crosslinking coupling component
In the presence of a solvent, selecting aniline derivatives with a reactive group, adding a cross-linking agent, and reacting at room temperature for 0.5-2 hours to obtain the double cross-linking type coupling component.
The aniline derivative having one reactive group may be selected from aniline derivatives having a hydroxyl group or an amino group. Particularly preferred are: N-ethyl-N-hydroxyethylaniline or N- (2-aminoethyl) -N-ethyl-m-toluidine.
The crosslinking agent is selected from any one of diisocyanate compounds or diformyl chloride compounds.
The molar ratio of the crosslinking agent to the aniline derivative having a hydroxyl group or an amino group is preferably 1.
The solvent is preferably dichloromethane.
Based on the above-mentioned methods, the double crosslinking type coupling components (1) -a, (1) -b, (1) -c, (1) -d were synthesized.
(1) -synthesis steps of a and (1) -b:
adding a diisocyanate compound into a three-neck flask, adding dichloromethane serving as a solvent, stirring after fully shaking and mixing in ultrasonic waves, then adding a hydroxyl-containing aniline derivative or an amino-containing aniline derivative, adding triethylamine, reacting at room temperature for 0.5-2 hours, and evaporating dichloromethane after the reaction is finished to obtain the double-crosslinking coupling components (1) -a and (1) -b, wherein the products are directly used for the next coupling reaction.
(1) -synthesis steps of c and (1) -d:
adding a dicarbonyl chloride compound into a three-neck flask, adding dichloromethane serving as a solvent, stirring after fully shaking and mixing in ultrasonic waves, adding a hydroxyl-containing aniline derivative or an amino-containing aniline derivative, adding triethylamine, reacting at room temperature for 0.5-2 hours, evaporating dichloromethane after the reaction is finished to obtain double-crosslinking coupling components (1) -c and (1) -d, and directly using the products in the next coupling reaction.
The crosslinking reaction involves the following reaction equation:
in the formula:
r is alkyl, which can be selected from aliphatic alkyl or aromatic alkyl;
R 1 、R 2 can be independently H and CH 3 、OCH 3 Or NHCOCH 3 ；
X is H, CN, OCOCH 3 Or COOCH 3 And n is a natural number of 1 to 3.
(2) Synthesis of diazonium salts
With diazo component Ar-NH 2 The raw material is diazotized with sodium nitrite or nitrosyl sulfuric acid in the presence of inorganic acid to prepare the heavy metalA nitrogen salt (2).
The inorganic acid is hydrochloric acid or concentrated sulfuric acid; the reaction temperature is 0-5 ℃, and the reaction time is 1-2 h.
Further, the diazonium salt is prepared by one of the following methods:
the first synthesis method comprises the following steps: diazo component Ar-NH is added into a three-neck flask 2 Mixing with water and concentrated hydrochloric acid, stirring, heating to 80 deg.C, and waiting for diazo component Ar-NH 2 Completely dissolving, naturally cooling to room temperature after dissolving, then cooling to 0-5 ℃ in an ice bath for later use, placing sodium nitrite in a beaker, dissolving with water, placing in an ice water bath, cooling for 5min, and adding the diazo component Ar-NH 2 In the solution, the beaker is washed by water for multiple times to ensure that the sodium nitrite is completely added, after the temperature is kept between 0 and 5 ℃ for diazotization for 2 hours, the reaction progress is tracked by an amino reagent, and after the reaction is finished, sulfamic acid is added to quench excessive sodium nitrite.
And a second synthesis method comprises the following steps: the diazo component Ar-NH is added into a three-mouth bottle 2 And (3) starting stirring concentrated sulfuric acid, after the dissolution is finished, cooling to 0-5 ℃ in an ice bath, adding nitrosyl sulfuric acid (40%), reacting for 2 hours, and detecting the reaction end point by an ice water method.
The reaction equation for diazonium salt synthesis is as follows:
the diazo component Ar-NH 2 Preferably, the following components are used:
in the formula: y and Z may independently be NO 2 CN, cl, br or OCOCH 3 ，R 3 Is CH 3 Or OCH 3 。
(3) Synthesis of double-crosslinking type azo disperse dye
And sequentially adding an anionic surfactant, a hydrophobic emulsifier and an inorganic acid into the double-crosslinking type coupling component, stirring until the mixture is emulsified uniformly, and adding a diazonium salt to perform bilateral coupling reaction to prepare the double-crosslinking type azo disperse dye.
The anionic surfactant is selected from one or more of carboxylate, sulfonate, sulfate, phosphate, etc., and is especially preferably dispersant NNO or dispersant MF, with the amount of anionic surfactant being 2-4g/L.
The partial hydrophobic emulsifier is selected from one or more of fatty alcohol, alkylphenol ethoxylates, fatty alcohol-polyoxyethylene ether, fatty amine-polyoxyethylene ether, polyether compounds, alkyl glycoside type, fatty acid monoglyceride, fatty acid polyoxyethylene ester, sorbitan fatty acid ester (Span series), etc., and particularly preferred is oleic acid polyoxyethylene ester (EO-5) or n-dodecanol. The amount of the hydrophobic emulsifier is 0.05-1.5g/L
The inorganic acid is concentrated hydrochloric acid or concentrated sulfuric acid.
The bilateral coupling reaction is carried out at the reaction temperature of 0-5 ℃ for 2-6 h.
The reaction equation for the bilateral coupling reaction is as follows:
in the formula:
r is alkyl, can be aliphatic alkyl or aromatic alkyl;
R 1 、R 2 is H, CH 3 、OCH 3 Or NHCOCH 3 ；
X is H, CN, OCOCH 3 Or COOCH 3 ；
n is a natural number of 1 to 3.
The principle of the invention is as follows:
the synthesis technology of the double-crosslinking azo disperse dye is mainly divided into three steps, wherein in the first step, a coupling component Z (aniline derivatives containing hydroxyl or amino) is reacted by a crosslinking agent A (diisocyanate compound or diformylchloride compound) to obtain a double-crosslinking coupling component Z-A-Z (1); the second step is the preparation of the diazonium salt Ar-N + 2 (2) (ii) a The third step is the double cross-linking type coupling component Z-A-Z (1) and the diazonium salt Ar-N + 2 (2) Bilateral coupling occurs to obtain the double-crosslinking azo disperse dye (3) shown in the following formula.
In the above formula: a belongs to the group of crosslinking agents, Z is the coupling component to be crosslinked, and Ar is the hydrocarbon group of the diazo component. The compound (3') is a semi-finished product produced by a unilateral coupling reaction.
In the first step of crosslinking reaction, because the coupling component Z has small molecule and high solubility in organic solvent, the coupling component Z reacts with the crosslinking agent quickly and can be carried out at room temperature, the yield and the purity are high, and the obtained double-crosslinking coupling component can be directly used for the subsequent coupling reaction. The second diazotization step is a general diazotization reaction. The third step is that the coupled components after cross-linking have bilateral coupling reaction in sequence, which is a key link of the technology of the invention. Due to the relatively large molecular weight of the crosslinked coupling components Z-A-Z (1), they are difficult to dissolve in conventional acidic solutions and generally exist in the form of an oil phase. Therefore, the solubilizing effect of the double-crosslinking coupling component (1) is an important step in affecting the synthesis of the target product. Meanwhile, the molecular weight of the semi-finished product (3 ') after unilateral coupling is further increased, the semi-finished product is easy to aggregate into solid particles to generate sedimentation, the subsequent secondary coupling is influenced, and the dispersion and solubilization of the semi-finished product (3') also become another key technology.
Through research and experiments, the applicant finds that the two components can generate synergistic interaction by adding a proper amount of anionic surfactant and emulsifier with stronger oil solubility (partial hydrophobicity) in the coupling reaction. Specifically, the emulsifier with strong oil solubility can increase the solubility of the double-crosslinking coupling component Z-A-Z (1) and the unilateral coupling product (3'), so that the double-crosslinking coupling component Z-A-Z is easy to collide with diazonium salt molecules to generate coupling reaction, and meanwhile, the surface activity of an anionic surfactant can be increased, so that micelles are easy to form, the interfacial tension between oil/liquid and solid/liquid is reduced, and the solubilization effect of reactants is further improved; the main function of the anionic surfactant is to perform emulsification and dispersion stabilization of charge effect on an oil phase (double-cross coupling component) and a solid phase (single-side coupling product (3')), so that aggregation of a tiny oil phase or a tiny solid phase is prevented, and subsequent double-side coupling reaction is ensured to be performed smoothly.
Thus, by adding a proper amount of anionic surfactant and emulsifier with strong oil solubility (partial hydrophobicity), the dispersion and solubilization of the double-crosslinking coupling component and the single-side coupling semi-finished product are effectively solved, the aggregation and sedimentation problems caused by overlarge molecular weight are prevented, and the synthesis of the double-crosslinking azo disperse dye is ensured.
The invention has the following beneficial effects:
compared with the prior art: the invention firstly carries out cross-linking on a coupling component (aniline derivative) with a reaction group (hydroxyl or amino) through the reaction of a cross-linking agent (diisocyanate compound or diformylchloride compound) to obtain a symmetrical double cross-linking type coupling component, and then carries out bilateral coupling with diazonium salt to obtain the symmetrical double cross-linking type azo disperse dye. The invention can obtain series of double-crosslinking disperse dyes with different structures by changing the structures of aniline derivatives and diazonium salt, and the dye product has complete chromatogram and can meet the actual production requirement. In addition, comparison shows that the synthetic route of the invention has mild conditions, simple and convenient operation, high general yield (more than 90 percent), and is very suitable for large-scale industrial popularization.
The present invention will be further described with reference to the accompanying drawings and the following detailed description, which are given by way of illustration only and are not intended to limit the scope of the present invention.
Description of the drawings:
FIG. 1-1 is a photograph of dye 1 prepared in example 1 1 H NMR analysis spectrum;
FIGS. 1-2 are mass spectra of dye 1 prepared in example 1;
FIGS. 1-3 are graphs of IR spectroscopy analyses of dye 1 prepared in example 1;
FIGS. 1-4 are absorption spectra curves (DMF) of dye 1 solution prepared in example 1;
FIGS. 1-5 are pad-dyed samples of dye 1 prepared in example 1;
FIG. 2-1 shows dye 2 prepared in example 2 1 H NMR analysis spectrum;
FIG. 2-2 is a mass spectrum of dye 2 prepared in example 2;
FIGS. 2-3 are infrared spectroscopic analysis charts of dye 2 prepared in example 2;
FIGS. 2-4 are absorption spectra curves (DMF) of dye 2 solution prepared in example 2;
FIGS. 2-5 are pad-dyed swatches of dye 2 prepared in example 2;
FIG. 3-1 is a photograph of dye 3 prepared in example 3 1 An H NMR spectrum;
FIG. 3-2 is a mass spectrum of dye 3 prepared in example 3;
3-3 are infrared spectra of dye 3 prepared in example 3;
FIGS. 3-4 are absorption spectra curves (DMF) of dye 3 solution prepared in example 3;
FIGS. 3-5 are pad-dyed swatches of dye 3 prepared in example 3;
FIG. 4-1 shows dye 4 prepared in example 4 1 H NMR spectrum;
FIG. 4-2 is a mass spectrum of dye 4 prepared in example 4;
FIGS. 4-3 are graphs of infrared spectra of dye 4 prepared in example 4;
FIGS. 4-4 are absorption spectra curves (DMF) of dye 4 solution prepared in example 4;
FIGS. 4-5 are pad-dyed swatches of dye 4 prepared in example 4.
The specific implementation mode is as follows:
example 1:
(1) Synthesis of coupling component (1-1)
A250 mL three-necked flask was charged with p-phenylene diisocyanate (0.41g, 2.53mmol), followed by addition of methylene chloride (10 mL) as a solvent, followed by stirring after shaking sufficiently in ultrasonic waves, addition of N-ethyl-N-hydroxyethylaniline (0.8351mL, 5 mmol), and addition of triethylamine (3 drops). After the reaction was completed, methylene chloride was evaporated at 60 ℃ and the product was used directly in the next coupling reaction.
(2) Synthesis of diazonium salt (1-2)
P-nitroaniline (0.691g, 5 mmol), 10mL of water and 2.5mL of HCl (36.5%) are added into a 100mL three-neck flask, stirring is started, the temperature is heated to 80 ℃, then the p-nitroaniline is completely dissolved, after the dissolution is completed, the temperature is naturally reduced to the room temperature, and then the mixture is cooled to 0 ℃ in an ice bath for standby. Sodium nitrite (0.37g, 5.25mmol) is placed in a beaker and dissolved by water, the beaker is placed in an ice water bath to be cooled for 5min, then the solution is added into the paranitroaniline solution, the beaker is washed by water for a plurality of times to ensure that the sodium nitrite is completely added, and after the temperature is kept at 0 ℃, the beaker is diazotized for 2h, an amino reagent tracks the reaction progress. After the reaction is finished, the excessive sodium nitrite is quenched by adding sulfamic acid.
(3) Synthesis of disperse dyes (1-3)
Putting the coupling component (1-1) obtained in the step (1) into a 250mL three-necked bottle, adding 50mL of water, 0.15g of dispersant NNO,0.05g of polyoxyethylene oleate (EO-5) and 1mL of hydrochloric acid (36.5%), starting stirring, dissolving at room temperature, cooling to 0 ℃ in an ice bath, slowly dropping the diazonium salt prepared in the step (2) for about 30min, keeping the ice bath for 2h after dropping, and continuing to react for 4h after removing the ice bath; the crude dye was obtained with a crude yield of 95.6% by suction filtration.
The pure dye is obtained by recrystallization purification, the yield is 89.2 percent, and the pure dye is tested by a melting point test at mp 225-228 ℃.
The reaction equation is as follows:
and (3) product confirmation:
1. nuclear magnetic resonance 1 H NMR analysis
The dye is prepared by taking DMSO-D6 as a solvent and adopting AV400 nuclear magnetic resonance spectrometer of Bruker company 1 H NMR analysis, shown in FIG. 1-1:
1 H NMR(400MHz，DMSO-d 6 ，δ，ppm)：9.567(s，2H，-NH-)，8.339-8.375(m，J＝14.4Hz，4H，Ar-H)，7.916-7.952(m，J＝14.4Hz，4H，Ar-H),7.832-7.855(d，J＝9.2Hz，4H，Ar-H)，7.346(s，4H，Ar-H)，6.934-6.957(d，J＝9.2Hz，4H，Ar-H)，4.264-4.294(t，J＝12Hz，4H，-CH 2 CH 2 ),3.731-3.760(t，J＝11.6Hz，4H，-CH 2 CH 2 )，3.547-3.598(q，J＝20.4Hz，4H，-CH 2 CH 3 )，1.156-1.191(t，J＝14Hz，6H，-CH 2 CH 3 )。
2. mass Spectrometry (MS) analysis
The purified dye was mass analyzed using UPLC/XEVO TQD HPLC, U.S.A., waters corporation, with acetonitrile as the solvent, and the results are shown in FIGS. 1-2:
MS(+ESI)：m/z(％)＝788.30(100.0％)，m+1/z(％)＝789.31(44.0％)。
3. infrared (IR) analysis
The IR spectra of the pure dye products were determined by tabletting with potassium bromide and Shimadzu prestige 21FT-IR and are shown in FIGS. 1-3.
As can be seen from fig. 1-3: the dye is in 3313cm -1 Has a strong absorption band which is N-H telescopic vibration; 2972cm -1 Has weak absorption peak, which is C-H stretching vibration in methylene; 1703cm -1 C = O stretching vibration in carbamate; 1600cm -1 Stretching vibration for an aromatic ring C = C; 1514cm -1 A pi absorption band which is an amide group; 1409cm -1 For N = N telescopic vibration, 1388cm -1 、1320cm -1 Is NO 2 The stretching vibration of (2); 1230cm -1 C-N stretching vibration; 1134cm -1 C-H in-plane bending vibration of substituted benzene ring; 858cm -1 、688cm -1 The vibration is out-of-plane bending vibration of C-H surface of substituted benzene ring.
4. Spectral properties
The absorption spectrum of the DMF solution containing 5mg/L of dye 1 was measured by a spectrophotometer, and the results are shown in FIGS. 1 to 4. As can be seen from FIGS. 1 to 4, the maximum absorption wavelength was 489nm, the molar extinction coefficient was 57082.72, which is orange, and the half-peak width was 93.87nm.
5. Dyeing properties
Dyeing the polyester fabric by adopting a pad dyeing process, wherein the dyeing process comprises the following steps: the concentration of the pure dye is 5g/L, the JFC of a wetting agent is 2g/L, the MF of a dispersing agent is 1g/L, the ammonium sulfate is 1g/L, the sodium alginate (5%) is 10g/L, and the mangle expression is 65%. Before the dye is used, grinding the dye by using a dispersing agent FM, wherein the mass ratio of the dispersing agent MF to the dye is as follows: 1:1. After two-time soaking and two-time rolling, the fabric is pre-dried at 80 ℃, fixed for 3min at 220 ℃, cooled, reduced and cleaned (2 g/L sodium hydrosulfite, 2g/L caustic soda, bath ratio of 30, treatment for 15min at 85 ℃), and naturally dried.
The dye sample obtained by pad dyeing of the dye 1 is subjected to color measurement by adopting a Datacolor SF600 color measuring and matching instrument under the conditions of a D65 light source and a 10-degree visual angle, the chromaticity performance of the color is represented by a CIELab color space, and the result is shown in a table 1-1:
TABLE 1-1 chroma Properties of pad-dyed dye sample of dye 1
Combining table 1-1 and fig. 1-5: the dye sample of the dye is orange, the color is bright, the color difference delta E is only 0.11 and less than 0.25, the color is very uniform, the suspension-shaped dye solution containing 5g/L of pure dye is used for pad dyeing, the color of the obtained dye sample reaches 1.
The fastness to soaping was determined using the method ISO 105-C06: C1S, the fastness to light using the method ISO 105-B02, and the fastness to rubbing using the method ISO 105-X12, the results of which are shown in tables 1-2:
TABLE 1-2 color fastness Properties of dye 1
The data analysis in the table shows that the dye 1 has excellent fastness, soaping fastness, sublimation fastness and dry-wet rubbing fastness of more than 4-5 grades, and light fastness of 7 grades.
Example 2:
(1) Synthesis of coupling component (2-1)
A250 mL three-necked flask was charged with p-phenylene diisocyanate (0.41g, 2.53mmol), followed by addition of methylene chloride (10 mL) as a solvent, followed by sufficient shaking and mixing under ultrasonic waves, stirring, addition of N- (2-aminoethyl) -N-ethyl-m-toluidine (0.928mL, 5 mmol), and addition of triethylamine (3 drops). After the reaction was completed, methylene chloride was evaporated at 60 ℃ and the product (2-1) was used directly for the next coupling reaction.
(2) Synthesis of diazonium salt (2-2)
Adding p-nitroaniline (0.69g, 5 mmol), 10mL of water and 2.5mL of HCl (36.5%) into a 100mL three-neck flask, starting stirring, heating to 80 ℃, waiting for the p-nitroaniline to be completely dissolved, naturally cooling to room temperature after the dissolution is finished, and then cooling to 0 ℃ in an ice bath for later use; putting sodium nitrite (0.37g and 5.25mmol) into a beaker, dissolving with water, putting into an ice water bath, cooling for 5min, adding into the p-nitroaniline solution, washing the beaker with water for multiple times to ensure that the sodium nitrite is completely added, and diazotizing for 2h at the temperature of 0 ℃ until an amino reagent tracks the reaction progress; after the reaction is finished, the excessive sodium nitrite is quenched by adding sulfamic acid.
(3) Synthesis of disperse dye (2-3)
And (2) putting the coupling component (2-1) obtained in the step (1) into a 250mL three-necked bottle, adding 50mL of water, 0.15g of dispersant NNO,0.05g of polyoxyethylene oleate (EO-5) and 1mL of hydrochloric acid (36.5%), starting stirring, dissolving at room temperature, cooling to 0 ℃ in an ice bath, slowly dropping the diazonium salt prepared in the step (2) for about 30min, keeping the ice bath for reacting for 2h after dropping, and continuing to react for 4h after removing the ice bath. The crude dye was obtained with suction filtration in a crude yield of 98.2%.
The pure dye is obtained after recrystallization purification, the yield is 92.9 percent, and the pure dye is 258-260 ℃ through a melting point test.
The reaction equation involved is as follows:
and (3) product confirmation:
1. nuclear magnetism 1 H NMR analysis
The dye is prepared by taking DMSO-D6 as a solvent and adopting AV400 nuclear magnetic resonance spectrometer of Bruker company 1 H NMR analysis, shown in FIG. 2-1:
1 H NMR(400MHz，DMSO-d 6 ，δ，ppm)：8.422(s，2H，-NH-)，8.335-8.358(q，J＝9.2Hz，4H，Ar-H)，7.905-7.928(q，J＝9.2Hz，4H，Ar-H)，7.721-7.744(d，J＝9.2Hz，2H，Ar-H)，7.272(s，4H，Ar-H)，6.797-6.817(d，J＝8Hz，4H，Ar-H)，6.197(s，2H，-NH-)，3.498-3.533(t，J＝14Hz，8H，-CH 2 CH 2 )，3.293-3.310(d，J＝6.8Hz，4H，-CH 2 CH 3 )，2.634(s，6H，Ar-CH 3 )，1.156-1.191(t，J＝14Hz，6H，-CH 2 CH 3 )。
2. mass Spectrometry (MS) analysis
The purified dye was mass analyzed in acetonitrile as solvent using UPLC/XEVO TQD HPLC, a company of waters, USA, and the results are shown in FIGS. 2-2:
MS(+ESI)：m/z(％)＝814.37(100.0％)，m+1/z(％)＝815.37(46.2％)。
3. infrared (IR) analysis
The IR spectra of the pure dye products were determined by tabletting with potassium bromide and Shimadzu prestige 21FT-IR and are shown in FIGS. 2-3. As can be seen from FIGS. 2-3, this dye is at 3464cm -1 The absorption band is strong, N-H stretching vibration is generated, and a wider and stronger absorption band is caused by intermolecular association; 2904cm -1 Has weak absorption peak, which is C-H stretching vibration in methylene; 1637cm -1 C = O stretching vibration in carbamate; 1604cm -1 、1560cm -1 Has a medium-intensity absorption peak, and is the stretching vibration of an aromatic ring C = C; 1508cm -1 A pi absorption band which is an amide group; 1357cm -1 、1330cm -1 Is NO 2 The stretching vibration of (2); 1244cm -1 C-N stretching vibration; 1190cm -1 、1101cm -1 Has an absorption peak which is the C-H in-plane bending vibration of the substituted benzene ring; 858cm -1 The vibration is out-of-plane bending vibration of C-H surface of substituted benzene ring.
4. Spectral properties
The absorption spectrum of the DMF solution containing 5mg/L of dye 2 was measured by a spectrophotometer, and the results are shown in FIGS. 2 to 4. As can be seen from FIGS. 2 to 4, the maximum absorption wavelength was 511nm, the molar extinction coefficient was 73357.68, the color was red, and the half-width was 98.46nm.
5. Dyeing properties
Dyeing the polyester fabric by adopting a pad dyeing process, wherein the dyeing process comprises the following steps: the concentration of pure dye is 5g/L, the concentration of wetting agent JFC is 2g/L, the concentration of dispersing agent MF is 1g/L, the concentration of ammonium sulfate is 1g/L, the concentration of sodium alginate (5%) is 10g/L, and the mangle rolling rate is 65%. Before the dye is used, grinding the dye by using a dispersing agent FM, wherein the mass ratio of the dispersing agent MF to the dye is as follows: 1:1. After two-time soaking and two-time rolling, the fabric is pre-dried at 80 ℃, fixed for 3min at 220 ℃, cooled, reduced and cleaned (2 g/L sodium hydrosulfite, 2g/L caustic soda, bath ratio of 30, 1, treatment for 15min at 85 ℃), and naturally dried.
The dye sample obtained by pad dyeing of the dye 2 is subjected to color measurement by adopting a Datacolor SF600 color measuring and matching instrument under the conditions of a D65 light source and a 10-degree visual angle, the chromaticity performance of the color is represented by a CIELab color space, and the result is shown in a table 2-1:
TABLE 2-1 chromaticity performance of dye 2 pad dyeing sample
As can be seen from Table 2-1 and FIGS. 2-5: the dye sample of the dye is reddish orange, the color is bright, the color difference delta E is 0.16 and less than 0.25, the color is very uniform, the suspension-shaped dye solution containing 5g/L of pure dye is used for pad dyeing, the K/S value of the obtained dye sample is 4.67, the color is light, and the color reaches 1/3 standard color.
The soaping fastness of the dyed sample is measured by the method of standard ISO 105-C06: C1S, the light fastness is measured by the method of standard ISO 105-B02, the rubbing fastness is measured by the method of standard ISO 105-X12, and the results are shown in a table 2-2:
TABLE 2-2 color fastness Properties of dye 2
From the analysis of the data in the table above, the dye 2 has excellent fastness, soaping fastness, sublimation fastness and dry-wet rubbing fastness of more than 4-5 grades, and light fastness of only 3 grades. This may be associated with lighter shades which only reach 1/3 of the standard shade.
Example 3:
1. synthesis of coupling component (3-1)
Terephthaloyl chloride (0.51g, 2.5 mmol) was added to a 250mL three-necked flask, followed by addition of methylene chloride (10 mL) as a solvent, followed by sufficient shaking and mixing under ultrasonic waves, stirring was started, followed by addition of N-ethyl-N-hydroxyethylaniline (0.84mL, 5 mmol) and addition of triethylamine (1 mL). After the reaction was completed, methylene chloride was evaporated at 60 ℃ and the product was used directly in the next coupling reaction.
2. Synthesis of diazonium salt (3-2)
Adding 2-chloro-4-nitroaniline (1.04g, 6 mmol) and 4mL concentrated sulfuric acid (98%) into a 100mL three-necked bottle, starting stirring, cooling to 0 ℃ in an ice bath after dissolution is finished, adding 1mL nitrosyl sulfuric acid (40%), reacting for 2h, and detecting the reaction end point by an ice water method.
3. Synthesis of coupled disperse dye (3-3)
And (2) putting the coupling component (3-1) obtained in the step (1) into a 250mL three-necked bottle, adding 50mL of water, 0.15g of dispersing agent NNO,0.05g of oleic acid polyoxyethylene ester (EO-5) and 1mL of hydrochloric acid (36.5%), starting stirring, dissolving at room temperature, cooling to 0 ℃ in an ice bath, slowly dropping the diazonium salt prepared in the step (2) for about 30min, keeping the ice bath for reacting for 2h after dropping, and continuing to react for 4h after removing the ice bath. The crude dye was obtained with suction filtration in a crude yield of 94.8%.
The pure dye is obtained after recrystallization purification, the yield is 86.2 percent, and the melting point test is 185-188 ℃.
The reaction equation involved is as follows:
and (3) product confirmation:
1. nuclear magnetic resonance 1 H NMR analysis
The dye is prepared by taking DMSO-D6 as a solvent and adopting AV400 nuclear magnetic resonance spectrometer of Bruker company 1 H NMR analysis, shown in FIG. 3-1:
1 H NMR(400MHz，CDCI3，δ，ppm)：8.40(d，J＝2.4Hz，2H)，8.16(dd，J＝8.8，2.4Hz,2H),8.06(s,4H),7.96(d,J＝9.2Hz,4H),7.79(d,J＝8.8Hz,2H),6.89(d,J＝9.2Hz,4H),4.58(t,J＝6.4Hz,4H),3.85(t,J＝6.4Hz,4H),3.60(q,J＝6.8Hz,4H),1.29(t,J＝100，6.8Hz,6H)。
2. mass Spectrometry (MS) analysis
The purified dye was mass analyzed in acetonitrile as solvent using UPLC/XEVO TQD HPLC, a company of waters, USA, and the results are shown in FIG. 3-2:
MS(+ESI)：m/z(％)＝826.92(100.0％)，m+1/z(％)＝828.75(70.2％)。
3. infrared (IR) analysis
The IR spectra of the pure dye products were determined by tabletting with potassium bromide and Shimadzu prestige 21FT-IR and are shown in FIGS. 3-3. As can be seen from FIGS. 3-3, the dye is 2900cm -1 Has weak absorption peak, which is C-H stretching vibration in methylene; 1720cm -1 C = O stretching vibration in carbamate; 1600cm -1 Stretching vibration for an aromatic ring C = C; 1516cm -1 A pi absorption band which is an amide group; 1332cm -1 Is NO 2 The stretching vibration peak of (1); 1263cm -1 C-N stretching vibration; 1118cm -1 C-H in-plane bending vibration of substituted benzene ring; 887cm -1 、727cm -1 The vibration is out-of-plane bending vibration of C-H surface of substituted benzene ring.
4. Spectral properties
The absorption spectrum of the DMF solution containing 5mg/L of dye 3 was measured by a spectrophotometer, and the results are shown in FIGS. 3 to 4. As can be seen from FIGS. 3 to 4, the maximum absorption wavelength was 508nm, the molar extinction coefficient was 71374, the color was red, and the half-width was 100.93nm.
5. Dyeing properties
Dyeing the polyester fabric by adopting a pad dyeing process, wherein the dyeing process comprises the following steps: the concentration of the pure dye is 5g/L, the JFC of a wetting agent is 2g/L, the MF of a dispersing agent is 1g/L, the ammonium sulfate is 1g/L, the sodium alginate (5%) is 10g/L, and the mangle expression is 65%. Before the dye is used, grinding the dye by using a dispersing agent FM, wherein the mass ratio of the dispersing agent MF to the dye is as follows: 1:1. After two-time soaking and two-time rolling, the fabric is pre-dried at 80 ℃, fixed for 3min at 220 ℃, cooled, reduced and cleaned (2 g/L sodium hydrosulfite, 2g/L caustic soda, bath ratio of 30, 1, treatment for 15min at 85 ℃), and naturally dried.
The dye sample obtained by pad dyeing of the dye 3 is subjected to color measurement by adopting a Datacolor SF600 color measuring and matching instrument under the conditions of a D65 light source and a 10-degree visual angle, the chromaticity performance of the color is represented by a CIELab color space, and the result is shown in a table 3-1:
TABLE 3-1 chromaticity Properties of dye 3 pad dyeing samples
As can be seen from Table 3-1 and FIGS. 3-5: the dye sample of the dye is reddish orange, the color is bright, the color difference delta E is 0.25, the color is uniform, the pad dyeing is carried out on suspension dye liquor containing 5g/L of pure dye, the K/S value of the obtained dye sample is 12.85, and the color reaches 1.
The fastness to soaping was determined using the method ISO 105-C06: C1S, the fastness to light using the method ISO 105-B02, and the fastness to rubbing using the method ISO 105-X12, the results of which are shown in tables 3-2:
TABLE 3-2 color fastness Properties of dye 3
From the analysis of the data in the table above, it can be seen that the dye 3 has excellent fastness, soaping fastness, sublimation fastness and dry-wet rubbing fastness of 4-5 grades, and high light fastness of 7 grades.
Example 4:
1. synthesis of coupling component (4-1)
Terephthaloyl chloride (0.51g, 2.5 mmol) was added to a 250mL three-necked flask, and then methylene chloride (10 mL) was added as a solvent, and after sufficiently shaking and mixing by ultrasonic wave, stirring was started, then N- (2-aminoethyl) -N-ethyl-m-toluidine (0.928mL, 5 mmol) was added, and then triethylamine (1 mL) was added. After the reaction was completed, methylene chloride was evaporated at 60 ℃ and the product was used directly in the next coupling reaction.
2. Synthesis of diazonium salt (4-2)
P-nitroaniline (0.69g, 5 mmol), 10mL of water and 2.5mL of HCl (36.5%) are added into a 100mL three-neck flask, stirring is started, the temperature is heated to 80 ℃, then the p-nitroaniline is completely dissolved, after the dissolution is completed, the temperature is naturally reduced to the room temperature, and then the mixture is cooled to 0 ℃ in an ice bath for standby. Sodium nitrite (0.37g, 5.25mmol) is placed in a beaker and dissolved by water, the beaker is placed in an ice water bath to be cooled for 5min and then is added into the paranitroaniline solution, the beaker is washed by water for a plurality of times to ensure that the sodium nitrite is completely added, and after the temperature is kept at 0 ℃ and diazotization is carried out for 2h, an amino reagent tracks the reaction progress; after the reaction is finished, sulfamic acid is added to quench excessive sodium nitrite.
3. Synthesis of disperse dye (4-3)
And (2) putting the coupling component (4-1) obtained in the step (1) into a 250mL three-necked bottle, adding 50mL of water, 0.15g of dispersing agent NNO,0.05g of oleic acid polyoxyethylene ester (EO-5) and 1mL of hydrochloric acid (36.5%), starting stirring, dissolving at room temperature, cooling to 0 ℃ in an ice bath, slowly dropping the diazonium salt prepared in the step (2) for about 30min, keeping the ice bath for reacting for 2h after dropping is finished, and continuing to react for 4h after the ice bath is removed. The crude dye was obtained with suction filtration in a crude yield of 98.5%.
The pure dye is obtained by recrystallization purification, the yield is 95.2 percent, and the pure dye is 222-230 ℃ by a melting point test.
The reaction equation involved is as follows:
and (3) product confirmation:
1. nuclear magnetism 1 H NMR analysis
The dye is prepared by taking DMSO-D6 as a solvent and adopting AV400 nuclear magnetic resonance spectrometer of Bruker company 1 H NMR analysis, shown in FIG. 4-1:
1 H NMR(400MHz，DMSO-d 6 ，δ，ppm)：8.799-8.827(t，J＝11.2Hz，2H，-NH-)，8.343-8.365(t，J＝8.8Hz，4H，Ar-H)，7.910-7.955(t，J＝18Hz，8H，Ar-H)，7.715-7.738(d，J＝9.2Hz，2H，Ar-H)，6.771-6.826(m，J＝22Hz，4H，Ar-H)，3.586-3.614(t，J＝11.2Hz，4H，-CH 2 CH 3 )，3.519-3.535(d，J＝6.4Hz，8H，-CH 2 CH 2 )，2.632(s，6H，Ar-CH 3 )，1.150-1.185(t，J＝14Hz，6H，-CH 2 CH 3 )。
2. mass Spectrometry (MS) analysis
The purified dye was mass analyzed in acetonitrile as solvent using UPLC/XEVO TQD HPLC, a company of waters, USA, and the results are shown in FIG. 4-2:
MS(+ESI)：m/z(％)＝784.34(100.0％)，m+1/z(％)＝785.35(46.2％)。
3. infrared (IR) analysis
The IR spectra of the pure dye products were determined by tabletting with potassium bromide and Shimadzu prestige 21FT-IR and are shown in FIGS. 4-3. As can be seen from FIGS. 4-3, this dye is present at 3292cm -1 The absorption band is N-H telescopic vibration; the dye was at 2922cm -1 Has weak absorption peak, which is C-H stretching vibration in methylene; 1637cm -1 C = O stretching vibration in carbamate; 1600cm -1 Stretching vibration for an aromatic ring C = C; 1510cm -1 A pi absorption band which is an amide group; 1432cm -1 A stretching vibration peak of N = N; 1382cm -1 、1332cm -1 Is NO 2 The stretching vibration peak of (1); 1238cm -1 C-N stretching vibration; 1190cm -1 、1097cm -1 C-H in-plane bending vibration of substituted benzene ring; 856cm -1 、690cm -1 The vibration is out-of-plane bending vibration of C-H surface of substituted benzene ring.
4. Spectral properties
The absorption spectrum of the DMF solution containing 5mg/L of dye 4 was measured by a spectrophotometer, and the results are shown in FIGS. 4 to 4. As is clear from FIGS. 4 to 4, the maximum absorption wavelength was 507nm, the molar extinction coefficient was 72567.04, the color was red, and the half-value width was 97.68nm.
5. Dyeing properties
Dyeing the polyester fabric by adopting a pad dyeing process, wherein the dyeing process comprises the following steps: the concentration of pure dye is 5g/L, the concentration of wetting agent JFC is 2g/L, the concentration of dispersing agent MF is 1g/L, the concentration of ammonium sulfate is 1g/L, the concentration of sodium alginate (5%) is 10g/L, and the mangle rolling rate is 65%. Before the dye is used, grinding the dye by using a dispersing agent FM, wherein the mass ratio of the dispersing agent MF to the dye is as follows: 1:1. After two-time soaking and two-time rolling, the fabric is pre-dried at 80 ℃, fixed for 3min at 220 ℃, cooled, reduced and cleaned (2 g/L sodium hydrosulfite, 2g/L caustic soda, bath ratio of 30, 1, treatment for 15min at 85 ℃), and naturally dried.
The dye sample obtained by pad dyeing of the dye 4 is subjected to color measurement by adopting a Datacolor SF600 color measuring and matching instrument under the conditions of a D65 light source and a 10-degree visual angle, the chromaticity performance of the color is represented by a CIELab color space, and the result is shown in a table 4-1:
TABLE 4-1 chroma Properties of dye 4 pad dyeing samples
As can be seen from Table 4-1 and FIGS. 4-5: the dye sample of the dye is red, the color is bright, the color difference delta E is 0.11, the color is very uniform, the pad dyeing is carried out on the suspension dye liquor containing 5g/L of pure dye, the K/S value of the obtained dye sample is 7.86, and the color reaches 1 standard color.
The soaping fastness of the dyed sample is measured by the method of standard ISO 105-C06: C1S, the light fastness is measured by the method of standard ISO 105-B02, the rubbing fastness is measured by the method of standard ISO 105-X12, and the results are shown in the following table 4-2:
TABLE 4-2 color fastness Properties of dye 4
From the data analysis in the table above, it can be seen that the dye 4 has excellent fastness, soaping fastness, sublimation fastness, dry and wet rubbing fastness all of 4-5 grades, and light fastness of 6 grades.
Compared with the prior art:
in the following, taking dye 1 prepared in example 1 and dye 3 prepared in example 3 as examples, comparison and evaluation were performed with the prior patent application techniques (CN 201410175095.0, cn201510103344. X) of the present inventors, respectively.
Patent technology 1 (CN 201410175095.0):
the synthetic route of patent technology 1 is: the target product (3-1) was obtained by a crosslinking reaction with a diisocyanate compound (here, p-phenylene diisocyanate) (J1) using an existing commercial disperse dye (here, c.i. disperse red 1) (D1) having a reactive group (hydroxyl group or amino group) in the molecule.
The method comprises the following specific steps:
weighing 2.0 g of C.I. disperse red 1 (D1) parent dye purified by recrystallization and dried in vacuum, adding the dye into a 1000ml three-neck flask provided with a reflux device (connected with a calcium chloride drying tube), adding 600ml of toluene subjected to dehydration treatment, starting magnetic stirring to dissolve the dye, adding 10ml of stannous octoate, and gradually heating to 85 ℃. Accurately weighing 0.51g of p-phenylene diisocyanate (J1), diluting and dissolving the p-phenylene diisocyanate (J1) by using 40ml of toluene solvent, slowly dripping the diluted solution into a reactor within 120min, keeping the temperature for reaction for 2h, stopping heating, cooling to room temperature, separating out a product, filtering to obtain 1.27 g of a dye 1 product (3-1), wherein the crude yield is 50.45%, and purifying by using a recrystallization method to obtain 0.82 g of a pure dye, and the yield is 32.45%.
And (3) analysis:
as can be seen from the examples of patent technology 1, the synthesis yield of patent technology 1 is generally low, and the reason for this analysis may be: in the synthesis reaction of patent technology 1, the temperature is controlled at 85 ℃, the cross-linking agent (p-phenylene diisocyanate) is a very active compound, the temperature is too high, self-polymerization is easy to generate, on one hand, a plurality of byproducts are generated, on the other hand, the loss of raw materials is caused, and the yield is obviously lower.
Patent technology 2 (cn201510103344. X):
the synthetic route of patent technology 2 is: the target product (3-3) was obtained by a crosslinking reaction with a diformyl chloride compound (J2) (here, terephthaloyl chloride) using an existing commercial disperse dye (here, c.i. disperse red 13) (D2) having a reactive group (hydroxyl group or amino group) in the molecule.
The specific synthesis steps are as follows:
2.09g of purified and vacuum-dried C.I. disperse Red 13 (D2) dye was added to a 1000-ml three-necked flask, an appropriate amount of dehydrated 600-ml methylene chloride was added as a solvent, the mixture was stirred to completely dissolve the disperse dye, 1.21g of dehydrated triethylamine was added, 0.79g of terephthaloyl chloride (J2) was precisely weighed, dissolved and diluted with an appropriate amount of a reaction solvent, slowly dropped into the stirred reactor in an ice bath, and the mixture was allowed to react at room temperature for 2 to 4 hours. Thin-layer sample application tracks the reaction process, 100mI dilute acid solution is added after the reaction is finished, extraction separation is carried out, the dye liquor is subjected to rotary evaporation to remove dichloromethane solvent, then an appropriate amount of sodium carbonate solution is used for washing and filtering, and clear water is used for washing to obtain 2.32g of a crude product of the dye 3 (3-3), wherein the crude yield is 80.56%, and the pure dye is purified by a recrystallization method to obtain 1.97 g of pure dye, and the yield is 68.47%.
And (3) analysis:
in the synthesis reaction of patent technology 2, an existing commercial azo disperse dye (c.i. disperse red 13) (D2) is dissolved in an organic solvent (dichloromethane), and then a crosslinking agent (terephthaloyl chloride) (J2) is added to perform a reaction, so that a target product (3-3) is obtained. Since the solubility of the disperse dye D2 in the organic solvent is limited, and the electron-withdrawing group (chlorine) in the diazo component also reduces the electron cloud density of the active group (hydroxyl group), thereby reducing the nucleophilic substitution reaction capability with the acyl chloride group, the yield obtained by the synthesis reaction of patent technology 2 is not very high overall, and the number of byproducts is also large.
Compared with the prior patent technology of the inventor, the synthesis method of the invention has generally higher yield (all can reach more than 90 percent), and the analysis reasons are mainly as follows: firstly, optimizing a synthetic route; and secondly, in the bilateral coupling reaction, the anionic surfactant and the emulsifier with strong oil solubility (partial hydrophobicity) have synergistic effect, so that the yield is effectively improved.
To sum up:
the invention firstly carries out cross-linking on a coupling component (aniline derivative) with a reaction group (hydroxyl or amino) through the reaction of a cross-linking agent (diisocyanate compound or diformylchloride compound) to obtain a symmetrical double cross-linked coupling component, and then carries out bilateral coupling on the symmetrical double cross-linked coupling component and diazonium salt to obtain the symmetrical double cross-linked azo disperse dye. Because the coupling component (aniline derivative) has high solubility in organic solvent and small molecular volume, the yield of the crosslinking reaction is high, and the product is relatively pure and can be directly subjected to the coupling reaction of the subsequent second step. Although the molecular weight of the cross-linked coupling component is larger, the cross-linked coupling component can be smoothly subjected to bilateral coupling to obtain a target product through the synergistic effect of the combined auxiliary agents (the anionic surfactant and the partial hydrophobic emulsifier), and the yield is obviously improved.
Claims (14)
1. A synthetic method of a double-crosslinking azo disperse dye is characterized by comprising the following steps: aniline derivatives with a reaction group are selected, cross-linking reaction is carried out through a cross-linking agent to obtain a double cross-linking type coupling component, and then the double cross-linking type coupling component and diazonium salt are subjected to bilateral coupling to obtain the double cross-linking type azo disperse dye.
2. The synthesis method of the double-crosslinking azo disperse dye according to claim 1, which is characterized by comprising the following steps:
(1) Preparation of a double-crosslinking coupling component
In the presence of a solvent, selecting aniline derivatives with a reaction group, adding a cross-linking agent, and reacting for 0.5-2 hours at room temperature to obtain a double cross-linking type coupling component;
(2) Synthesis of diazonium salts
With diazo component Ar-NH 2 Carrying out diazotization reaction on the raw material and sodium nitrite or nitrosyl sulfuric acid in the presence of inorganic acid to prepare diazonium salt;
(3) Synthesis of double-crosslinking type azo disperse dye
And (3) sequentially adding an anionic surfactant, a hydrophobic emulsifier and an inorganic acid into the double-crosslinking type coupling component, stirring until emulsification is uniform, and adding the diazonium salt prepared in the step (2) to perform bilateral coupling reaction to prepare the double-crosslinking type azo disperse dye.
3. The method for synthesizing the double-crosslinking azo disperse dye according to claim 2, wherein the method comprises the following steps: in the step (1), the aniline derivative with one reactive group is selected from aniline derivatives with hydroxyl or amino.
4. The method for synthesizing the double-crosslinking type azo disperse dye according to claim 3, wherein the method comprises the following steps: in the step (1), the aniline derivative with a reactive group is selected from N-ethyl-N-hydroxyethyl aniline or N- (2-aminoethyl) -N-ethyl m-toluidine.
5. The method for synthesizing the double-crosslinking type azo disperse dye according to claim 2, wherein the method comprises the following steps: in the step (1), the crosslinking agent is selected from any one of diisocyanate compounds or diformyl chloride compounds.
6. The method for synthesizing the double-crosslinking type azo disperse dye according to claim 5, wherein the method comprises the following steps: in the step (1), the solvent is dichloromethane.
7. The method for synthesizing the double-crosslinking azo disperse dye according to claim 2, wherein the method comprises the following steps: in the step (2), the inorganic acid is hydrochloric acid or concentrated sulfuric acid; the reaction temperature is 0-5 ℃, and the reaction time is 1-2 h.
8. The method for synthesizing the double-crosslinking type azo disperse dye according to claim 2, wherein the method comprises the following steps: in the step (2), the diazo component Ar-NH 2 One selected from the following compounds:
in the formula: y and Z may independently be NO 2 CN, cl, br or OCOCH 3 ，R 3 Is CH 3 Or OCH 3 。
9. The method for synthesizing the double-crosslinking azo disperse dye according to claim 2, wherein the method comprises the following steps: in the step (3), the anionic surfactant is selected from one or more of carboxylates, sulfonates, sulfates and phosphates, and the dosage of the anionic surfactant is 2-4g/L.
10. The method for synthesizing the bis-crosslinked azo disperse dye according to claim 9, wherein the method comprises the following steps: in the step (3), the anionic surfactant is selected from dispersant NNO or dispersant MF.
11. The method for synthesizing the double-crosslinking azo disperse dye according to claim 2, wherein the method comprises the following steps: in the step (3), the partial hydrophobic emulsifier is selected from any one or more of fatty alcohol, alkylphenol ethoxylates, fatty alcohol-polyoxyethylene ether, fatty amine-polyoxyethylene ether, polyether compounds, alkyl glycoside type, fatty acid monoglyceride, fatty acid-polyoxyethylene ester and sorbitan fatty acid ester, and the dosage of the partial hydrophobic emulsifier is 0.05-1.5g/L.
12. The method for synthesizing the bis-crosslinked azo disperse dye according to claim 11, wherein the method comprises the following steps: in the step (3), the partial hydrophobic emulsifier is selected from polyoxyethylene oleate or n-dodecanol.
13. The method for synthesizing the double-crosslinking azo disperse dye according to claim 2, wherein the method comprises the following steps: in the step (3), the inorganic acid is hydrochloric acid or sulfuric acid.
14. The method for synthesizing the double-crosslinking azo disperse dye according to claim 2, wherein the method comprises the following steps: in the step (3), the bilateral coupling reaction is carried out at the reaction temperature of 0-5 ℃ for 2-6 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211331358.3A CN115637057B (en) | 2022-10-28 | 2022-10-28 | Synthesis method of double-crosslinking azo disperse dye |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211331358.3A CN115637057B (en) | 2022-10-28 | 2022-10-28 | Synthesis method of double-crosslinking azo disperse dye |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115637057A true CN115637057A (en) | 2023-01-24 |
| CN115637057B CN115637057B (en) | 2023-10-20 |
Family
ID=84946074
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211331358.3A Active CN115637057B (en) | 2022-10-28 | 2022-10-28 | Synthesis method of double-crosslinking azo disperse dye |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115637057B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103952007A (en) * | 2014-04-28 | 2014-07-30 | 绍兴文理学院 | Crosslinking modification method of azo-disperse dye |
| CN104672103A (en) * | 2015-03-10 | 2015-06-03 | 绍兴文理学院 | Disperse dye compound as well as preparation method and application thereof |
| CN109135322A (en) * | 2018-08-20 | 2019-01-04 | 绍兴文理学院 | A kind of azo dispersion dyes compound and its synthetic method and purposes |
| CN109233338A (en) * | 2018-08-20 | 2019-01-18 | 绍兴文理学院 | A kind of disperse dye compound and its synthetic method and purposes |
| CN111635644A (en) * | 2020-06-30 | 2020-09-08 | 绍兴文理学院 | Azo disperse dye compound and preparation and application method thereof |
| CN111718594A (en) * | 2020-06-30 | 2020-09-29 | 绍兴文理学院 | Disperse dye and preparation and application methods thereof |
| US20210071025A1 (en) * | 2018-05-09 | 2021-03-11 | Papierfabrik August Koehler Se | Heat-sensitive recording material |
-
2022
- 2022-10-28 CN CN202211331358.3A patent/CN115637057B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103952007A (en) * | 2014-04-28 | 2014-07-30 | 绍兴文理学院 | Crosslinking modification method of azo-disperse dye |
| CN104672103A (en) * | 2015-03-10 | 2015-06-03 | 绍兴文理学院 | Disperse dye compound as well as preparation method and application thereof |
| US20210071025A1 (en) * | 2018-05-09 | 2021-03-11 | Papierfabrik August Koehler Se | Heat-sensitive recording material |
| CN109135322A (en) * | 2018-08-20 | 2019-01-04 | 绍兴文理学院 | A kind of azo dispersion dyes compound and its synthetic method and purposes |
| CN109233338A (en) * | 2018-08-20 | 2019-01-18 | 绍兴文理学院 | A kind of disperse dye compound and its synthetic method and purposes |
| CN111635644A (en) * | 2020-06-30 | 2020-09-08 | 绍兴文理学院 | Azo disperse dye compound and preparation and application method thereof |
| CN111718594A (en) * | 2020-06-30 | 2020-09-29 | 绍兴文理学院 | Disperse dye and preparation and application methods thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115637057B (en) | 2023-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fang et al. | Synthesis and application of urethane-containing azo disperse dyes on polyamide fabrics | |
| TW593555B (en) | Phthalimidyl azo dyes, processes for the preparation thereof and the use thereof | |
| KR101035841B1 (en) | Phthalimidyl-azo dyes, and process for their preparation | |
| Patel et al. | Synthesis and characterization of reactive dyes based on 2-phenyl-3-[4′-(4 ″-aminophenylsulphonamido)] phenyl-4 (3H)-quinazolinone-6-sulphonic acid | |
| Riaz et al. | Synthesis, characterization, solvatochromic study, and application of new heterocyclic monoazo acid dyes | |
| CN113666869B (en) | Naphthoimide dye containing amino group in supercritical CO 2 In (a) synthesis and dyeing method | |
| Li et al. | Urea-containing azo disperse dyes: Synthesis, application, and structure–property relationship for nylon fabrics | |
| CN114989088A (en) | Meta-aramid fiber color development method and used treating agent | |
| CN109054438B (en) | Supercritical CO2Azo dye special for anhydrous dyeing of natural fibers in fluid and preparation method thereof | |
| Maradiya | Disperse dyes based on 2-aminothiazole derivatives for cellulose triacetate fabric | |
| Qian et al. | An alternative strategy for the synthesis of disazo disperse dyes and their application on polyester fabric | |
| CN115637057B (en) | Synthesis method of double-crosslinking azo disperse dye | |
| Rădulescu et al. | Disperse dyes' derivatives from compact condensed system 2-aminothiazolo [5, 4-c] pyridine: Synthesis and characterization | |
| Wang et al. | Theoretical design, prediction and synthesis of a magenta dye SCFX-AYRL for sustainable coloration of natural fibers in SCF-CO2 | |
| Patel et al. | Monoazo disperse dyes derived from 11H-7-amino-2-chloro-isoindolo [2, 1-a] benzimidazole-11-one | |
| CN109135322B (en) | Azo disperse dye compound and synthesis method and application thereof | |
| CN115386242B (en) | Preparation and application of flexible chain-connected disazo orange high-water-washing disperse dye compound | |
| CN115386243B (en) | Preparation and application of disazo red high-washing disperse dye compound connected by flexible chains | |
| Maradiya et al. | Synthesis of novel azo dyes containing the thiophene moiety | |
| Otutu et al. | Synthesis of disazo disperse dye compounds derived from 4-bromoaniline and 3-aminophenol as potential near infra-red absorbers. | |
| CN111704807A (en) | Azo dye and preparation method and application thereof | |
| Qian et al. | Disazo disperse dyes crosslinked with varied characteristic groups: their synthesis, characterization, and application on polyester fabrics | |
| Rădulescu et al. | Synthesis and characterization of new cationic dyes for synthetic fibres | |
| Ding et al. | Improved Dyeing Performance of Blue Disperse Dyes with N-Acetoxyethyl Groups in D5 Non-aqueous Media System | |
| CN102504584A (en) | Azo type blue reactive dye, and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |