CN103233370A - Disperse dye application - Google Patents
Disperse dye application Download PDFInfo
- Publication number
- CN103233370A CN103233370A CN2012105940353A CN201210594035A CN103233370A CN 103233370 A CN103233370 A CN 103233370A CN 2012105940353 A CN2012105940353 A CN 2012105940353A CN 201210594035 A CN201210594035 A CN 201210594035A CN 103233370 A CN103233370 A CN 103233370A
- Authority
- CN
- China
- Prior art keywords
- compound
- preferred
- fibre
- equation
- reaction
- 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
- DZCHYXGECDCZAI-UHFFFAOYSA-N CC(CCc1c2)=Nc1cc(Cl)c2Cl Chemical compound CC(CCc1c2)=Nc1cc(Cl)c2Cl DZCHYXGECDCZAI-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a disperse dye application. The invention provides the application of a compound represented by the formula 1 in dyeing and printing of fiber products, wherein R1 is C1-4 alkoxy or hydrogen, R2 is C1-4 acylamino or hydrogen, R3 is C1-4 alkyl, R4 is C1-4 alkyl, and D is represented as the following. The disperse dye provided by the invention has a novel structure, high sublimation fastness and comprehensive fastness, and bright color. The disperse dye is suitable to be used in dyeing and printing of polyester fiber textile materials and blended fiber products, and is especially suitable to be used in dyeing and printing of outdoor sports textile fabrics such as swimwear fabrics.
Description
Technical field
The present invention relates to a kind of application of DISPERSE DYES.
Background technology
DISPERSE DYES is that a class formation is simple, and is water-soluble low, mainly is the non-ionic dye that dispersity exists with molecule in dye bath.Just come out as far back as early 1920s, be mainly used in the dyeing of acetate fibre at that time, therefore be also referred to as cellulose acetate dye.In recent years, along with synthetic fiber developing rapidly of polyester fiber particularly, DISPERSE DYES becomes one of the fastest dyestuff of modern development gradually.Be mainly used in dyeing and the stamp of polyester fiber at present, also can be used for the dyeing of hydrophobicity textile materials such as acetate fibre and polyamide fiber.Along with the raising of people's living standard, the consumer is also more and more higher for weaving official ceremonial dress performance demands, as requires dyed textiles to have higher fastness to sublimation, multinomial fastness such as sun-resistant.Some conventional DISPERSE DYES of using such as C.I. are red 153, C.I. purple 93, C.I. blue 291 and C.I. orange 288 etc., then are not suitable for the application that fastness to sublimation is had relatively high expectations.
Being reflected at of phenol and epoxychloropropane has the similar structures compound to synthesize the introduction of method among the US Patent No. 2010279997A1; In addition, be the explanation that related methods of synthesis is also arranged in the CAS database of 122-60-1 at CAS number.But the synthetic method reaction time that above patent documentation is mentioned is long, post-processing operation is loaded down with trivial details, and needs the participation of a large amount of solvents, very uneconomic environmental protection.
The reaction of preparation compound 4 has the introduction of the synthetic method of similar structures compound in US Patent No. 4448719A;
In addition, at document Russian Journal of Organic Chemistry, 43(8), 1176-1179; The introduction of the synthetic method of dependency structure compound is also arranged in 2007.But preparation technology's course of reaction complexity of document report, post-processing operation is loaded down with trivial details.
The reaction of preparation compound 2, still there is not the patent documentation report at present, has only the reaction of similar acylated hydroxy, at document Russian Journal of Organic Chemistry, 43(8), 1176-1179 has similar reaction in 2007, but is to adopt chloroacetic chloride to come hydroxyl is carried out acidylate in the document; Do reaction raw materials with acyl chlorides, toxicity is big, and requirement of shelter is higher, and environmental pollution is serious in the last handling process.
Summary of the invention
Technical problem to be solved by this invention is in order to overcome existing low, the comprehensive fastness difference of dye sublimation fastness and to the defectives such as Color difference of polyester fiber textile material and blend fibre goods thereof, and a kind of application of DISPERSE DYES is provided.Disperse dyes structure novelty of the present invention has higher sublimation reliability and comprehensive fastness, bright-colored, be applicable to dyeing and the stamp of polyester fiber textile material or its blend fibre goods, be specially adapted to dyeing and the stamp of outdoor exercises weaving face fabrics such as swimming suit, and the synthesis technique of DISPERSE DYES of the present invention is simple, easy operating, environmental friendliness.
The invention provides a kind of compound as shown in Equation 1
Wherein, R
1Be C
1-4Alkoxyl or hydrogen; R
2Be C
1-4Acylamino-or hydrogen; R
3Be C
1-4Alkyl; R
4Be C
1-4Alkyl; D is
Wherein, R
1Be preferably methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy or hydrogen.R
2Be preferably formamido group, acetylamino, propionamido, butyrylamino or hydrogen.R
3Be preferably methyl, ethyl, propyl group or butyl.R
4Be preferably methyl, ethyl, propyl group or butyl.R
1More preferably methoxyl group, ethyoxyl or hydrogen.R
2More preferably acetylamino, propionamido or hydrogen.R
3More preferably methyl or ethyl.R
4More preferably methyl or ethyl.Described compound 1 is a kind of DISPERSE DYES.
The present invention also provides the preparation method of compound as shown in Equation 1, and it may further comprise the steps: in solvent, under the acid catalyzed condition, diazol as shown in Equation 3 and as shown in Equation 2 compound are carried out coupling reaction, obtain compound 1 and get final product;
Wherein, A is Cl
-, CH
2COO
-, H
2PO
4 -, HSO
4 -Or NO
3 -, R
1Be C
1-4Alkoxyl or hydrogen; R
2Be C
1-4Acylamino-or hydrogen; R
3Be C
1-4Alkyl; R
4Be C
1-4Alkyl; D is
In the method for preparing compound 1, R
1Be preferably methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy or hydrogen.R
2Be preferably formamido group, acetylamino, propionamido, butyrylamino or hydrogen.R
3Be preferably methyl, ethyl, propyl group or butyl.R
4Be preferably methyl, ethyl, propyl group or butyl.R
1More preferably methoxyl group, ethyoxyl or hydrogen.R
2More preferably acetylamino, propionamido or hydrogen.R
3More preferably methyl or ethyl.R
4More preferably methyl or ethyl.Described compound 1 is a kind of DISPERSE DYES.
In the method for preparing compound 1, described coupling reaction can be carried out according to the conventional method of such reaction in this area, preferred following reaction condition and step:
In the method for preparing compound 1, described solvent preferred water.
In the method for preparing compound 1, the volume mass of described solvent and described compound 2 is than preferred 4mL/g～12mL/g, further preferred 6mL/g～9mL/g.
In the method for preparing compound 1, one or more in the preferred hydrochloric acid of described acid, acetic acid, phosphoric acid, nitric acid and the sulfuric acid, one or more in further preferred hydrochloric acid, acetic acid and the sulfuric acid, further preferably sulfuric acid and/or hydrochloric acid again.Described acid can participate in reaction with the form of aqueous acid, the mass percent concentration of described aqueous acid preferred 1%～20%, further preferred 3%～15%.
In the method for preparing compound 1, the volume ratio of described acid and described solvent preferred 0.005～0.02, further preferred 0.008～0.012.
In the method for preparing compound 1, the preferred 1:1～1:1.5 of mol ratio of the diazol of described compound 2 and compound 3, further preferred 1:1～1:1.2.
In the method for preparing compound 1, preferred-10 ℃～30 ℃ of the temperature of described coupling reaction, further preferred-10 ℃～10 ℃, further preferred-5 ℃～5 ℃ again.
In the method for preparing compound 1, the process of described coupling reaction can be monitored by conventionally test method in this area (oozing the circle method as filter paper), no longer is reaction end with reaction, and the preferred reaction time is 1h～3h, further preferred 2h.
Above-mentioned diazol as shown in Equation 3 can make by the following method: under the condition that acid exists, with nitrite or nitrosyl sulfuric acid, carry out diazo-reaction with as shown in Equation 8 aromatic amine, the diazol that obtains compound 3 gets final product; Making compound 1 according to the above-mentioned method for preparing compound 1 again gets final product;
Wherein, A is Cl
-, CH
2COO
-, H
2PO
4 -, HSO
4 -Or NO
3 -D is
Described diazo-reaction can be carried out according to the conventional method in this area, preferred following reaction condition:
In described diazo-reaction, described solvent preferred water.
In described diazo-reaction, one or more in the preferred hydrochloric acid of described acid, acetic acid and the sulfuric acid, further preferably sulfuric acid and/or hydrochloric acid.Described acid can participate in reaction with the form of aqueous acid, the mass percent concentration of described aqueous acid preferred 10%～90%, further preferred 20%～80%.
In described diazo-reaction, the preferred natrium nitrosum of described nitrite.
In described diazo-reaction, the volume mass of described solvent and described aromatic amine as shown in Equation 8 is than preferred 1mL/g～10mL/g, further preferred 2mL/g～5mL/g.
In described diazo-reaction, described aromatic amine and the preferred 1:1～1:1.2 of mol ratio of described nitrite or nitrosyl sulfuric acid, further preferred 1:1～1:1.1 as shown in Equation 8.
In described diazo-reaction, preferred-10 ℃～30 ℃ of the temperature of described reaction, further preferred-10～20 ℃.
The process of described diazo-reaction can be by conventionally test method (as TLC) monitoring in this area, and disappearing with described aromatic amine as shown in Equation 8 is reaction end, and the preferred reaction time is 1h～5h, further preferred 2h ~ 3h.
Above-claimed cpd 2 can make by following method: compound 4 and acid anhydrides are as shown in Equation 5 carried out acylation reaction, obtain compound 2 and get final product;
Prepare compound 3 according to the above-mentioned method for preparing compound 3 again, prepare compound 1 according to the above-mentioned method for preparing compound 1 again and get final product; Wherein, R
1Be C
1-4Alkoxyl or hydrogen; R
2Be C
1-4Acylamino-or hydrogen; R
3Be C
1-4Alkyl; R
4Be C
1-4Alkyl.
In the method for preparing compound 2, R
1Be preferably methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy or hydrogen.R
2Be preferably formamido group, acetylamino, propionamido, butyrylamino or hydrogen.R
3Be preferably methyl, ethyl, propyl group or butyl.R
4Be preferably methyl, ethyl, propyl group or butyl.R
1More preferably methoxyl group, ethyoxyl or hydrogen.R
2More preferably acetylamino, propionamido or hydrogen.R
3More preferably methyl or ethyl.R
4More preferably methyl or ethyl.Described compound 1 is a kind of DISPERSE DYES.
In the method for preparing compound 2, described acylation reaction can be carried out according to the conventional method of this area, preferred especially following reaction condition among the present invention:
In the method for preparing compound 2, described reaction can be carried out in solvent, also can carry out under solvent-free condition.The preferred organic acid of described solvent, the preferred acetic acid of described organic acid.
In the method for preparing compound 2, the volume mass of described solvent and described compound 4 is than preferred 1mL/g～10mL/g, further preferred 1mL/g～5mL/g.
In the method for preparing compound 2, the preferred 1:1～1:1.2 of mol ratio of described acid anhydrides 5 and described compound 4, further preferred 1:1～1:1.1.
In the method for preparing compound 2, preferred 20 ℃～100 ℃ of the temperature of described acylation reaction, further preferred 25 ℃～75 ℃, further preferred 50 ℃ again.
In the method for preparing compound 2, the process of described acylation reaction can be by conventionally test method (as HPLC) monitoring in this area, and having reacted with compound 4 is reaction end, and the preferred reaction time is 2h～6h, further preferred 4～5h.
Above-claimed cpd 4 can make by following method: compound 6 and amine are as shown in Equation 7 reacted, obtain compound 4 and get final product;
Make compound 2 according to the above-mentioned method for preparing compound 2 again, prepare compound 3 according to the above-mentioned method for preparing compound 3 again, prepare compound 1 according to the above-mentioned method for preparing compound 1 again and get final product; Wherein, R
1Be C
1-4Alkoxyl or hydrogen; R
2Be C
1-4Acylamino-or hydrogen; R
3Be C
1-4Alkyl.
In the method for preparing compound 4, R
1Be preferably methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy or hydrogen.R
2Be preferably formamido group, acetylamino, propionamido, butyrylamino or hydrogen.R
3Be preferably methyl, ethyl, propyl group or butyl.R
4Be preferably methyl, ethyl, propyl group or butyl.R
1More preferably methoxyl group, ethyoxyl or hydrogen.R
2More preferably acetylamino, propionamido or hydrogen.R
3More preferably methyl or ethyl.R
4More preferably methyl or ethyl.Described compound 1 is a kind of DISPERSE DYES.
In the method for preparing compound 4, described reaction can be carried out according to the conventional method of this area, preferred especially following reaction condition among the present invention:
In the method for preparing compound 4, described reaction can be carried out also can carrying out under solvent-free condition in solvent.The preferred organic acid of described solvent, the preferred acetic acid of described organic acid.
In the method for preparing compound 4, the volume mass of described solvent and described compound 7 is than preferred 1mL/g～10mL/g, further preferred 1mL/g～5mL/g.
In the method for preparing compound 4, the preferred 1:1～1:2 of mol ratio of described compound 6 and described compound 7, further preferred 1:1～1:1.1.
In the method for preparing compound 4, preferred 20 ℃～100 ℃ of the temperature of described reaction, further preferred 25 ℃～75 ℃, further preferred 50 ℃ again.
In the method for preparing compound 4, the process of described reaction can be by conventionally test method (as HPLC) monitoring in this area, and having reacted with compound 7 is reaction end, and the preferred reaction time is 1h～5h, further preferred 2h～4h.
Above-claimed cpd 6 can make by following method: in solvent, under the condition of alkali existence and catalyst, phenol and epoxychloropropane are reacted, obtain compound 6 and get final product;
Make compound 4 according to the above-mentioned method for preparing compound 4 again, make compound 2 according to the above-mentioned method for preparing compound 2, prepare compound 3 according to the above-mentioned method for preparing compound 3 again, prepare compound 1 according to the above-mentioned method for preparing compound 1 again and get final product.
In the method for preparing compound 6, described reaction can be carried out according to the conventional method of this area, preferred especially following reaction condition among the present invention:
In the method for preparing compound 6, described solvent preferred water.
In the method for preparing compound 6, the preferred PEG-400(PEG400 of described catalyst).
In the method for preparing compound 6, the mass percent of described catalyst and phenol is preferred 1%～30%, and is further preferred 5%～25%, and more further preferred 10%.
In the method for preparing compound 6, the volume mass of described solvent and described compound phenol is than preferred 1mL/g～10mL/g, further preferred 1mL/g～5mL/g.
In the method for preparing compound 6, the preferred 1:1～1:1.8 of the mol ratio of described phenol and epoxychloropropane, further preferred 1:1～1:1.5.
In the method for preparing compound 6, the preferred inorganic base of described alkali, one or more in the preferred NaOH of described inorganic base, potassium hydroxide, potash, sodium bicarbonate, saleratus and the sodium carbonate, further preferred NaOH.
In the method for preparing compound 6, described alkali can participate in reaction with the form of the aqueous solution of alkali, and the mass percent concentration of the aqueous solution of described alkali is preferred 10%～40%, and is further preferred 25%～35%, and more further preferred 30%.
In the method for preparing compound 6, the preferred 1:1 ~ 1:1.2 of the mol ratio of described alkali and phenol, further preferred 1:1.
In the method for preparing compound 6, preferred 0 ℃～100 ℃ of the temperature of described reaction, further preferred 20 ℃～75 ℃, further preferred 50 ℃～55 ℃ again.
In the method for preparing compound 6, the process of described reaction can be by conventionally test method (as HPLC) monitoring in this area, and intact with the phenol fundamental reaction is reaction end, and the preferred reaction time is 1h～6h, further preferred 2h～5h.
The invention provides a kind of preparation method of compound as shown in Equation 2, it may further comprise the steps: compound 4 and acid anhydrides are as shown in Equation 5 carried out acylation reaction, obtain compound 2 and get final product;
Wherein, R
1Be C
1-4Alkoxyl or hydrogen; R
2Be C
1-4Acylamino-or hydrogen; R
3Be C
1-4Alkyl; R
4Be C
1-4Alkyl.
In the method for preparing compound 2, R
1Be preferably methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy or hydrogen.R
2Be preferably formamido group, acetylamino, propionamido, butyrylamino or hydrogen.R
3Be preferably methyl, ethyl, propyl group or butyl.R
4Be preferably methyl, ethyl, propyl group or butyl.R
1More preferably methoxyl group, ethyoxyl or hydrogen.R
2More preferably acetylamino, propionamido or hydrogen.R
3More preferably methyl or ethyl.R
4More preferably methyl or ethyl.
In the method for preparing compound 2, described acylation reaction can be carried out according to the conventional method of this area, preferred especially following reaction condition among the present invention:
In the method for preparing compound 2, described reaction can be carried out in solvent, also can carry out under solvent-free condition.The preferred organic acid of described solvent, the preferred acetic acid of described organic acid.
In the method for preparing compound 2, the volume mass of described solvent and described compound 4 is than preferred 1mL/g～10mL/g, further preferred 1mL/g～5mL/g.
In the method for preparing compound 2, the preferred 1:1～1:1.2 of mol ratio of described acid anhydrides 5 and described compound 4, further preferred 1:1～1:1.1.
In the method for preparing compound 2, preferred 20 ℃～100 ℃ of the temperature of described acylation reaction, further preferred 25 ℃～75 ℃, further preferred 50 ℃ again.
In the method for preparing compound 2, the process of described acylation reaction can be by conventionally test method (as HPLC) monitoring in this area, and having reacted with compound 4 is reaction end, and the preferred reaction time is 2h～6h, further preferred 4～5h.
The invention provides the preparation method of compound 1, what it was preferable may further comprise the steps:
Step 1: in solvent, under the condition of alkali existence and catalyst, phenol and epoxychloropropane are reacted, obtain compound 6 and get final product;
Step 2: the compound that makes in the step 16 and as shown in Equation 7 amine are reacted, obtain compound 4 and get final product;
Step 3: the compound that makes in the step 24 and as shown in Equation 5 acid anhydrides are carried out acylation reaction, obtain compound 2 and get final product;
Step 4: under the condition that acid exists, as shown in Equation 8 aromatic amine and nitrite or nitrosyl sulfuric acid are carried out diazo-reaction, the diazol that obtains compound 3 gets final product;
Step 5: in solvent, under the acid catalyzed condition, the compound as shown in Equation 2 that makes in the diazol as shown in Equation 3 that makes in the step 4 and the step 3 is carried out coupling reaction, obtain compound 1 and get final product;
Wherein, R
1Be C
1-4Alkoxyl or hydrogen; R
2Be C
1-4Acylamino-or hydrogen; R
3Be C
1-4Alkyl; R
4Be C
1-4Alkyl; D is
Wherein, R
1Be preferably methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy or hydrogen.R
2Be preferably formamido group, acetylamino, propionamido, butyrylamino or hydrogen.R
3Be preferably methyl, ethyl, propyl group or butyl.R
4Be preferably methyl, ethyl, propyl group or butyl.R
1More preferably methoxyl group, ethyoxyl or hydrogen.R
2More preferably acetylamino, propionamido or hydrogen.R
3More preferably methyl or ethyl.R
4More preferably methyl or ethyl.Described compound 1 is a kind of DISPERSE DYES.
In the method for preparing compound 6, described reaction can be carried out according to the conventional method of this area, preferred especially following reaction condition among the present invention:
In the method for preparing compound 6, described solvent preferred water.
In the method for preparing compound 6, the preferred PEG-400(PEG400 of described catalyst).
In the method for preparing compound 6, the mass percent of described catalyst and phenol is preferred 1%～30%, and is further preferred 5%～25%, and more further preferred 10%.
In the method for preparing compound 6, the volume mass of described solvent and described compound phenol is than preferred 1mL/g～10mL/g, further preferred 1mL/g～5mL/g.
In the method for preparing compound 6, the preferred 1:1～1:1.8 of the mol ratio of described phenol and epoxychloropropane, further preferred 1:1～1:1.5.
In the method for preparing compound 6, the preferred inorganic base of described alkali, one or more in the preferred NaOH of described inorganic base, potassium hydroxide, potash, sodium bicarbonate, saleratus and the sodium carbonate, further preferred NaOH.
In the method for preparing compound 6, described alkali can participate in reaction with the form of the aqueous solution of alkali, and the mass percent concentration of the aqueous solution of described alkali is preferred 10%～40%, and is further preferred 25%～35%, and more further preferred 30%.
In the method for preparing compound 6, the preferred 1:1 ~ 1:1.2 of the mol ratio of described alkali and phenol, further preferred 1:1.
In the method for preparing compound 6, preferred 0 ℃～100 ℃ of the temperature of described reaction, further preferred 20 ℃～75 ℃, further preferred 50 ℃～55 ℃ again.
In the method for preparing compound 6, the process of described reaction can be by conventionally test method (as HPLC) monitoring in this area, and intact with the phenol fundamental reaction is reaction end, and the preferred reaction time is 1h～6h, further preferred 2h～5h.
In the method for preparing compound 4, described reaction can be carried out according to the conventional method of this area, preferred especially following reaction condition among the present invention:
In the method for preparing compound 4, described reaction can be carried out also can carrying out under solvent-free condition in solvent.The preferred organic acid of described solvent, the preferred acetic acid of described organic acid.
In the method for preparing compound 4, the volume mass of described solvent and described compound 7 is than preferred 1mL/g～10mL/g, further preferred 1mL/g～5mL/g.
In the method for preparing compound 4, the preferred 1:1～1:2 of mol ratio of described compound 6 and described compound 7, further preferred 1:1～1:1.1.
In the method for preparing compound 4, preferred 20 ℃～100 ℃ of the temperature of described reaction, further preferred 25 ℃～75 ℃, further preferred 50 ℃ again.
In the method for preparing compound 4, the process of described reaction can be by conventionally test method (as HPLC) monitoring in this area, and having reacted with compound 7 is reaction end, and the preferred reaction time is 1h～5h, further preferred 2h～4h.
In the method for preparing compound 2, described acylation reaction can be carried out according to the conventional method of this area, preferred especially following reaction condition among the present invention:
In the method for preparing compound 2, described reaction can be carried out in solvent, also can carry out under solvent-free condition.The preferred organic acid of described solvent, the preferred acetic acid of described organic acid.
In the method for preparing compound 2, the volume mass of described solvent and described compound 4 is than preferred 1mL/g～10mL/g, further preferred 1mL/g～5mL/g.
In the method for preparing compound 2, the preferred 1:1～1:1.2 of mol ratio of described acid anhydrides 5 and described compound 4, further preferred 1:1～1:1.1.
In the method for preparing compound 2, preferred 20 ℃～100 ℃ of the temperature of described acylation reaction, further preferred 25 ℃～75 ℃, further preferred 50 ℃ again.
In the method for preparing compound 2, the process of described acylation reaction can be by conventionally test method (as HPLC) monitoring in this area, and having reacted with compound 4 is reaction end, and the preferred reaction time is 2h～6h, further preferred 4～5h.
Described diazo-reaction can be carried out according to the conventional method in this area, preferred following reaction condition:
In described diazo-reaction, described solvent preferred water.
In described diazo-reaction, one or more in the preferred hydrochloric acid of described acid, acetic acid and the sulfuric acid, further preferably sulfuric acid and/or hydrochloric acid.Described acid can participate in reaction with the form of aqueous acid, the mass percent concentration of described aqueous acid preferred 10%～90%, further preferred 20%～80%.
In described diazo-reaction, the preferred natrium nitrosum of described nitrite.
In described diazo-reaction, the volume mass of described solvent and described aromatic amine as shown in Equation 8 is than preferred 1mL/g～10mL/g, further preferred 2mL/g～5mL/g.
In described diazo-reaction, described aromatic amine and the preferred 1:1～1:1.2 of mol ratio of described nitrite or nitrosyl sulfuric acid, further preferred 1:1～1:1.1 as shown in Equation 8.
In described diazo-reaction, preferred-10 ℃～30 ℃ of the temperature of described reaction, further preferred-10～20 ℃.
Process in described diazo-reaction can be by conventionally test method (as TLC) monitoring in this area, and disappearing with described aromatic amine as shown in Equation 8 is reaction end, and the preferred reaction time is 1h～5h, further preferred 2h ~ 3h.
In the method for preparing compound 1, described coupling reaction can be carried out according to the conventional method of such reaction in this area, preferred following reaction condition and step:
In the method for preparing compound 1, described solvent preferred water.
In the method for preparing compound 1, the volume mass of described solvent and described compound 2 is than preferred 4mL/g～12mL/g, further preferred 6mL/g～9mL/g.
In the method for preparing compound 1, one or more in the preferred hydrochloric acid of described acid, acetic acid, phosphoric acid, nitric acid and the sulfuric acid, one or more in further preferred hydrochloric acid, acetic acid and the sulfuric acid, further preferably sulfuric acid and/or hydrochloric acid again.Described acid can participate in reaction with the form of aqueous acid, the mass percent concentration of described aqueous acid preferred 1%～20%, further preferred 3%～15%.
In the method for preparing compound 1, the volume ratio of described acid and described solvent preferred 0.005～0.02, further preferred 0.008～0.012.
In the method for preparing compound 1, the preferred 1:1～1:1.5 of mol ratio of the diazol of described compound 2 and compound 3, further preferred 1:1～1:1.2.
In the method for preparing compound 1, preferred-10 ℃～30 ℃ of the temperature of described coupling reaction, further preferred-10 ℃～10 ℃, further preferred-5 ℃～5 ℃ again.
In the method for preparing compound 1, the process of described coupling reaction can be monitored by conventionally test method in this area (oozing the circle method as filter paper), no longer is reaction end with reaction, and the preferred reaction time is 1h～3h, further preferred 2h.
The present invention also provide above-mentioned compound as shown in Equation 1 as DISPERSE DYES in the dyeing of fibre and the application in the stamp.
Compound 1 of the present invention can be handled according to the conventional treatment method in this area (as sand milling), obtains the commercialization DISPERSE DYES.
The commercialization DISPERSE DYES that compound of the present invention makes can be applied to dyeing and the stamp of polyester fiber goods or its blend fibre goods according to the normal dyeing method of this type disperse dye in this area.Described polyester fiber goods or its blend fibre goods can be polyester fiber goods or its blend fibre goods conventional in this area; The preferred pet fiber goods of described polyester fiber goods, described blend fibre goods preferred polyester/cotton or polyester/wool.DISPERSE DYES of the present invention further is preferred for outdoor exercises weaving face fabrics such as swimming suit; Outdoor exercises weaving face fabrics such as described swimming suit are polyester fiber goods or its blend fibre goods.Described polyester fiber goods or its blend fibre goods can be for the conventional existence form of this area, as fiber, yarn, woven fabric, knitted fabric or nonwoven.
The present invention also provides a kind of compound as shown in Equation 2:
Wherein, R
1Be C
1-4Alkoxyl or hydrogen; R
2Be C
1-4Acylamino-or hydrogen; R
3Be C
1-4Alkyl; R
4Be C
1-4Alkyl.
R
1Be preferably methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy or hydrogen.R
2Be preferably formamido group, acetylamino, propionamido, butyrylamino or hydrogen.R
3Be preferably methyl, ethyl, propyl group or butyl.R
4Be preferably methyl, ethyl, propyl group or butyl.R
1More preferably methoxyl group, ethyoxyl or hydrogen.R
2More preferably acetylamino, propionamido or hydrogen.R
3More preferably methyl or ethyl.R
4More preferably methyl or ethyl.
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, but any combination namely get the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material be commercially available getting all.
Room temperature among the present invention is 10 ℃～30 ℃.
Umber among the present invention all refers to mass fraction except specified otherwise.
LC-MS data described in the present invention are by Waters UPLC-SQD LC-MS instrument, and flowing is the acetonitrile/water system mutually, and 60%-90% acetonitrile V/V tests under the condition that column temperature is 40 ℃.
Positive progressive effect of the present invention is: disperse dyes structure novelty of the present invention has higher sublimation reliability and comprehensive fastness, bright-colored, be applicable to dyeing and the stamp of polyester fiber textile material and blend fibre goods thereof, be specially adapted to dyeing and the stamp of outdoor exercises weaving face fabrics such as swimming suit, and the synthesis technique of DISPERSE DYES of the present invention is simple, easy operating, environmental friendliness.
The specific embodiment
Mode below by embodiment further specifies the present invention, but does not therefore limit the present invention among the described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example according to conventional method and condition, or is selected according to catalogue.
The preparation of embodiment 1 compound 6
At ambient temperature, 67 parts heavy 30% sodium hydrate aqueous solutions are joined in the there-necked flask, under agitation add 47 parts of heavy benzol phenol then, 5 parts heavy PEG-400, stir, then at ambient temperature, slowly drip 66 parts heavy epoxychloropropane with dropping funel, drip 1～2h approximately, slowly being warming up to 50 ℃～55 ℃ after dripping reacts, raw material reaction is complete behind 3h～5h, adds water 50mL solid is fully dissolved, then standing demix, divide the phase of anhydrating, add water 100mL again and wash, and regulate pH to neutral with a small amount of watery hydrochloric acid, stir the back standing demix, collect oil phase, excessive epoxychloropropane and water are removed in decompression distillation.Get following formula: compound 52g, yield 70.5%, HPLC purity 96.4%.LC-MS(ESI)：[M+H]
+151.3，[M+Na]
+173.3。
Embodiment 2 compound 4(R
1Be H, R
2Be H, R
3Be ethyl) preparation
18 parts of heavy N-ethylanilines and 30 parts heavy acetic acid are joined in the there-necked flask, slowly be warming up to 50 ℃ after stirring, slowly drip 24 parts heavy compounds 6 from constant pressure funnel then, drip 3h～4h approximately, add the back and react completely at 50 ℃ of insulation 3h～4h, get compound 4(R
1Be H, R
2Be H, R
3Be ethyl) acetum, be directly used in next step reaction.Yield 97.3%, HPLC purity 92.4%, LC-MS (ESI): [M+H]
+272.2, [M+Na]
+294.2.
Embodiment 3 compound 2-1(R
1Be H, R
2Be H, R
3Be ethyl, R
4Be methyl) preparation
With 29 parts heavy compound 4(R
1Be H, R
2Be H, R
3Be ethyl) join in the there-necked flask, slowly be warmed up to 50 ℃, under this temperature, slowly drip 13 parts heavy acetic anhydride from constant pressure funnel, drip 2h approximately, and complete up to raw material reaction 50 ℃ of insulation reaction, get compound 2-1(R
1Be H, R
2Be H, R
3Be ethyl, R
4Be methyl) acetum, yield 96.1%, HPLC purity 94.3%, LC-MS (ESI): [M+H]
+314.4, [M+Na]
+336.4.
Method according to embodiment 1～3 prepares compound 2-1～2-12, and its related experiment data and structure appraising datum see Table 1.
The experimental data of table 1 compound 2-1～2-12 and structure appraising datum
Embodiment 4 compound 1-1(R
1Be H, R
2Be H, R
3Be ethyl, R
4Be methyl, D is
) preparation
144 parts of heavy concentrated sulfuric acids are joined in the reaction bulb 1, add 45 parts heavy 2-amino-5 down in stirring, the 6-dichlorobenzothiazole, be warmed up to 40 ℃～45 ℃ then, insulation 30min makes dissolving fully, cool to then and add 67 parts heavy nitrosyl sulfuric acids about 15 ℃ slowly, stir, cool to below 5 ℃ stand-by.In reaction bulb 2, add 92 parts of heavy water, under agitation add 139 parts of heavy concentrated sulfuric acids and 3 parts heavy nitric acid, stir, cool to below 0 ℃, sulfuric acid liquid in the slow dropwise reaction bottle 1 under-5 ℃～0 ℃ condition slowly drips 72 parts of heavy water simultaneously, about 1h adds, and is incubated 2.5-3h below 0 ℃.Drip in 1h with compound 2-1 then and finish coupling, by 0～5 ℃ of control reaction temperature on the rocks, and finish coupling at 0～5 ℃ of insulation 2h, be stirred to room temperature naturally, filter, washing is dried, and gets compound 1-1(R
1Be H, R
2Be H, R
3Be ethyl, R
4Be methyl, D is
) DISPERSE DYES filter cake 83g, yield 76.5%, HPLC purity 92.6%, LC-MS (ESI): [M+H]
+544.5, [M+Na]
+566.5.
Method according to embodiment 1～4 prepares compound 1-1～1-76.Related experiment data and structure appraising datum see Table 2.
The experimental data of table 2 compound 1-1～1-76 and structure appraising datum
Effect embodiment 1
Get commercialization DISPERSE DYES [the compound 1-1(R that 5 gram embodiment 4 make
1Be H, R
2Be H, R
3Be ethyl, R
4Be methyl, D is
)] be dispersed in 500 ml waters, draw 20 milliliters of water with 80 milliliters and mix, transferring dye bath pH with acetic acid is 4 ~ 5, being warming up to 70 ℃ puts into 5 gram polyester fiber cloth simultaneously and dyes, in 30 minutes, be warming up to 130 ℃ by 70 ℃, be incubated 50 minutes, be cooled to draining below 90 ℃ and clean.Cloth specimen is put into 100 milliliters of reduction cleaning liquid containing 1 grams per liter caustic soda and 3 grams per liter sodium hydrosulfites again and cleaned in 80 ℃, the time is 20 minutes.Adopt GB GB/T5718-1997 test fastness to sublimation, probe temperature is 180 ℃, and the time is 30 seconds.
Effect embodiment 2
Method according to effect embodiment 1 dyes to the DISPERSE DYES that compound 1-1～1-76 prepares, and tests their fastness to sublimation, and its test result sees Table 3.
The Color data of the DISPERSE DYES of table 3 compound 1-1～1-76 preparation
Claims (10)
- A compound as shown in Equation 1 as DISPERSE DYES in the dyeing of fibre and the application in the stamp,
Wherein, R 1Be C 1-4Alkoxyl or hydrogen; R 2Be C 1-4Acylamino-or hydrogen; R 3Be C 1-4Alkyl; R 4Be C 1-4Alkyl; D is
- 2. compound as shown in Equation 1 as claimed in claim 1, is characterized in that: work as R in the dyeing of fibre and the application in the stamp as DISPERSE DYES 1Be C 1-4Alkoxyl the time, described C 1-4Alkoxyl be methoxyl group, ethyoxyl, propoxyl group, isopropoxy or butoxy.
- 3. compound as shown in Equation 1 as claimed in claim 1, is characterized in that: work as R in the dyeing of fibre and the application in the stamp as DISPERSE DYES 2Be C 1-4Acylamino-the time, described C 1-4Acylamino-be formamido group, acetylamino, propionamido or butyrylamino.
- 4. compound as shown in Equation 1 as claimed in claim 1, is characterized in that: R in the dyeing of fibre and the application in the stamp as DISPERSE DYES 3Be methyl, ethyl, propyl group or butyl.
- 5. compound as shown in Equation 1 as claimed in claim 1, is characterized in that: R in the dyeing of fibre and the application in the stamp as DISPERSE DYES 4Be methyl, ethyl, propyl group or butyl.
- Compound as shown in Equation 1 as claimed in claim 1 as DISPERSE DYES in the dyeing of fibre and the application in the stamp, it is characterized in that: described compound as shown in Equation 1 is in the following table, general formula is compound 1, and group is the particular compound of the arbitrary situation among numbering 1-1～1-76:
- As each described compound as shown in Equation 1 of claim 1～6 as DISPERSE DYES in the dyeing of fibre and the application in the stamp, it is characterized in that: described compound is as shown in Equation 1 handled through frosted and is obtained DISPERSE DYES.
- 8. compound as shown in Equation 1 as claimed in claim 7, is characterized in that in the dyeing of fibre and the application in the stamp as DISPERSE DYES: described fibre is polyester fiber goods or its blend fibre goods;And/or the existence form of described polyester fiber goods or its blend fibre goods is fiber, yarn, woven fabric, knitted fabric or nonwoven;And/or described polyester fiber goods or its blend fibre goods are outdoor exercises weaving face fabrics such as swimming suit.
- 9. compound as shown in Equation 1 as claimed in claim 8, is characterized in that in the dyeing of fibre and the application in the stamp as DISPERSE DYES: described polyester fiber goods are the ethylene glycol terephthalate fibre.
- 10. compound as shown in Equation 1 as claimed in claim 8, is characterized in that in the dyeing of fibre and the application in the stamp as DISPERSE DYES: the blend fibre goods of described polyester fiber goods are polyester/cotton or polyester/wool.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210594035.3A CN103233370B (en) | 2012-12-31 | 2012-12-31 | Disperse dye application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210594035.3A CN103233370B (en) | 2012-12-31 | 2012-12-31 | Disperse dye application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103233370A true CN103233370A (en) | 2013-08-07 |
| CN103233370B CN103233370B (en) | 2015-03-04 |
Family
ID=48881434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210594035.3A Expired - Fee Related CN103233370B (en) | 2012-12-31 | 2012-12-31 | Disperse dye application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103233370B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105111775A (en) * | 2015-09-30 | 2015-12-02 | 上海安诺其集团股份有限公司 | Application of azo compound |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3709872A (en) * | 1968-11-07 | 1973-01-09 | Ciba Geigy Ag | Dispersible phenyl-azo-phenyl dyestuffs |
| US4078890A (en) * | 1974-04-24 | 1978-03-14 | Ciba-Geigy Corporation | Process for the dyeing and printing of polyester material |
| US4099909A (en) * | 1970-01-16 | 1978-07-11 | Ciba-Geigy Ag | Method of dyeing with dispersible azo anilino dyestuffs |
| CH622542A5 (en) * | 1976-12-22 | 1981-04-15 | Nii Orch Poluproduktov I Krasi | Process for the preparation of novel disperse monoazo dyestuffs |
-
2012
- 2012-12-31 CN CN201210594035.3A patent/CN103233370B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3709872A (en) * | 1968-11-07 | 1973-01-09 | Ciba Geigy Ag | Dispersible phenyl-azo-phenyl dyestuffs |
| US4099909A (en) * | 1970-01-16 | 1978-07-11 | Ciba-Geigy Ag | Method of dyeing with dispersible azo anilino dyestuffs |
| US4078890A (en) * | 1974-04-24 | 1978-03-14 | Ciba-Geigy Corporation | Process for the dyeing and printing of polyester material |
| CH622542A5 (en) * | 1976-12-22 | 1981-04-15 | Nii Orch Poluproduktov I Krasi | Process for the preparation of novel disperse monoazo dyestuffs |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105111775A (en) * | 2015-09-30 | 2015-12-02 | 上海安诺其集团股份有限公司 | Application of azo compound |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103233370B (en) | 2015-03-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102604413B (en) | Middle-temperature type disperse dye compound and preparation method and application thereof | |
| CN106497139B (en) | A kind of supercritical CO2With vinyl-sulfone reactive disperse dyes and its preparation method and application | |
| CN102250485A (en) | Yellow disperse dye capable of dyeing in acid and alkaline baths | |
| KR20120098917A (en) | Disperse azo dyes | |
| CN103232408B (en) | Disperse dye compound | |
| CN105802278B (en) | A kind of Black reactive dye composition and its production and use | |
| CN104231659A (en) | Red thiazole heterocyclic disperse dye compound containing benzoate group and preparation and application thereof | |
| CN103232723B (en) | Easter compounds and preparation method thereof | |
| CN103232409B (en) | Preparation method of disperse dyestuff | |
| CN103233370B (en) | Disperse dye application | |
| CN104262992B (en) | High alkaline-resisting deep red dispersed dye and application thereof | |
| CN105254517B (en) | A kind of naphthalene cycle compound and preparation method thereof | |
| CN105218396B (en) | A kind of preparation method of azo-compound | |
| CN102174271A (en) | Temporarily water-soluble disperse dye and preparation method and application thereof | |
| CN105439896A (en) | Diaminoazobenzene compound | |
| BRPI0715862B1 (en) | dyes, their production process, dye mix, their uses, and ink for digital textile printing by inkjet process | |
| CN105111775A (en) | Application of azo compound | |
| CN105152964B (en) | Azo-compound | |
| CN106928751A (en) | A kind of bi-component disperse dyes and processing technology | |
| CN105647235A (en) | High dye uptake disperse dye composition and preparation method and application thereof | |
| CN105778563B (en) | A kind of Black reactive dye composition and its production and use | |
| CN106892874A (en) | The preparation method of monoazos | |
| CN105524483A (en) | Application of azoaniline compound as disperse dye | |
| CN105523959A (en) | Method for preparing azoaniline compound | |
| CN107337662A (en) | Water-soluble double fluorenyl quinoid thiophene derivant, preparation method and its tint applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB02 | Change of applicant information |
Address after: Liantang Town Pudong New Area Shanghai city 201717 Zhu Feng Road No. 6188 room 2622 Applicant after: SHANGHAI ANOKY GROUP CO., LTD. Address before: Liantang Town Pudong New Area Shanghai city 201717 Zhu Feng Road No. 6188 room 2622 Applicant before: Shanghai ANOKY Textile Chemicals Co., Ltd. |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: SHANGHAI ANOKY TEXTILE CHEMICALS CO., LTD. TO: SHANGHAI ANOKY GROUP CO., LTD. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150304 Termination date: 20201231 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |