CN104119693A - Orange reactive dye compound and application thereof - Google Patents
Orange reactive dye compound and application thereof Download PDFInfo
- Publication number
- CN104119693A CN104119693A CN201310454494.6A CN201310454494A CN104119693A CN 104119693 A CN104119693 A CN 104119693A CN 201310454494 A CN201310454494 A CN 201310454494A CN 104119693 A CN104119693 A CN 104119693A
- Authority
- CN
- China
- Prior art keywords
- compound
- dyeing
- dyestuff
- dye
- formula
- 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.)
- Pending
Links
Abstract
The invention provides an orange reactive dye compound with a hydrazone type structure and an application thereof. The compound not only has excellent perspiration-light fastness but also has extremely high fixation rate, better dye depth and better levelling property and wet processing fastness, and the non-fixation part is easy to wash out. When applied to printing and dyeing of fiber materials, the reactive dye compound has excellent perspiration-light resistance, high dye uptake and fixation rate, good improving property, levelling property and dyeing stability and bright and full color.
Description
(1) technical field
The present invention relates to a kind of orange active dye compound, be specifically related to a kind of orange active dye compound and application thereof with hydrazone formula structure.
(2) background technology
The degree of fixation of dyeing and weaving thing on reactive dyestuffs, fastness to wet rubbing is the Focal point and difficult point during printing and dyeing are produced always, generally only 50～80%, cause that on fabric, set dyestuff must be through abundant washing, the removal of soaping, not only caused the wasting of resources, and the colour fastness that has reduced textiles wet colour fastness particularly, and between set dyestuff and cotton fibre, not there is not Intermolecular Forces, after soaping, still have part to remain on fabric, simultaneously, covalent linkage between part reactive dyestuffs and cotton fibre is subject to the impact of ambient conditions, easily there is scission of link hydrolysis, thereby cause the color fastness decreased of DYED FABRICS.
In addition, along with the raising of people to the requirement of textiles ecological, environmental protective performance, sweat proof light fastness to reactive dyestuffs is had higher requirement, because under sweat and daylight dual function, metal ion-chelant due to the amino acid in sweat or related substances and metallized dye, make it depart from dye matrix, so just fade or variable color.The dyestuff and the byproduct of reaction thereof that depart from textiles also can directly contact skin, and the safety in utilization of human body is caused to infringement.The problem of cotton reactive dye sweat proof-light fastness is more outstanding at present.
(3) summary of the invention
The object of this invention is to provide a novel orange active dye compound class economy, that there is hydrazone formula structure, this compound not only has excellent sweat proof-light fastness, also there is high degree of fixation, preferably depth, preferably level-dyeing property and wet colour fastness, and non-fixing part is easy to eccysis.
The technical solution used in the present invention is:
An orange active dye compound, structure is as shown in formula I:
In formula I:
R
1, R
2, R
3independent is separately H ,-SO
3m, C
1～C
4alkyl or C
1～C
4alkoxyl group, is preferably-H ,-SO
3m ,-CH
3or-OCH
3; Y
1, Y
2be-CH=CH independently separately
2or-C
2h
4oSO
3m, M is H or basic metal, described basic metal is selected from Li, Na or K.
Above-claimed cpd (I) structural formula is preferably as follows:
Described compound is preferably one of following formula:
Preferably, in described compound, M is H, Na or K.
The orange active dye compound of formula I of the present invention, can free acid or preferably with the form of an alkali metal salt (particular certain cancers or sylvite), prepare, and according to usual method, it can be changed into by free acid form the form of an alkali metal salt.Concrete, described method comprises: first by formula (a) and compound (b) under the existence of hydrochloric acid or sulfuric acid, according to this area ordinary method, at-5 ℃～5 ℃, carry out diazotization with Sodium Nitrite, gained diazonium compound is carried out coupling with the compound shown in formula (c) again under the condition of pH value 1～7.5, makes described orange active dye compound;
In formula (a)～(c):
R
1, R
2, R
3independent is separately H ,-SO
3m, C
1～C
4alkyl or C
1～C
4alkoxyl group, is preferably-H ,-SO
3m ,-CH
3or-OCH
3; Y
1, Y
2be-CH=CH independently separately
2or-C
2h
4oSO
3m, M is H or basic metal, described basic metal is selected from Li, Na or K.
Preferably, described method can be as follows:
(1) diazotization: after compound (a) is added to and is stirred in water, be cooled to 0-10 ℃, add hydrochloric acid, making beating 30～60min drips sodium nitrite solution at 0～5 ℃ from liquid level, drip and reaction process in keep Sodium Nitrite micro-excessive.Diazotization, after terminal, is eliminated excessive Sodium Nitrite with thionamic acid, obtains the diazo liquid of compound (a);
(2) diazotization: after compound (b) is added to and is stirred in water, be cooled to 0-5 ℃, and maintain 0-5 ℃ and slowly drip hydrochloric acid and Sodium Nitrite, at this temperature, stir 0.5～2 hour, with thionamic acid, eliminate excessive Sodium Nitrite, obtain the diazo liquid of compound (b);
(3) coupling: the diazonium salt of step (1) is joined in the suspension of compound (c), carry out a coupling at-5～10 ℃.After coupling completes, continue to maintain-5～10 ℃, the diazo liquid that slowly adds step (2) reaction to obtain, regulating pH is 5～6.8, carries out coupled reaction for the second time, after having reacted, continue to add alkali and regulate pH to 7.0～7.5, drying, the dyestuff of hydrazone formula structure shown in acquisition formula I.
Formula (a)～(c) compound is known dyestuff intermediate, can prepare easily or buy from market.The dyestuff of the formula I making can carry out separation in accordance with known methods, for example, use an alkali metal salt (particular certain cancers or sylvite) to saltout, and filters and is dried.
The application of described orange active dye compound in preparing active orange dye.
Utilize the dyestuff finished product that the compounds of this invention is made can be with solid particulate, Powdered or liquid form exists, and conventionally contain the electrolyte salt of common reactive dyestuffs in synthetic, as sodium-chlor, Repone K and sodium sulfate, the dyestuff of solid form also contains the auxiliary agent being common in commercial dyestuff, if by the pH value stabilization of the aqueous solution at 3～7 buffer substance, as Sodium Tetraborate, sodium bicarbonate, Trisodium Citrate, SODIUM PHOSPHATE, MONOBASIC and Sodium phosphate dibasic, and a small amount of siccative, or, if they exist as liquid or the aqueous solution (comprising the common thickening material for the slurry of printing and dyeing).
Reactive dye compound of the present invention, is applicable to the printing and dyeing of cellulosic fibre, tynex and fabric thereof, and wherein, the preferred cotton fibre of cellulosic fibre and regenerated fibre, also can comprise other vegetative fiber, certainly as bast-fibre or fabric; Tynex preferably includes skin, hair or silk at interior animal fiber material, and the filamentary material such as synthetic nylon 6, nylon 66.While adopting the above-mentioned filamentary material of active dye printing of the present invention, can carry out in accordance with known reactive dyes dyeing method, as conventional reactive dyestuffs in exhaustion staining and pad dyeing staining, described exhaust dyeing be by textile impregnation in dye liquor, make dyestuff go up gradually the method for dyeing and weaving thing, conventionally need dyed-fixation-washing-soap boiling-washing-dehydration-operations such as oven dry.Described pad dyeing be first textile impregnation in dye liquor, then make fabric pass through roll, dye liquor is evenly rolled into fabric, the dyeing process of processing through decatize or hot melt etc. again, conventionally need be through padding dye liquor-oven dry-(padding fixation liquid)-decatize or bake-wash-soap-wash-operation such as dry.
Conventionally, due to the difference that on fabric, dyeing pool requires, dyestuff usage quantity also can be different, while using dip method dyeing, dye level is generally 0.1～10%(dyestuff to fabric weight), bath raio 1:2～1:60, preferred 1:10～1:30, just dye temperature and control 30～60 ℃, dyeing time 10～30 minutes, 85～95 ℃ of soap boiling temperature, 10～15 minutes soap boiling time, 60～100 ℃ of color fixing temperatures, 10～50 minutes fixation time, fixation pH value 9～11.While using pad dyeing method dyeing, the pick-up of cellulosic fibre is generally 60～80%, 100～103 ℃ of steam temperatures, steaming time 1～3 minute.In pad dyeing method, current more use be cold-rolling heap staining method, dyestuff and alkaline matter are incorporated in pad fix machine, and at room temperature clot banks up and within 2～30 hours, carries out fixation, carry out afterwards thorough rinsing.
Reactive dye compound of the present invention, while being applied to the printing and dyeing of above-mentioned filamentary material, its sweat proof-optical property is excellent, and dye uptake and degree of fixation are high, and enhancing, level-dyeing property, dye stability are good, and color and luster is vivid full.
(4) accompanying drawing explanation
Fig. 1 is embodiment 1 compound N MR collection of illustrative plates.
(5) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
Compound with chemical formulation in embodiment writes out with the form of its sodium salt, and this is because they are prepared with separated with the form of its sodium salt conventionally, and also with the form of sodium salt for dyeing.The initial compounds described in the following example can free acid form or similarly with the form of its sodium salt for the synthesis of in.
Embodiment 1:
(1) diazotization: the sulfonation para-ester of 36.1g (being 4-β-ethyl sulfuryl sulfate ester aniline-2-sulfonic acid) is added to stirring to pulp in 150mL water, the 2-5 ℃ that cools on the rocks, the 31%(w/w that adds 5.6ml) hydrochloric acid, making beating 30min, at 0～5 ℃, from liquid level, slowly drip 24.5g30%(w/w) sodium nitrite solution, control 5～10 ℃ of temperature, pH value 1.0～1.2, in the situation that potassium iodide starch paper develops the color, stirring reaction is approximately 3 hours, with thionamic acid, eliminate excessive Sodium Nitrite, obtain the diazo liquid of sulfonation para-ester.
(2) diazotization: the para-ester of 28.1g (to (beta-hydroxyethyl sulfone sulfate) aniline) is added to stirring to pulp in 80mL water, the 1-3 ℃ that cools on the rocks, slowly drip 11.2g31% hydrochloric acid, the Sodium Nitrite that adds 24.5g30% in 20～30min, control 2～5 ℃ of temperature, pH value 1.0～1.2, stirring reaction approximately 2 hours, with thionamic acid, eliminate excessive Sodium Nitrite, obtain the diazo liquid of para-ester.
(3) coupling: by 2 of 18.8g, 4-diamino benzene sulfonic acid adds water stirring to pulp, the diazo liquid that slowly adds step (1), adjusting pH is 1.0～2.0, and control temperature-5-5 ℃, coupled reaction 4～6 hours, obtain coupling solution one time, continue holding temperature-5-5 ℃, the diazo liquid that adds step (2) reaction to obtain in 10～20min, 30% sodium hydroxide solution adjust pH 5.0～6.5, carry out coupling for the second time, coupled reaction 3～5 hours, after having reacted, adjust pH value 7.0～7.5, dry, the dyestuff (seeing Fig. 1 nuclear magnetic resonance map) of hydrazone formula structure shown in main acquisition formula (I-1), and account for the by product that total content is no more than 30% formula (II-1)～(II-2), on this dyestuff, dyeing and weaving thing is hues of orange.
Above-mentioned formula (I-1), (II-1)～(II-2) are sodium-salt form, and M is Na;
The by product of above-mentioned formula (II-1)～(II-2) is need not be especially separated, can be present in the dyestuff of formula (I-1) jointly painted for filamentary material.
There is absorption peak in spectrum elucidation: 9.3ppm, 9.7ppm and 11.35ppm, should be quinone hydrazone structure, due in about 16ppm without absorption peak, so without intramolecular hydrogen bond; The absorption peak of 5.35ppm phenyl amine H;
3.-4.1ppm there is CH
2absorption peak; 7.7-8.3ppm is 8 H on phenyl ring and former phenyl ring.
Embodiment 2～8:
According to the preparation method described in embodiment 1 or similar method, different: to adopt respectively the arylamine in the arylamine 1, arylamine 2 alternative steps (1), step (2) of equimolar amount in table 1 to carry out diazotization, can make hydrazone formula dyestuff as shown in table 1, upper dyeing and weaving thing presents bright orange.
Table 1
Application Example:
At 60 ℃, respectively 100 grams of cotton fabrics are added in the dye bath of 1500 grams of 45g/L sodium-chlor and 2 grams of reactive dyestuffs compositions that obtain according to embodiment 1～8.At this temperature, dye after 45 minutes, add the sodium carbonate solution of 20g/L, keep this temperature to dye again 45 minutes.Then, rinse product dyed thereby, with nonionic detergent, soap 15 minutes, post rinse is also dry, records its basic dyeing behavior eigenwert in Table 2:
Table 2: basic dyeing characteristic value S.E.R.F
| Project | S value | E value | F value | R value |
| Embodiment 1 | 52.2% | 98.9% | 90.3% | 75.7% |
| Embodiment 2 | 52.0% | 96.8% | 89.1% | 77.4% |
| Embodiment 3 | 51.6% | 96.4% | 88.5% | 75.2% |
| Embodiment 4 | 50.7% | 97.3% | 87.5% | 75.0% |
| Embodiment 5 | 51.1% | 96.2% | 89.8% | 74.5% |
| Embodiment 6 | 52.4% | 98.4% | 90.7% | 73.9% |
| Embodiment 7 | 49.1% | 95.6% | 87.2% | 73.1% |
| Embodiment 8 | 51.5% | 97.6% | 89.3% | 77.2% |
In upper table:
S value represents the size of dyestuff to fiber affinity.S value is large, shows that dyestuff is large to the avidity of fiber, inhales look fast, but migration property meeting variation, easily washing property is poor to dye rear unconjugated dyestuff.
E value represents the degree of exhaustion of dyestuff.E value is large, represents that the clean absorption rate of dyestuff is high, and the utilization ratio of general remark dyestuff is high, and depth is good, and the pollution level of dyeing waste is little.
F value represents the degree of fixation of dyestuff.F value is large, illustrate to generate with fiber that covalent linkage reacts and the dyestuff of set is many, and dyestuff and unreacted dyestuff that generation is hydrolyzed is few, and dye utilization rate is high.
The reactive height of R value representation dyestuff.R value is large, illustrates that dyestuff is strong with the ability that fiber generation covalent linkage reacts under alkaline condition, and speed of reaction is fast, but the too high aberration end to end that easily causes.
From above-mentioned table 1, reactive dyestuffs S value of the present invention and R value are moderate, illustrate that avidity and level-dyeing property are all good; E value and F value are large, illustrate that dyestuff depth is good, and degree of fixation is high, and dye utilization rate is high.
In addition, by method definite in GB/T3921, GB/T3920 and GB/T14576, test respectively that it is water-fastness, antifriction scrape along sweat proof-photorecombination colour fastness, the results are shown in Table 3:
Table 3: colour fastness
To sum up, hydrazone formula structure-activity dyestuff of the present invention, while being applied to dye, has preferably comprehensive dyeing behavior, and depth is good, degree of fixation is high, level-dyeing property is good, wet colour fastness is excellent.
Claims (4)
1. an orange active dye compound, structure is as shown in formula I:
In formula I:
R
1, R
2, R
3independent is separately H ,-SO
3m, C
1～C
4alkyl or C
1～C
4alkoxyl group; Y
1, Y
2be-CH=CH independently separately
2or-C
2h
4oSO
3m, M is H or basic metal.
2. compound as claimed in claim 1, is characterized in that described compound is one of following formula:
3. compound as claimed in claim 1 or 2, is characterized in that in described compound, M is H, Na or K.
4. the application of compound as claimed in claim 1 in preparing orange active dye.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310454494.6A CN104119693A (en) | 2013-04-28 | 2013-09-27 | Orange reactive dye compound and application thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310156061.2 | 2013-04-28 | ||
| CN201310156061 | 2013-04-28 | ||
| CN201310454494.6A CN104119693A (en) | 2013-04-28 | 2013-09-27 | Orange reactive dye compound and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104119693A true CN104119693A (en) | 2014-10-29 |
Family
ID=51765340
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310454494.6A Pending CN104119693A (en) | 2013-04-28 | 2013-09-27 | Orange reactive dye compound and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104119693A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR900004223B1 (en) * | 1987-06-10 | 1990-06-18 | 이화산업 주식회사 | Process for the preparation of reactive disazo dyes |
| CN1163291A (en) * | 1996-01-19 | 1997-10-29 | 希巴特殊化学控股公司 | Active dye, their preparation and use |
| CN1195678A (en) * | 1997-04-07 | 1998-10-14 | 希巴特殊化学控股公司 | Mixtures of reactive dyes and their use |
| CN101173113A (en) * | 2007-10-30 | 2008-05-07 | 上海科华染料工业有限公司 | Reactive dye composition |
-
2013
- 2013-09-27 CN CN201310454494.6A patent/CN104119693A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR900004223B1 (en) * | 1987-06-10 | 1990-06-18 | 이화산업 주식회사 | Process for the preparation of reactive disazo dyes |
| CN1163291A (en) * | 1996-01-19 | 1997-10-29 | 希巴特殊化学控股公司 | Active dye, their preparation and use |
| CN1195678A (en) * | 1997-04-07 | 1998-10-14 | 希巴特殊化学控股公司 | Mixtures of reactive dyes and their use |
| CN101173113A (en) * | 2007-10-30 | 2008-05-07 | 上海科华染料工业有限公司 | Reactive dye composition |
Non-Patent Citations (2)
| Title |
|---|
| J. KELEMEN ET AL: "Azo—hydrazone tautomerism in azo dyes. III. The tautomeric structure of 1-(4′-nitrophenylazo)-2-naphthylamine from crystal structure determination", 《DYES AND PIGMENTS》, no. 4, 31 July 2001 (2001-07-31), pages 249 - 271 * |
| J.KELEMEN ET AL: "Azo—hydrazone tautomerism in azo dyes. II. Raman, NMR and mass spectrometric investigations of 1-phenylazo-2-naphthylamine and 1-phenylazo-2-naphthol derivatives", 《DYES AND PIGMENTS》, no. 1, 31 July 2001 (2001-07-31), pages 27 - 47 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100533181B1 (en) | Reactive dye mixtures and how to dye or print using them | |
| CN101555360B (en) | Active tricolor dye composition | |
| CN101935466B (en) | Active red dye composition | |
| CN101880473B (en) | Active orange dye composition | |
| CN101362864A (en) | Composite activity black dyes | |
| CN101555361B (en) | Active red dye composition | |
| CN1995153A (en) | Composite active dye | |
| CN105647238B (en) | A kind of grey reactive dye compound and its production and use | |
| CN101880474B (en) | Orange red reactive dyestuff composition | |
| CN105199427B (en) | A kind of polyazo reactive dye compound and preparation method thereof | |
| CN104119694A (en) | Orange reactive dye compound and application | |
| CN100375762C (en) | Composite reactive red and its formualtion | |
| CN104119692A (en) | Orange reactive dye compound and application thereof | |
| CN103773074A (en) | Yellow reactive dye compound | |
| CN102433030B (en) | Active yellow dye composition | |
| CN101565553B (en) | Brown azo dye and preparation and application thereof | |
| EP2000511A2 (en) | Trisazo reactive dyestuff compound | |
| CN107987555B (en) | Reactive blue-to-black dye composition and dye product | |
| CN101880475B (en) | Active scarlet dye composition | |
| CN102504582B (en) | Reactive dark blue bisazo dye and preparation method thereof | |
| CN103773072A (en) | Yellow reactive dye compound | |
| CN104119691A (en) | Orange red reactive dye compound and application thereof | |
| CN104119693A (en) | Orange reactive dye compound and application thereof | |
| CN109320996B (en) | Composite active black dye mixture and application thereof | |
| CN103773071A (en) | Yellow reactive dye compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20141029 |