CN103553983B - A kind of novel dye intermediate and the reactive dye as made from the intermediate - Google Patents
A kind of novel dye intermediate and the reactive dye as made from the intermediate Download PDFInfo
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- CN103553983B CN103553983B CN201310535664.3A CN201310535664A CN103553983B CN 103553983 B CN103553983 B CN 103553983B CN 201310535664 A CN201310535664 A CN 201310535664A CN 103553983 B CN103553983 B CN 103553983B
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Abstract
The present invention relates to a kind of novel dye intermediate and the reactive dye as made from the intermediate, the structural formula such as formula of the dyestuff intermediate（I）It is shown：The R is H, SO3H、‑COCH3、‑SO2NH2Or COCH=CH2。
Description
Technical field
The present invention relates to reactive dyestuff field, more particularly to a kind of new dyestuff intermediate and by the dyestuff intermediate system
Standby reactive dye.
Background technology
Present dyestuff main on the market still based on acid dyes, mordant dyes and premetallized dye, on
The dyestuff for stating type contaminates that material fastness is not good enough, and coloured light is not bright-coloured enough, and degree of fixation is low, big for environment pollution, particularly metal network
The free heavy metal that conjunction dyestuff is likely to occur has harm to human body and to environment.Due to the restriction of environmental ecology, for dyestuff
A kind of requirement more and more higher of dye uptake, degree of fixation and modifying porcelain, it is therefore desirable to high performance dyestuff and can
Improve the new dyestuff intermediate of dyestuff performance.
The content of the invention
It is an object of the present invention to provide a kind of new dyestuff intermediate, the dyestuff intermediate is compared to conventional dyestuff
Intermediate 4- nitro -2- sulfonic acid chlorobenzenes, amination is carried out using 2- ethylaminoethanols, so as to reach the purpose for introducing N- ethoxys, so
Laggard single step reaction prepares the intermediate of new KN type reactive dye.It is a further object of the present invention to provide by the new dyestuff
Reactive dye made from intermediate, cost of material needed for the reactive dye is low, and product solubility is high, and bright in colour, application
Excellent performance, strong applicability, and preparation process can reduce environmental pollution.
The technical solution adopted by the present invention is：
A kind of dyestuff intermediate, the structural formula such as formula of the dyestuff intermediate（I）It is shown：
The R is-H ,-SO3H、-COCH3、-SO2NH2Or-COCH=CH2。
Present invention also offers formula（I）The preparation method of compound, comprises the following steps：
1), neutralize
Paranitrochlorobenzene ortho-sulfonic acid is beaten with water, NaOH solution is added, after reaction, NaCl solids is added and saltouts；Filtering
White filter cake is obtained, crushing is dried, obtains white solid powder, treat next step.
2), amination
By step 1) gained white solid powder be beaten with alcohol, be allowed to scattered, heating systems to 80 DEG C or so systems reach
Boiling point to alcohol starts backflow, and 2- ethylaminoethanols are slowly added dropwise to system, and reaction is complete, then system is diluted to while hot filled
Diluted in the beaker of frozen water mixing, obtain yellow precipitate, 6-6.5 is arrived into pH regulations with HCl solution, plus salt is saltoutd, and is filtered
To yellow powder.
3), hydrogenating reduction
By step 2) gained yellow powder, put into autoclave, add catalyst Raney's nickel, sealing autoclave is thereto
Nitrogen is passed through, the air of the inside is displaced, hydrogen is then passed through again, 100 DEG C are heated to, holding is passed through Hydrogen Vapor Pressure 1.2MPa,
Cooling discharge after reaction completely, adds refined salt, and analysis of material is filtrated to get final product (4-N- ethoxys) aniline -3- sulfonic acid, that is, tied
Structure（I）-1；
When by structure（I）It is added to after -1 drying in oleum, in 50 DEG C or so fully reactions, by body after reaction fully
System is diluted in frozen water, keeps dilution temperature to be less than 10 DEG C, is added NaCl and is saltoutd, obtains red powder solid i.e. product (4-
N- ethylene hydroxy sulfuric acids ester group) aniline -3- sulfonic acid, i.e. structure（I）-2；
When by structure（I）It is added in acetic acid, is fully reacted at 75 DEG C or so after -1 drying, it is after reaction fully that system is dilute
Release in frozen water, keep dilution temperature to be less than 10 DEG C, add NaCl and saltout, obtain white powdery solids and obtain product structure
（I）-3；
When by structure（I）It is mixed to join after -1 dries with dry sulfamic acid in solid phase reactor, high-speed stirred,
System, is diluted in frozen water by 120 DEG C or so fully reactions after reaction fully, keeps dilution temperature to be less than 10 DEG C, by dilution
Drying goes water to obtain white powdery solids and obtains product structure（I）-4.
When by structure（I）It is added to after -1 drying in acrylic acid, in 40 DEG C or so fully reactions, by system after reaction fully
It is diluted in frozen water, keeps dilution temperature to be less than 10 DEG C, adds KCl and saltout, obtain white powdery solids i.e. product i.e. structure
（I）-5；
Present invention also offers formula（I）Application of the dyestuff intermediate in reactive dye are prepared.
Present invention also offers a kind of applying equation（I）The dyestuff that the dyestuff intermediate is prepared, the dyestuff has formula
（Ⅱ）Structural formula.
Present invention also offers a kind of applying equation（I）The dyestuff that the dyestuff intermediate is prepared, the dyestuff has formula
（Ⅲ）Structural formula：
The present invention is had the advantage that：
Intermediate of the present invention is used to prepare dyestuff, high using dye product solubility made from intermediate of the present invention, color and luster
Bright-coloured, application performance is excellent, strong applicability.
Embodiment
With reference to specific embodiment, the invention will be further described, but does not limit protection scope of the present invention.
The number referred in the embodiment of the present invention is molfraction.
Embodiment 1
A kind of intermediate for being used to prepare dyestuff, the structural formula such as formula of the intermediate（I）Shown in -1：
1), neutralize
By 1 part of paranitrochlorobenzene ortho-sulfonic acid, it is beaten with appropriate water, configures the NaOH of equimolar amounts（20%）Solution, slowly
It is added in slurries, quick stirring, and remains that system temperature is less than 30 DEG C, system becomes more sticky, accelerates stirring.
As pH=7-7.5, stop plus alkali.After stirring is a little, NaCl solids are suitably added according to precipitation situation and saltoutd.It is filtrated to get white
Color filter cake, dries crushing, obtains white solid powder, treat next step.
2), amination
By step 1) gained dry 1 part of white solid powder, 3 parts of use alcohol mashing, be allowed to scattered.Heating systems are extremely
80 DEG C or so systems reach that the boiling point of alcohol starts backflow, and 2.5 parts of 2- ethylaminoethanols are slowly added dropwise to system, and 40min is dripped off,
With dropwise addition, slurries gradually dissolve, and drip off and continue to maintain the reflux for 2h.Now, solution is homogeneous phase transparent shape, and reaction is complete, by body
System is diluted in the beaker for filling frozen water mixing while hot to be diluted.Yellow precipitate is obtained, HCl is used（30%）6- is arrived into pH regulations
6.5, suitably add salt to saltout, be filtrated to get yellow powder.
3), hydrogenating reduction
By step 2) gained yellow powder, put into autoclave, add a small amount of catalyst Raney's nickel, sealing autoclave to
Nitrogen is wherein passed through, the air of the inside is displaced, hydrogen is then passed through again, 100 DEG C are heated to, holding is passed through Hydrogen Vapor Pressure
1.2MPa, cooling discharge after reaction completely adds refined salt, and analysis of material is filtrated to get final product (4-N- ethoxys) aniline -3- sulphurs
Acid, i.e. structure（I）-1.
Product analysis
Chromatography chromatographic purities are carried out to final product and reach more than 97%, its production is calculated using chemistry titration amino value
Thing content, calculated yield reaches 75%-80%.
The reaction principle that above-mentioned steps are related to is as follows：
Paranitrochlorobenzene ortho-sulfonic acid
(4-N- ethoxys) aniline -3- sulfonic acid.
Embodiment 2
A kind of intermediate for being used to prepare dyestuff, the structural formula such as formula of the intermediate（I）Shown in -2：
By 1 part of dry structure（I）- 1 compound is added in 6 parts of oleums, is slowly warming up to 50 DEG C or so, holding
2h.System, is diluted in frozen water by chromatography or chromatography reaction process after reaction fully, keeps dilution temperature to be less than 10
DEG C, the appropriate NaCl that adds saltouts, and obtains red powder solid i.e. product (4-N- ethylene hydroxy sulfuric acids ester group) aniline -3- sulfonic acid,
That is structure（I）-2.
Product analysis
Chromatography chromatographic purities are carried out to final product and reach more than 95%, are surveyed using chemistry titration amino value and ester value
Its product assay is calculated, calculated yield reaches 70-75%.
The reaction principle that above-mentioned steps are related to is as follows：
Embodiment 3
A kind of intermediate for being used to prepare dyestuff, the structural formula such as formula of the intermediate（I）Shown in -3：
By 1 part of dry structure（I）- 1 compound is added in 8 parts of acetic acid, is slowly warming up to 75 DEG C or so, keeps 2-
3h.System, is diluted in frozen water by chromatography or chromatography reaction process after reaction fully, keeps dilution temperature to be less than 10
DEG C, the appropriate NaCl that adds saltouts, and obtains white powdery solids and obtains product structure（I）-3.
Product analysis
Chromatography chromatographic purities are carried out to final product and reach more than 92%, are surveyed using chemistry titration amino value and ester value
Its product assay is calculated, calculated yield reaches 68-70%.
The reaction principle that above-mentioned steps are related to is as follows：
Embodiment 4
A kind of intermediate for being used to prepare dyestuff, the structural formula such as formula of the intermediate（I）Shown in -4：
By 1 part of dry structure（I）- 1 compound and the 1.2 parts of sulfamic acids dried are mixed to join solid phase reactor
In, high-speed stirred is slowly warming up to 120 DEG C or so, keeps 5h or so.Chromatography or chromatography reaction process, reaction are abundant
System is diluted in frozen water afterwards, keeps dilution temperature to be less than 10 DEG C, dilution is dried and goes water to obtain white powdery solids
Obtain product structure（I）-4.
Product analysis
Chromatography chromatographic purities are carried out to final product and reach more than 90%, are surveyed using chemistry titration amino value and ester value
Its product assay is calculated, calculated yield reaches 60-65%.
Embodiment 5
A kind of intermediate for being used to prepare dyestuff, the structural formula such as formula of the intermediate（I）Shown in -5：
By 1 part of dry structure（I）- 1 compound is added in 5.5 parts of acrylic acid, is slowly warming up to 40 DEG C or so, holding
2h.System, is diluted in frozen water by chromatography or chromatography reaction process after reaction fully, keeps dilution temperature to be less than 10
DEG C, the appropriate KCl that adds saltouts, and obtains white powdery solids i.e. product i.e. structure（I）-5.
Product analysis
Chromatography chromatographic purities are carried out to final product and reach more than 96%, are surveyed using chemistry titration amino value and ester value
Its product assay is calculated, calculated yield reaches 75-80%.
The reaction principle that above-mentioned steps are related to is as follows：
Embodiment 6
A kind of blue active dye, shown in the structural formula such as formula (II) of the reactive dye：
Formula（Ⅱ）The preparation method of dyestuff is as follows：
1）, color base prepare:
1 part of bromamine acid is put into system and dissolved by heating, 2.5 parts of sodium bicarbonate are sequentially added, 1 part of M acid (3,5- diaminourea-
2,4,6- tri-methyl p-toluenesulfonates), 1 part of stannous chloride, temperature keeps 80-90 DEG C of reaction 4-5h, then cools less than 40 DEG C, adds
Appropriate diatomite, persistently stirs 1h, crosses elimination insoluble matter, then adjusts filtrate pH=7.0-7.5, then the 50-60 that heats up with hydrochloric acid
DEG C, elimination insoluble matter is crossed after adding proper amount of active carbon, stirring 1h, secondary filtrate systems are then warming up to 70-75 DEG C, one is added
Quantitative hydrochloric acid, stirs 2h, adds refined salt and saltouts, and stirs sampling analysis, it is qualified after be filtrated to get color base filter cake, then again in acidity
Under the conditions of be beaten, make the solid content of color base slurries after 35%-40%, long agitation, sampling analysis obtains color base slurries, qualified
It is stand-by afterwards.
2）, one contracting reaction:
1 part of Cyanuric Chloride is added in mixture of ice and water and is beaten, 0-5 DEG C, step 1 is added dropwise under the conditions of pH=2-3) gained
Color base slurries, reaction obtains a contracting thing；
3）, two contracting reaction:
1 part of dyestuff intermediate (4-N- ethoxys) aniline -3- sulfonic acid water is dissolved, step 2 is added drop-wise to) obtained by a contracting
In thing, pH=7-7.5 is controlled, 30-40 DEG C of reaction of temperature obtains formula（Ⅱ）Dye solution.
4）, it is refined
Above-mentioned dyestuff is added into diatomite in right amount, elimination insoluble matter is crossed, then using the pair in precision equipment removal system
Product and inorganic salts, blending is treated after measure is qualified.
5）, standardization blending
Require that it is to obtain dyestuff finished product to carry out blending according to standard
It is structural formula produced by the present invention below（Ⅱ）Reactive dye performance：
Embodiment 7
A kind of purple active dye, shown in the structural formula such as formula (III) of the reactive dye：
Formula（Ⅲ）The preparation method of dyestuff is as follows：
1）, structural formula（I）- 2 diazotising
By 1 part of structure（I）- 2 compounds are added to the water, mashing, after stirring 0.5h, add 2.3 parts of HCl（30%）, use
Ice-water bath cools to 0 DEG C or so, rapidly joins 1.1 parts of NaNO2Solution, is kept stirring for, and after low-temp reaction 2h, uses sulfamic acid
Unnecessary NaNO in removing system2, pH=2.0-2.2 is adjusted with sodium acid carbonate, diazo liquid a is obtained, it is standby；
2）, acid coupling
Sour (7- methylamino -4- hydroxyl -2- naphthalene sulfonic acids) powder, temperature control of the N- methyl J of 1 part of addition into diazo liquid a
At 10-15 DEG C, 10h is persistently stirred, sour even liquid b is obtained；
3）, para-ester diazotising
1 part of para-ester is added to the water mashing, 2.3 parts of HCl is added（30%）, less than 5 DEG C are cooled to, is rapidly joined
1.1 parts of NaNO2Solution, is kept stirring for, after low temperature 2h, with NaNO unnecessary in sulfamic acid removing system2, obtain diazo liquid
C, it is standby;
4）, alkaline coupling
By step 3）In diazo liquid c be added drop-wise in sour even liquid b, use Na2CO3PH=7-7.5 is adjusted, temperature control is in 15-
20 DEG C, 3-4h, flaggy or chromatogram detection reaction end are kept, reaction mixture d is obtained;
5）, saltout
Add NaCl into reaction mixture d to saltout, additional proportion is 10-15g：Filter, obtain after 100ml, stirring 1-1.5h
To dyestuff filter-cakes e;
6）, spray drying
Dyestuff filter-cakes e is added to the water mashing, is spray-dried, obtains structural formula（Ⅲ）Finished product dyestuff.
It is structure produced by the present invention below（Ⅲ）Reactive dye performance：
Under the enlightenment of embodiment 6,7, corresponding dyestuff is made in the replacement that those skilled in the art can carry out intermediate
Structure.
Claims (3)
1. a kind of dyestuff intermediate, it is characterised in that：Shown in the structural formula of the dyestuff intermediate such as formula (I)：
The R is-COCH3、-SO2NH2Or-COCH=CH2。
2. the preparation method of dyestuff intermediate described in claim 1, it is characterised in that：Comprise the following steps：
1), neutralize
Paranitrochlorobenzene ortho-sulfonic acid is beaten with water, NaOH solution is added, after reaction, NaCl solids is added and saltouts；It is filtrated to get
White filter cake, dries crushing, obtains white solid powder, treat next step；
2), amination
By step 1) gained white solid powder be beaten with alcohol, be allowed to scattered, heating systems to 80 DEG C or so systems reach wine
The boiling point of essence starts backflow, and 2- ethylaminoethanols are slowly added dropwise to system, and reaction is complete, then system is diluted to while hot fills frozen water
Diluted in the beaker of mixing, obtain yellow precipitate, 6-6.5 is arrived into pH regulations with HCl solution, plus salt is saltoutd, and is filtrated to get Huang
Color powder；
3), hydrogenating reduction
By step 2) gained yellow powder, put into autoclave, add catalyst Raney's nickel, sealing autoclave is passed through thereto
Nitrogen, displaces the air of the inside, hydrogen is then passed through again, is heated to 100 DEG C, holding is passed through Hydrogen Vapor Pressure 1.2MPa, reacts
Cooling discharge after completely, adds refined salt, and analysis of material is filtrated to get final product, i.e. structure (I) -1；
It is added in oleum, is fully reacted at 50 DEG C or so after structure (I) -1 is dried, it is after reaction fully that system is dilute
Release in frozen water, keep dilution temperature to be less than 10 DEG C, add NaCl and saltout, obtain red powder solid, i.e. structure (I) -2；
It is added in acetic acid, in 75 DEG C or so fully reactions, is diluted to system after reaction fully after structure (I) -1 is dried
In frozen water, keep dilution temperature be less than 10 DEG C, add NaCl saltout, obtain white powdery solids obtain product structure (I)-
3；
It is mixed to join after structure (I) -1 is dried with dry sulfamic acid in solid phase reactor, high-speed stirred, 120
DEG C or so fully reaction, reaction fully after system is diluted in frozen water, keep dilution temperature be less than 10 DEG C, dilution is dried
Go water to obtain white powdery solids and obtain product structure (I) -4；
It is added in acrylic acid, in 40 DEG C or so fully reactions, dilutes system after reaction fully after structure (I) -1 is dried
Into frozen water, keep dilution temperature be less than 10 DEG C, add KCl saltout, obtain white powdery solids i.e. product i.e. structure (I)-
5；
3. the dyestuff that dyestuff intermediate described in a kind of application claim 1 is prepared, it is characterised in that：The dyestuff has formula
(III) structural formula：
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| CN201310535664.3A CN103553983B (en) | 2013-10-31 | 2013-10-31 | A kind of novel dye intermediate and the reactive dye as made from the intermediate |
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| CN103553983B true CN103553983B (en) | 2017-10-24 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111517997B (en) * | 2020-04-17 | 2022-06-07 | 杭州博拓生物科技股份有限公司 | Ethyl sulfate artificial antigen, preparation method and application |
| CN112745247A (en) * | 2020-12-31 | 2021-05-04 | 湖北丽源科技股份有限公司 | Novel dye intermediate, novel dye and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB805562A (en) * | 1956-03-14 | 1958-12-10 | Ici Ltd | New phthalocyanine compounds |
| CN1158926A (en) * | 1995-11-23 | 1997-09-10 | 希巴特殊化学控股公司 | Process for dichromatic or trichromatic dyeing or printing |
| CN1266870A (en) * | 1999-03-15 | 2000-09-20 | 西巴特殊化学品控股有限公司 | Active dye, preparing method and use thereof |
| CN101235217A (en) * | 2008-01-22 | 2008-08-06 | 天津市德凯化工有限公司 | Black reactive dyestuff and preparation method thereof |
| CN102911523A (en) * | 2012-09-25 | 2013-02-06 | 天津德凯化工股份有限公司 | Blue reactive dye and preparation method thereof |
-
2013
- 2013-10-31 CN CN201310535664.3A patent/CN103553983B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB805562A (en) * | 1956-03-14 | 1958-12-10 | Ici Ltd | New phthalocyanine compounds |
| CN1158926A (en) * | 1995-11-23 | 1997-09-10 | 希巴特殊化学控股公司 | Process for dichromatic or trichromatic dyeing or printing |
| CN1266870A (en) * | 1999-03-15 | 2000-09-20 | 西巴特殊化学品控股有限公司 | Active dye, preparing method and use thereof |
| CN101235217A (en) * | 2008-01-22 | 2008-08-06 | 天津市德凯化工有限公司 | Black reactive dyestuff and preparation method thereof |
| CN102911523A (en) * | 2012-09-25 | 2013-02-06 | 天津德凯化工股份有限公司 | Blue reactive dye and preparation method thereof |
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Inventor after: Zhang Xinghua Inventor after: Zhang Youheng Inventor after: Zhang Yuqing Inventor after: Li Jiyou Inventor after: Li Rongcai Inventor before: Zhang Xinghua Inventor before: Zhang Youheng Inventor before: Zhang Yuqing Inventor before: Li Rongcai |
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Free format text: CORRECT: INVENTOR; FROM: ZHANG XINGHUA ZHANG YOUHENG ZHANG YUQING LI RONGCAI TO: ZHANG XINGHUA ZHANG YOUHENG ZHANG YUQING LI JIYOU LI RONGCAI |
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