CN102127308A - Read active dye and preparation method thereof - Google Patents
Read active dye and preparation method thereof Download PDFInfo
- Publication number
- CN102127308A CN102127308A CN2010106126611A CN201010612661A CN102127308A CN 102127308 A CN102127308 A CN 102127308A CN 2010106126611 A CN2010106126611 A CN 2010106126611A CN 201010612661 A CN201010612661 A CN 201010612661A CN 102127308 A CN102127308 A CN 102127308A
- Authority
- CN
- China
- Prior art keywords
- preparation
- reactive dyes
- dye solution
- red reactive
- add
- 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
Landscapes
- Coloring (AREA)
Abstract
The invention provides a red active dye with low salt content, and high solubility, fixation and color yield, and a preparation method thereof. The invention abandons a method of obtaining a finished product and salting out in the prior art, and adopts a flow of coupling, salting out, performing secondary condensation and salting out again; and the prepared red active dye has extremely low salt content, and high solubility, fixation and color yield, and can meet Reach by European union and Otex-100 standard.
Description
Technical field
The present invention is applicable to the pad dyeing of cotton, silk, viscose fabric and a kind of red reactive dyes of stamp, is specifically related to the preparation method of a kind of red reactive dyes and this dyestuff.
Background technology
Reactive dyestuffs have lovely luster, application performance excellence, distinguishing feature such as easy to use.In recent years, because the restriction of technology trade barriers such as Otex-100 and the Reach of European Union rules, require more and more higher to the security of reactive dyestuffs and degree of fixation, enhancing etc.Research and development high colour-fast rate, high-dissolvability, high enhancing and the environmental protection reactive dyestuffs that do not contain forbidding aromatic amine and heavy metal ion are dealt with the pressing for of trade green barrier of global textiles.Along with the requirement of dyeing to automatic liquid matching and automatic blended size system, the invention performance is better than reactive red No. 24 (Reactive Brilliant Red K-2BP), adaptation automatic liquid matchings, the particulate state and the liquid reactive dye of blended size system will be developing direction automatically simultaneously
And the general preparation process of at present domestic red reactive dyes is: H acid and cyanuric chloride condensation---ORTHO AMINO PHENOL SULPHONIC diazotization---condensated liquid carry out coupling in diazonium salt, and saltouing after must finished product promptly makes red reactive dyes again.But the dyestuff saltiness height that utilizes this kind technology to obtain, and dissolution rate, degree of fixation and dye yield are all lower, do not meet the requirement for red reactive dyes of Otex-100 and the Reach of European Union rules.
Summary of the invention
At above the deficiencies in the prior art, it is low to the invention provides a kind of saltiness, the red reactive dyes that solubleness, degree of fixation and dye yield are all higher and the preparation method of this dyestuff.
The present invention is achieved by the following technical solutions:
First scheme of the present invention provides a kind of structural formula of red reactive dyes,
Wherein X is Li, Na, K or H.
Alternative plan of the present invention provides the preparation method of above-mentioned red reactive dyes, at first with the condensated liquid of H acid and cyanuric chloride, carry out coupling in the diazonium salt of adding ORTHO AMINO PHENOL SULPHONIC, after disappearing, diazonium salt saltouts and suction filtration, filter cake making beating dissolving with gained, it is 75%～85% that UV analyzes color base content, add Ortho Toluidine again and carry out the secondary condensation, temperature is controlled at 5～25 ℃, pH value is controlled at 6～6.5, reacted 4～6 hours, disappearing to the liquid chromatographic detection Ortho Toluidine is to get dye solution A by terminal point.
After in dye solution A, adding flocculating aids removal impurity, filtrate is carried out desalting treatment, get dye solution B.In the actually operating, with dye solution A be diluted to be about 10% solid content after, add diatomite and remove impurity as flocculating aids, utilize reverse osmosis membrane to carry out desalination and concentration again to the dye solution B that is about 20% solid content.
In dye solution B, add in ε-Ji Neixianan, the urea one or both, dispersion agent and PH stablizer, spraying drying makes the particulate state reactive dyestuffs.This moment, the structural formula of dyestuff was
After the dye solution B that perhaps will be about 20% solid content is diluted to and is about 10%, utilize reverse osmosis membrane to carry out desalination and concentration again to the solid content that is about 20%, the control specific conductivity is less than 1ms/cm, add concentration then and be 10% Aqueous Lithium Salts (as lithium chloride or lithium oxalate), temperature is controlled at 35～45 ℃, stirred 1.5～2.5 hours, carry out reverse osmosis membrane desalination and concentration to solid content again and be about 50%, add again in ε-Ji Neixianan, the urea one or both, sanitas, make liquid reactive dye.
Aqueous Lithium Salts herein act as sodium ion in the substitutional solution, in order to the stability of enhance liquid reactive dyestuffs.Therefore this moment, most of dyestuff converted lithium salts to, and its structural formula is
In addition, because in preparation process, repeatedly need to use acid, alkali comes the pH value of regulator solution, if use K
2CO
3Perhaps other sylvite are regulated PH, then the structural formula of dyestuff can for
If adopt the method for acid out to come sublimation dye, or dyestuff transferred to acidity, then its structural formula also can for
The beneficial effect of the invention: the present invention has abandoned and has got the method that finished product is saltoutd again in the prior art, saltout earlier after adopting coupling, pass through the secondary condensation again, the flow process of saltouing again, the active orchil that makes has extremely low saltiness, high solubleness, high degree of fixation, high dye yield, can satisfy the Reach of European Union rules and Otex-100 standard-required.
Can be used for automatic blended size system and high performance red reactive dyes particle, saltiness is extremely low, 20 ℃ of solubleness reach 200g/L, 4～5 grades of light fastnesss, 4～5 grades of calico staining fastnesses, 3～4 grades of fastness to wet rubbings can directly apply to the dry powder spreading stamp of sizing mixing, and the aqueous solution can be used for the automatic blended size system of stamp; Making liquid dye can directly use, and normal temperature is exerted oneself part up to 33%, can store under the normal temperature 1 year, and degree of fixation descends less than 5%, can be directly used in automatic liquid mixing system, also can be directly used in ink-jet printed preparation with ink.
The active orchil that the present invention makes is compared with commercially available reactive red K-BP, has that saltiness is low, solubleness is high, degree of fixation is high, the high advantages such as (lifting forces) of dye yield, is widely used in pad dyeing, the stamp of various cellulosic fibres.During the simultaneous test data are listed in the table below.
Table 1: saltiness, solubleness, degree of fixation contrast
Table 2, dye yield (lifting force) contrast
Following standard is adopted in the test of performance index in table:
The general condition regulation that the GB/T2374-1994 dyeing is measured
The measuring method of GB/T2388-1980 printing with reactive dye coloured light and intensity
The measuring method of GB/T2393-1980 printing with reactive dye degree of fixation
The mensuration of GB/T3671.1-1996 water-soluble dye solubleness and steady dissolution
GB/T4841.1-1984 1/1 dyeing standard depth colour atla
GB/T6678-1986 Chemicals sampling general provisions
The mensuration of GB/T 21875-2008 dyestuff lifting force
Embodiment
Below in conjunction with embodiment the present invention is described in further details.
Embodiment 1
Step 1, H acid and cyanuric chloride condensation
19.5g cyanuric chloride solid is added in the 1000ml beaker that contains 200g ice, water, and making beating was stirred 45 minutes; Folding 100%H acid 34.1g regulates PH=6.5～7 with 40% liquid caustic soda is dissolved into 15% aqueous solution, controlled temperature is 3～8 ℃ then, congo-red test paper is dark blue, the H acid solution is dropped in the cyanuric chloride suspension, reinforced 45～60 minutes time, add reaction 3～5 hours, detecting free H acid content is terminal point less than 0.5%.After terminal point arrives, filter and remove impurity, collect filtrate for later use.
Step 2, ORTHO AMINO PHENOL SULPHONIC diazotization
To roll over 100% ORTHO AMINO PHENOL SULPHONIC 17.3g and put into the 1000ml beaker, and add water 50ml, ice 100g, regulate PH=7～7.5, add 35% hydrochloric acid 29ml then with 40% liquid caustic soda.Add the 6.9g Sodium Nitrite, 0～10 ℃ of controlled temperature, congo-red test paper is dark blue, and the little indigo plant of KI starch test paper is carried out diazotization reaction, in 30～45 minutes reaction times, eliminates little excessive nitrite sodium with thionamic acid at last.
Step 3, coupling
H acid and cyanuric chloride condensated liquid be added in the above-mentioned diazonium salt of finishing carry out coupling, 0～5 ℃ of controlled temperature is regulated PH=5.5～6 with sodium bicarbonate and is carried out coupled reaction, and in 4 hours reaction times, it is terminal point that the test diazonium salt disappears.Add 170g sodium-chlor and saltout, saltout and stirred 2 hours, suction filtration separate filter cake.
Step 4, the condensation of Ortho Toluidine secondary
Above-mentioned filter cake is placed in the 1000ml beaker, adds water 800ml making beating dissolving, UV analyzes color base content, and the color base yield is 78%, adds Ortho Toluidine 8.2g, 5～25 ℃ of controlled temperature, and sodium bicarbonate is regulated PH=6～6.5, reacts 4～6 hours.The liquid chromatographic detection Ortho Toluidine disappears and is terminal point.Get the about 1000ml dye solution of volume A.
The preparation of step 5, particulate state dyestuff
With the above-mentioned dye solution A 500ml that makes, be diluted to 10% solid content that is about, add the 25g diatomite filtration and remove impurity, collect filtrate.Filtrate is concentrated into the dye solution B that is about 20% solid content with reverse osmosis membrane processing.Add ε-Ji Neixianan 2.5g, dispersion agent N5g, PH stablizer SODIUM PHOSPHATE, MONOBASIC 0.5g and Sodium phosphate dibasic 2g,, get 50g red granules shape dyestuff 350～550 ℃ of spraying dryings.
The preparation of step 6, liquid dye
With other 500ml dye solution A, be diluted to 10% solid content that is about, add the 25g diatomite filtration and remove impurity, collect filtrate.Filtrate is concentrated into the dye solution B that is about 20% solid content with reverse osmosis membrane processing.Thin up is to being about 10% again, the continuation film is handled to be concentrated into and is about 20% solid content, the control specific conductivity adds 10% lithium chloride aqueous solution 40g, 35～45 ℃ of controlled temperature then less than 1ms/cm, stirred 1.5～2.5 hours, film is handled to be concentrated into and is about 50% then, adds urea 15g, sanitas PROXEL 0.1g, agitation and filtration, collect filtrate, 150g intensity is 33% red liquid reactive dyestuffs.
Preparation method of the present invention has abandoned and has got the method that finished product is saltoutd again in the prior art, saltout earlier after adopting coupling, pass through the secondary condensation again, the flow process of saltouing again, the active orchil that makes has extremely low saltiness, high solubleness, high degree of fixation, high dye yield, can satisfy the Reach of European Union rules and Otex-100 standard-required.
Can be used for automatic blended size system and high performance red reactive dyes particle, saltiness is extremely low, 20 ℃ of solubleness reach 200g/L, 4～5 grades of light fastnesss, 4～5 grades of calico staining fastnesses, 3～4 grades of fastness to wet rubbings can directly apply to the dry powder spreading stamp of sizing mixing, and the aqueous solution can be used for the automatic blended size system of stamp; Making liquid dye can directly use, and normal temperature is exerted oneself part up to 33%, can store under the normal temperature 1 year, and degree of fixation descends less than 5%, can be directly used in automatic liquid mixing system, also can be directly used in ink-jet printed preparation with ink.
Claims (9)
1. red reactive dyes is characterized in that the structural formula of described dyestuff is as follows:
Wherein X is Li, Na, K or H.
2. the preparation method of a red reactive dyes is characterized in that
With the condensated liquid of H acid and cyanuric chloride, add in the diazonium salt of ORTHO AMINO PHENOL SULPHONIC and carry out coupling, after disappearing, diazonium salt saltouts, and add Ortho Toluidine again and carry out the secondary condensation, disappearing to the liquid chromatographic detection Ortho Toluidine is to get dye solution A by terminal point.
3. the preparation method of red reactive dyes according to claim 2 is characterized in that behind the adding flocculating aids removal impurity, filtrate being carried out desalting treatment in dye solution A, gets dye solution B.
4. the preparation method of red reactive dyes according to claim 3, it is characterized in that in dye solution B, adding in ε-Ji Neixianan, the urea one or both, dispersion agent and PH stablizer, spraying drying makes the particulate state reactive dyestuffs.
5. the preparation method of red reactive dyes according to claim 3, it is characterized in that dye solution B desalting treatment and control specific conductivity less than 1ms/cm, add Aqueous Lithium Salts, continue desalting treatment, in adding ε-Ji Neixianan, the urea one or both, sanitas make liquid reactive dye.
6. the preparation method of red reactive dyes according to claim 2, the back suction filtration that it is characterized in that saltouing, with the filter cake making beating dissolving of gained, it is 75%～85% that UV analyzes color base content, adds Ortho Toluidine again and carries out the secondary condensation.
7. the preparation method of red reactive dyes according to claim 6 is characterized in that described secondary condensation temp is controlled at 5～25 ℃, and pH value is controlled at 6～6.5, reacts 4～6 hours.
8. the preparation method of red reactive dyes according to claim 3, it is characterized in that with dye solution A be diluted to be about 10% solid content after, add diatomite and remove impurity, utilize reverse osmosis membrane to carry out desalination and concentration again to the dye solution B that is about 20% solid content as flocculating aids.
9. according to the preparation method of claim 5 or 8 described red reactive dyes, after the dye solution B that it is characterized in that being about 20% solid content is diluted to and is about 10%, utilize reverse osmosis membrane to carry out desalination and concentration again to the solid content that is about 20%, the control specific conductivity is less than 1ms/cm, add concentration then and be 10% Aqueous Lithium Salts, temperature is controlled at 35～45 ℃, stirs 1.5～2.5 hours, carries out reverse osmosis membrane desalination and concentration to solid content again and is about 50%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106126611A CN102127308A (en) | 2010-12-29 | 2010-12-29 | Read active dye and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106126611A CN102127308A (en) | 2010-12-29 | 2010-12-29 | Read active dye and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102127308A true CN102127308A (en) | 2011-07-20 |
Family
ID=44265596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010106126611A Pending CN102127308A (en) | 2010-12-29 | 2010-12-29 | Read active dye and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102127308A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103013169A (en) * | 2012-12-06 | 2013-04-03 | 青岛大学 | Spray drying method of azo-based organic dye aqueous solution |
| CN105694534A (en) * | 2016-01-18 | 2016-06-22 | 浙江劲光数码科技有限公司 | Liquid dye for active ink and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61101576A (en) * | 1984-10-23 | 1986-05-20 | Orient Kagaku Kogyo Kk | Water based ink composition |
| CN1254735A (en) * | 1998-11-11 | 2000-05-31 | 德意志戴斯达纺织品及染料两合公司 | Dye mixture and its preparing process and application |
| CN101486842A (en) * | 2009-02-23 | 2009-07-22 | 湖北得宝染料工业有限公司 | Red active dye, and preparation method and use thereof |
| CN101565560A (en) * | 2009-04-14 | 2009-10-28 | 丽源(湖北)科技有限公司 | Red reactive dye mixture and preparation and application thereof |
| CN101880474A (en) * | 2010-06-29 | 2010-11-10 | 上海科华染料工业有限公司 | Orange red reactive dyestuff composition |
| CN101880475A (en) * | 2010-06-29 | 2010-11-10 | 上海科华染料工业有限公司 | Active scarlet dye composition |
| CN101914302A (en) * | 2010-07-17 | 2010-12-15 | 青岛大学 | K-type active light-resistant red azo dye and preparation method thereof |
-
2010
- 2010-12-29 CN CN2010106126611A patent/CN102127308A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61101576A (en) * | 1984-10-23 | 1986-05-20 | Orient Kagaku Kogyo Kk | Water based ink composition |
| CN1254735A (en) * | 1998-11-11 | 2000-05-31 | 德意志戴斯达纺织品及染料两合公司 | Dye mixture and its preparing process and application |
| CN101486842A (en) * | 2009-02-23 | 2009-07-22 | 湖北得宝染料工业有限公司 | Red active dye, and preparation method and use thereof |
| CN101565560A (en) * | 2009-04-14 | 2009-10-28 | 丽源(湖北)科技有限公司 | Red reactive dye mixture and preparation and application thereof |
| CN101880474A (en) * | 2010-06-29 | 2010-11-10 | 上海科华染料工业有限公司 | Orange red reactive dyestuff composition |
| CN101880475A (en) * | 2010-06-29 | 2010-11-10 | 上海科华染料工业有限公司 | Active scarlet dye composition |
| CN101914302A (en) * | 2010-07-17 | 2010-12-15 | 青岛大学 | K-type active light-resistant red azo dye and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 《精细化学品大全 染料卷》 20001231 周学良主编；何海兰编写 《精细化学品大全 染料卷》 浙江科学技术出版社 516-519 1 , 第1版 * |
| 周学良主编；何海兰编写: "《精细化学品大全 染料卷》", 31 December 2000, article "《精细化学品大全 染料卷》", pages: 516-519 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103013169A (en) * | 2012-12-06 | 2013-04-03 | 青岛大学 | Spray drying method of azo-based organic dye aqueous solution |
| CN105694534A (en) * | 2016-01-18 | 2016-06-22 | 浙江劲光数码科技有限公司 | Liquid dye for active ink and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103228739B (en) | Azo dye | |
| CN103694739B (en) | Composite liquid reactive red dye | |
| CN102493223B (en) | A kind of composition of aqueous solution of reactive dye for pad dyeing and compound method | |
| CN102796400B (en) | Yellow azo metallized dye composition, method and application thereof | |
| CN102127308A (en) | Read active dye and preparation method thereof | |
| CN103214877B (en) | A kind of active red dye composition | |
| CN102504580A (en) | Azo-series red reactive dye and preparation method thereof | |
| CN107828240B (en) | A kind of preparation method and application of dark blue reactive dye mill base | |
| CN104927396B (en) | A kind of composite reactive crimson and its preparation method and application | |
| CN106986953A (en) | A kind of chitosan derivatives as dispersant and its application in fabrics printing and dyeing | |
| CN103421344A (en) | Preparation technology of cochineal pigment with colorful effect | |
| CN109338747A (en) | A kind of colouring method of reducing dye thiourea dioxide low-temperature reduction | |
| GB1569259A (en) | Concentrated aqueous solutions of disazo dyes | |
| CN105038312B (en) | A kind of red reactive dyes compound and its preparation and application | |
| CN110243820A (en) | A kind of copper ion test paper based on novel azo compound | |
| CN103173037A (en) | Dye composition, dye, preparation method and raw material composition of dye thereof | |
| CN102051068A (en) | Brown reactive dye and preparation method thereof | |
| CN104559317B (en) | Composite active bright yellow dye composition | |
| CN106543075B (en) | A kind of cotton yellow dye and its synthesis and wastewater treatment method | |
| CN106987153B (en) | A kind of salt-free dyeing type yellow cationic reactive dye and its preparation method and application | |
| CN109651839A (en) | A kind of preparation method of orange reactive printing dyes | |
| CN104277490A (en) | Reactive dye for nylon and preparation method of reactive dye | |
| CN107033628A (en) | A kind of reactive yellow dye compounds and its preparation method and application | |
| CN102702787B (en) | Acid dye composition for nylon dyeing | |
| CN103788696A (en) | Bright orange active azo dye |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20110720 |