CN1844257A - Method for preparing alizarin red rare-earth chromium dye - Google Patents
Method for preparing alizarin red rare-earth chromium dye Download PDFInfo
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- CN1844257A CN1844257A CN 200610049923 CN200610049923A CN1844257A CN 1844257 A CN1844257 A CN 1844257A CN 200610049923 CN200610049923 CN 200610049923 CN 200610049923 A CN200610049923 A CN 200610049923A CN 1844257 A CN1844257 A CN 1844257A
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- chromium
- alizarin red
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Abstract
The invention selects rare earth chloride or nitric rare earth, chromic chloride or chromic nitrate and alizarin red dyes with displayed constitutional formula as raw materials. The method consists of heating rare earth, chrome and alizarin red with a mole ratio of 1:1:5 or 3:1:11 in solution with PH 5-6 for some time to prepare alizarin red rare earth dyes. The products are of low content of chromic ion, bright-colored, of plump colored light, of good miscellaneous stability, of simple method for synthesizing, of milder reaction condition, suitable for commercial manufacture, so has a wide industry application prospect.
Description
Technical field
The present invention relates to a kind of metallized dye preparation method technical field that belongs to.
Background technology
Metallized dye is one of main kind of dyestuff, so far obtained developing rapidly from earlier 1900s, it has almost related to whole dye field, be used for the dyeing of various linings, used metal ion comprises chromium, cobalt, copper, nickel, iron, manganese, aluminium etc., wherein based on chromium, chromium, cobalt, copper, nickel are strict metals of limiting the quantity of by standard in the dye well DYED FABRICS.The chromium metallized dye has washing and the good advantage of light fastness that opacifying property good, dyeing is simple, dye product; But its painted deficiency is that darker in color is old, low in glossiness.
Find successively from late 1970s, rare earth compound has good helping and dyes effect in the dyeing of numerous products such as hair, silk, cotton, fiber crops, synthon and leather, can increase the vividness of dyeing articles, improve dyefastness, make and dye the sample softness, and can improve the dye uptake of dyestuff, save dyestuff, reduce the usage quantity of the potassium bichromate in the mordant dyeing technology, the environmental pollution that alleviates chromium.
Sodium alizarinsulfonate is used for the mordant dying of hair, silk fabrics mainly as acid mordant dye, and fastness is good, but dyeing is dark, and is big to the damage of fabric fibre, and has serious chromium (VI) to pollute.Also can make matching stain, though silk dyeing is bright-colored, fastness is not enough.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of alizarin red rare-earth chromium dye, it makes dyeing increase gorgeous effect rare earth and chromium is unified in the same dyestuff effect that increases the jail of dyeing, prepare a kind of bright-colored, coloured light is full, every dyefastness reaches GB alizarin red rare-earth chromium dye, to remedy the deficiency of the dark and sodium alizarinsulfonate dyefastness difference of sodium alizarinsulfonate mordant dyeing technology, chromium metal complex dyestuff dyeing, alleviate the environmental pollution of chromium, simplify rare earth and use technology, improve the dyeing quality of textile fabrics.
The present invention solves the problems of the technologies described above the technical scheme that is adopted to be: a kind of method for preparing alizarin red rare-earth chromium dye, it is characterized in that sodium alizarinsulfonate heating for dissolving with following structural I is in water, pH value with the acetic acid regulator solution is 5-6, is mixed with 0.02-0.1molL
-1The alizarin red aqueous solution of concentration range; By rare earth ion, the chromium ion ratio 0.9-1.1 with dyestuff sodium alizarinsulfonate amount of substance: 0.9-1.1: 4.9-5.1 or 2.9-3.1: 0.9-1.1: 10.9-11.1 adds alizarin red aqueous solution in the solution of rare earth ion, chromium ion, be heated with stirring to simultaneously and boil, react after 3-6 hour, cooling, ageing 6-12 hour, filter also washing, filter cake was descended dry 6-12 hour at 60-85 ℃, promptly get the slightly different amaranth product alizarin red rare-earth chromium dye of the depth.
Sodium alizarinsulfonate structural formula I
The crystal water of a no crystal water or a molecule in the sodium alizarinsulfonate dye structure.
What be highly profitable is above-mentioned rare earth ion, chromium ion Cr
3+With the ratio of dyestuff sodium alizarinsulfonate amount of substance 1: 1: 5 or 3: 1: 11, it made the product dyestuff can obtain good dyeing silk effect, and it is bright-colored, and coloured light is full.
Described rare earth ion is that the ion of lanthanum element, neodymium element or yttrium is La
3+, Nd
3+, Y
3+
Concentration with rare earth chloride or rare earth nitrate among the present invention is prepared rare-earth ion solution for the 0.1-0.5mol/L scope, and rare earth chloride or rare earth nitrate can be Lanthanum trichloride, Neodymium trichloride, Yttrium trichloride, lanthanum nitrate, neodymium nitrate or Yttrium trinitrate.
Concentration with chromium chloride or chromium nitrate among the present invention is come chromium ion in the obtain solution for the 0.05-0.2mol/L scope.
Described water is distilled water or deionized water.
Carried out silk dyeing with prepared alizarin red rare-earth chromium dye, its technology is: one in the silk of the suitable size of clip, take by weighing its quality, and the 1%-4% according to the silk quality takes by weighing dyestuff of the present invention again.Before the dyeing silk is placed in the distilled water, under 30 ℃-50 ℃ water-bath, soaked 10-20 minute.The dyestuff that weighs up is dissolved in the distilled water by bath raio 1: 30-100 (quality), and the pH value of using NaAc-HAc buffered soln regulator solution is between 4.0～5.0.Put into the wetted silk, dye 40 ℃ of beginnings, be warming up to 80-100 ℃ with the speed dye bath of 1 ℃/min, contaminated 45-55 minute, the limit is dyed Bian Buting and is shaken, and reduces to 20 ℃-50 ℃ after having dyed and takes out silks, and water fully cleans.This dyeing is simple, is easy to industrial applications.
The painted silk color even of products obtained therefrom, because of rare earth or composition be not all red-purple to purplish red, coloured light is full, every fastness meets the requirement (seeing Table 1) of GB/T15551-1995 standard acceptable end product or goods of inferior quality.
Table 1 alizarin red rare-earth chromium dye dyeing silk fastness test result
| The dyestuff title | Fastness to washing | Perspiration fastness (acidity) | Perspiration fastness (alkalescence) | Crock fastness | Exposure to Sunlight | |||||||
| Former state is faded | Staining | Former state is faded | Staining | Former state is faded | Staining | Unlubricated friction | Wet rubbing | |||||
| Cotton | Silk | Cotton | Silk | Cotton | Silk | |||||||
| 115LaCrR 115NdCrR 115YCrR 3111LaCrR 3111NdCrR 3111YCrR Cr-R R | 4-5 4 4 4 4 4 4 2 | 4-5 4-5 4-5 4-5 4-5 4-5 4-5 4-5 | 4 4 4 4 4 4 4 4 | 3-4 3-4 3-4 4 4 3 4 2 | 4-5 4 4 4 4 4 4-5 4 | 2-3 2-3 2-3 2-3 2-3 2-3 4 2-3 | 4-5 4-5 4 4 4 4-5 4 2 | 4 3-4 3 3-4 3-4 4 4-5 2-3 | 3 2-3 3 3 3 2-3 4 2 | 4-5 4-5 4-5 4-5 4-5 4-5 4-5 4-5 | 3-4 3-4 4 3-4 3-4 3-4 4 4-5 | 4 5 4-5 3-4 4 5 4-5 |
* R is a sodium alizarinsulfonate
* the fastness rank is 1-5, and the high more fastness of rank is good more
* the front coefficient is the amount of substance ratio
Compared with prior art, the invention has the advantages that making dyeing increase the effect that gorgeous effect and chromium makes dyeing increase the jail rare earth is unified in the same dyestuff, prepare a kind of bright-colored, coloured light is full, every dyefastness reaches GB alizarin red rare-earth chromium dye, remedied sodium alizarinsulfonate mordant dyeing technology, the dyeing of chromium metal complex dyestuff is dark and the deficiency of sodium alizarinsulfonate dyefastness difference, improved the dyeing quality of silk, alleviate the environmental pollution of chromium, simplify rare earth and use technology, synthetic method is simple, reaction conditions is gentle, is easy to suitability for industrialized production.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
The preparation of preparation example 1. sodium alizarinsulfonate lanthanum chromic color 115LaCrR
(1) preparation lanthanum ion solution
Take by weighing lanthanum trioxide 8.15g (amount of substance of lanthanum is 0.05mol), wetting with 10ml distilled water, slowly adding concentration is 3molL in the wetting lanthanum trioxide
-1Hydrochloric acid stirs while adding heating, and lanthanum trioxide and hydrochloric acid are fully reacted, and dissolves fully until lanthanum trioxide.Use 0.5molL
-1The NaOH solution of concentration is regulated the pH value of lanthanum ion solution to 5-6, and in the volumetric flask of 500ml, being made into concentration is 0.1molL the solution constant volume of being joined
-1La
3+Solion.
(2) preparation chromium ion solution
Take by weighing CrCl
36H
2O 13.32g (amount of substance of chromium is 0.05mol) uses dissolved in distilled water, and being mixed with concentration with the 1000ml volumetric flask is 0.05molL
-1Cr
3+Solion
(3) preparation of sodium alizarinsulfonate dye solution
Take by weighing and have a part crystal water sodium alizarinsulfonate 3.60g (0.01mol) in the molecular structure, use the distilled water heating for dissolving, cooling back constant volume is in the 500ml volumetric flask.Being made into the pH value is 0.02molL for 5-6, concentration
-1Alizarin red aqueous solution.
(4) sodium alizarinsulfonate lanthanum chromic color 115LaCrR's is synthetic
In reactor, add lanthanum ion solution 10ml (0.1molL
-1), chromium ion solution 20ml (0.05molL
-1), heated and stirred is when temperature rises to 70 ℃, with 250ml (0.02molL
-1) dye solution adds in the reactor, continues stirring heating 3 hours.Heating is finished, reaction solution left standstill, and naturally cooling 10 hours, sodium alizarinsulfonate lanthanum chromic color precipitation is separated out, and use the B suction filtration, and washing 80 ℃ of dryings 12 hours down, promptly gets amaranth sodium alizarinsulfonate lanthanum chromic color 115LaCrR with filter cake.
The preparation of preparation example 2. sodium alizarinsulfonate lanthanum chromic color 3111LaCrR
(1) preparation lanthanum ion solution
Take by weighing lanthanum trioxide 24.45g (amount of substance of lanthanum is 0.15mol), press example 1 method, being mixed with the pH value is 0.3molL for 5-6, concentration
-1La
3+Solion.
(2) preparation chromium ion solution
Take by weighing CrCl
36H
2O 27.24g (amount of substance of chromium is 0.1mol), being mixed with concentration by example 1 method is 0.1molL
-1Cr
3+Solion
(3) preparation of sodium alizarinsulfonate dye solution
Take by weighing in the molecular structure not sodium alizarinsulfonate 10.27g (0.03mol) with crystal water.Being made into the pH value by example 1 is 0.06molL for 5-6, concentration
-1Alizarin red aqueous solution.
(4) sodium alizarinsulfonate lanthanum chromic color 3111LaCrR's is synthetic
In reactor, add lanthanum ion solution 10ml (0.3molL
-1), chromium ion solution 10ml (0.1molL
-1), heated and stirred is when temperature rises to 70 ℃, with 183ml (0.06molL
-1) dye solution adds in the reactor, constantly stirring heating is 4 hours.Heating is finished, reaction solution left standstill, and naturally cooling 10 hours, lanthanum chromic color precipitation is separated out, and use the B suction filtration, and washing 80 ℃ of dryings 10 hours down, promptly gets amaranth sodium alizarinsulfonate lanthanum chromic color 3111LaCrR with filter cake.
The preparation of preparation example 3. sodium alizarinsulfonate neodymium chromic color 115NdCrR
(1) preparation neodymium ion solution
Take by weighing Neodymium trioxide 8.41g, the amount of substance of its neodymium is 0.05mol, and being made into the pH value by example 1 method is 0.1molL for 5-6, concentration
-1Nd
3+Solution.
(2) be 0.05molL by example 1 method compound concentration
-1Cr
3+Solution.
(3) be that 5-6, concentration are 0.02molL by example 1 method secure ph
-1Alizarin red aqueous solution.
(4) sodium alizarinsulfonate neodymium chromic color 115NdCrR's is synthetic
In reactor, add neodymium ion solution 10ml (0.1molL
-1), chromium ion solution 20ml (0.05molL
-1), heated and stirred is when temperature rises to 70 ℃, with 250ml (0.02molL
-1) dye solution adds in the reactor, after adding, continues stirring heating 3 hours.Heating is finished, reaction solution left standstill, and naturally cooling 10 hours, neodymium chromic color precipitation is separated out, and use the B suction filtration, and washing 80 ℃ of dryings 12 hours down, promptly gets amaranth sodium alizarinsulfonate neodymium chromic color 115NdCrR with filter cake.
The preparation of preparation example 4. sodium alizarinsulfonate neodymium chromic color 3111NdCrR
(1) take by weighing Neodymium trioxide 42.05g, the amount of substance of neodymium is 0.25mol, and being made into the pH value by example 1 method is 0.5molL for 5-6, concentration
-1Nd
3+Solion.
(2) preparation chromium ion solution
Take by weighing CrCl
36H
2O 53.28g, the amount of substance of chromium are 0.2mol, and being made into concentration by example 1 method is 0.2molL
-1Cr
3+Solion
(3) preparation of sodium alizarinsulfonate dye solution
Take by weighing in the molecular structure not sodium alizarinsulfonate 17.11g (0.05mol) with crystal water.Being made into the pH value by example 1 method is 0.1molL for 5-6, concentration
-1Alizarin red aqueous solution.
(4) sodium alizarinsulfonate neodymium chromic color 3111NdCrR's is synthetic
In reactor, add neodymium ion solution 12ml (0.5molL
-1), chromium ion solution 10ml (0.2molL
-1), heated and stirred is when temperature rises to 70 ℃, with 220ml (0.1molL
-1) dye solution adds in the reactor, constantly stirring heating is 3 hours.Heating is finished, reaction solution left standstill, and naturally cooling 10 hours, lanthanum chromic color precipitation is separated out, and use the B suction filtration, and washing 80 ℃ of dryings 10 hours down, promptly gets amaranth sodium alizarinsulfonate neodymium chromic color 3111NdCrR with filter cake.
Application example 5. sodium alizarinsulfonate lanthanum chromic color 115LaCrR dyeing silk technology
One in the silk of clip 20*30cm takes by weighing its quality 3.85g, takes by weighing dyestuff 0.074g of the present invention according to 2% of silk quality again.Before the dyeing silk is placed in the distilled water, under 40 ℃ water-bath, soaked 10 minutes.The dyestuff that weighs up is dissolved in the 155ml distilled water by bath raio at 1: 50, adds the NaAc-HAc buffered soln of 40ml pH value for 4-5.Put into the wetted silk, dye 40 ℃ of beginnings, be warming up to 90 ℃ with the speed dye bath of 1 ℃/min, contaminated 45 minutes in the time of 90 ℃, the limit is dyed Bian Buting and is shaken, and reduces to 50 ℃ after having dyed, and taking-up sample silk water fully cleans airing.The sample silk is the red-purple of color even.Its every fastness test result such as table 1 meet the requirement of GB/T15551-1995 standard acceptable end product.
Application example 6. sodium alizarinsulfonate neodymium chromic color 3111NdCrR dyeing silk technology
One in the silk of clip 20*30cm takes by weighing its quality 3.88g, takes by weighing dyestuff 0.076g of the present invention according to 2% of silk quality again.Before the dyeing silk is placed in the distilled water, under 40 ℃ water-bath, soaked 10 minutes.The dyestuff that weighs up is dissolved in the 154ml distilled water by bath raio at 1: 50, adds the NaAc-HAc buffered soln of 40mlpH value for 4-5.Put into the stained specimens silk, dye 40 ℃ of beginnings, be warming up to 90 ℃ with the speed dye bath of 1 ℃/min, contaminated 45 minutes in the time of 90 ℃, the limit is dyed Bian Buting and is shaken, and reduces to 50 ℃ of taking-up sample silks after having dyed, and water fully cleans, airing.The sample silk is the bright-coloured red-purple of color even.Its every fastness test result such as table 1 meet the requirement of GB/T15551-1995 standard acceptable end product.
Claims (6)
1. method for preparing alizarin red rare-earth chromium dye is characterized in that sodium alizarinsulfonate heating for dissolving with following structural I in water, is 5-6 with the pH value of acetic acid regulator solution, makes 0.02-0.1molL
-1The alizarin red aqueous solution of concentration range, by rare earth ion, the chromium ion ratio 0.9-1.1 with dyestuff sodium alizarinsulfonate amount of substance: 0.9-1.1: 4.9-5.1 or 2.9-3.1: 0.9-1.1: 10.9-11.1 adds alizarin red aqueous solution to the pH value in the solution that contains rare earth ion, chromium ion of 5-6, be heated with stirring to simultaneously and boil, react after 3-6 hour, cooling ageing 6-12 hour, is filtered and washing, filter cake was descended dry 6-12 hour at 60-85 ℃, promptly get the product alizarin red rare-earth chromium dye.
Sodium alizarinsulfonate structural formula I
2. method for preparing alizarin red rare-earth chromium dye according to claim 1 is characterized in that described rare earth ion, chromium ion Cr
3+With the ratio of dyestuff sodium alizarinsulfonate amount of substance 1: 1: 5 or 3: 1: 11.
3. method for preparing alizarin red rare-earth chromium dye according to claim 1 and 2 is characterized in that described rare earth ion is the ion of lanthanum element, neodymium element or yttrium.
4. method for preparing alizarin red rare-earth chromium dye according to claim 1 is characterized in that the described solution that contains rare earth ion is that the concentration of rare earth chloride or rare earth nitrate is 0.1-0.5molL with rare earth chloride or rare earth nitrate preparation
-1Scope.
5. method for preparing alizarin red rare-earth chromium dye according to claim 1 is characterized in that the described solution that contains chromium ion is that the concentration of chromium chloride or chromium nitrate is 0.05-0.2molL with chromium chloride or chromium nitrate preparation
-1Scope.
6. method for preparing alizarin red rare-earth chromium dye according to claim 1 is characterized in that described water is distilled water or deionized water.
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|---|---|---|---|
| CNB2006100499231A CN100404627C (en) | 2006-03-21 | 2006-03-21 | Method for preparing alizarin red rare-earth chromium dye |
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|---|---|---|---|
| CNB2006100499231A CN100404627C (en) | 2006-03-21 | 2006-03-21 | Method for preparing alizarin red rare-earth chromium dye |
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|---|---|
| CN1844257A true CN1844257A (en) | 2006-10-11 |
| CN100404627C CN100404627C (en) | 2008-07-23 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106544895A (en) * | 2016-12-01 | 2017-03-29 | 西南大学 | Colouring method of the alizarin to wool fabric |
| CN107501992A (en) * | 2017-08-17 | 2017-12-22 | 吴江市生态纺织有限公司 | A kind of madder haematochrome preparation method and application |
| CN110607704A (en) * | 2019-09-29 | 2019-12-24 | 泉州师范学院(石狮)生态智能织物工程技术研究院 | Rare earth coordination-based natural dye dyeing method with ultraviolet resistance |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2010823C1 (en) * | 1991-04-24 | 1994-04-15 | Кемеровский государственный университет | Black dye composition for phenol plastics |
| FR2802214B1 (en) * | 1999-12-09 | 2005-07-22 | Biomerieux Sa | NOVEL ALIZARIN CHROMOGENIC SUBSTRATES, USES THEREOF AND COMPOSITIONS CONTAINING SUCH SUBSTRATES |
-
2006
- 2006-03-21 CN CNB2006100499231A patent/CN100404627C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106544895A (en) * | 2016-12-01 | 2017-03-29 | 西南大学 | Colouring method of the alizarin to wool fabric |
| CN107501992A (en) * | 2017-08-17 | 2017-12-22 | 吴江市生态纺织有限公司 | A kind of madder haematochrome preparation method and application |
| CN110607704A (en) * | 2019-09-29 | 2019-12-24 | 泉州师范学院(石狮)生态智能织物工程技术研究院 | Rare earth coordination-based natural dye dyeing method with ultraviolet resistance |
| CN110607704B (en) * | 2019-09-29 | 2022-03-15 | 泉州师范学院(石狮)生态智能织物工程技术研究院 | Rare earth coordination-based natural dye dyeing method with ultraviolet resistance |
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