CN108084343B - Preparation method of formaldehyde-free color fixing agent - Google Patents
Preparation method of formaldehyde-free color fixing agent Download PDFInfo
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- CN108084343B CN108084343B CN201711160212.6A CN201711160212A CN108084343B CN 108084343 B CN108084343 B CN 108084343B CN 201711160212 A CN201711160212 A CN 201711160212A CN 108084343 B CN108084343 B CN 108084343B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/02—After-treatment
- D06P5/04—After-treatment with organic compounds
- D06P5/08—After-treatment with organic compounds macromolecular
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Abstract
The invention discloses a preparation method of a formaldehyde-free color fixing agent. Reacting allyl glycidyl ether with ethylenediamine to obtain an intermediate L; and under the action of an initiator ammonium persulfate, carrying out copolymerization reaction on the intermediate L and dimethyl diallyl ammonium chloride to obtain the formaldehyde-free color fixing agent. The color fixing agent has strong cationic groups in the molecules, can be combined with anionic groups of the dye through ionic bonds to form color lake, contains reactive groups-NH-, and can be combined with active chlorine in the molecules of the active dye through covalent bonds, so that the water solubility of the dye is reduced, and the color fixing effect is good.
Description
Technical Field
The invention relates to a formaldehyde-free color fixing agent, in particular to a preparation method of the formaldehyde-free color fixing agent.
Background
With the increasing perfection of the national environmental protection regulations, some production enterprises which can not meet the national environmental protection requirements face the condition of stopping production and stopping production, which makes the raw materials for synthesizing the color fixing agent on the market seriously lack. Diallyl amine is used as one of important raw materials for industrially producing the formaldehyde-free color fixing agent, so that domestic manufacturers are few, and the yield is difficult to meet the market demand. In order to meet the market demand, the development of other formaldehyde-free color fixing agents suitable for industrial production is urgently needed.
US 2001/0054209 a1 shows that the reactive group-NH-is of great help to improve the fixing properties of the fixing agent. U.S. Pat. No. 4, 2001/0054209, 1 copolymerizes allylamine and dimethyldiallylammonium chloride to obtain a color fixing agent, which contains nucleophilic group-NH-in its structure, and can be covalently bonded with active chlorine in the reactive dye molecule, so that the water solubility of the dye is reduced, and the copolymer has strong cationic property, and can be ionically bonded with anionic dye to generate color lake, and the fastness to soaping before and after color fixing is directly faded and the white cloth is stained by 3 grades to 5 grades.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a formaldehyde-free color fixing agent which is prepared by reacting allyl glycidyl ether with ethylenediamine to obtain an intermediate L, carrying out copolymerization reaction on the intermediate L and dimethyl diallyl ammonium chloride under the action of an initiator ammonium persulfate, and polymerizing; the molecule of the color fixing agent not only has strong cationic groups which can be combined with anionic groups of dye by ionic bonds to form lake, but also has a structure containing a reactive group-NH-, and is combined with active chlorine in the molecule of the active dye by covalent bonds, so that the water solubility of the dye is reduced, and the color fixing effect is good.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the formaldehyde-free color fixing agent comprises the following steps:
(1) 60 parts of ethylenediamine and 150 parts of deionized water are added into a reactor provided with a thermometer, a stirrer, a condensation reflux pipe and a dropping funnel; adding 230-240 parts of allyl glycidyl ether into a dropping funnel;
starting stirring to uniformly mix ethylenediamine and water, heating to 50-55 ℃ under the protection of nitrogen, then dropwise adding allyl glycidyl ether, controlling the dropwise adding speed to completely drip the ethylene diamine in 2-2.5 hours, continuously preserving the heat at 50-55 ℃ for 1-2 hours after the dropwise adding is completed, then heating to 70-75 ℃ and preserving the heat for 2.5-3 hours, and obtaining an intermediate L solution after the reaction is completed; the structural formula of the intermediate L is as follows:
(2) adding 440-450 parts of the intermediate L solution synthesized in the step (1), 2700 parts of a dimethyldiallylammonium chloride solution with the mass fraction of 60%, 60-100 parts of anhydrous citric acid and 80-120 parts of hydrochloric acid with the mass fraction of 30% into a reaction container provided with an electric stirrer, a condensation reflux pipe, a thermometer and a dropping funnel; dissolving 20-24 parts of ammonium persulfate in 200-240 parts of deionized water, and placing the dissolved ammonium persulfate solution in a dropping funnel for later use;
starting a stirrer, heating to 80-85 ℃ under the protection of nitrogen to completely dissolve the anhydrous citric acid, then dropwise adding an initiator ammonium persulfate solution, controlling the dropwise adding speed to completely dropwise add the initiator ammonium persulfate solution within 2-3 hours, keeping the temperature at 80-85 ℃ for 1-2 hours after the dropwise adding is finished, heating to 90-95 ℃ and keeping the temperature for 0.5 hour, and finishing the reaction to obtain the formaldehyde-free color fixing agent.
Preferably, the solvent in the 60% dimethyl diallyl ammonium chloride solution in the step (2) is water.
Wherein the raw materials in the step (1) and the step (2) are in parts by weight.
The invention is characterized in that:
1. the structure of the intermediate L synthesized by the invention contains-NH-group and-C ﹦ C-group; the group-C ﹦ C-enables the intermediate L to have copolymerization reaction with dimethyl diallyl ammonium chloride to obtain an aldehyde-free color fixing agent, the color fixing agent contains a-NH-group in the structure, and can be combined with active chlorine in active dye molecules by covalent bonds, so that the water solubility of the dye is reduced, and the color fixing performance is improved;
2. the dye fixing agent prepared by the invention has strong cationic groups in molecules, can be combined with dye anionic groups through ionic bonds to form lakes, reduces the water solubility of the dye, and has more remarkable color fixing performance;
3. the synthetic process is simple and controllable, the raw materials are conventional and easy to obtain, the method is suitable for industrial production, and a new choice is provided for the preparation of the color fixing agent under the condition that the supply of the conventional crosslinking monomer diallyl amine is short.
The invention is a preparation method of the formaldehyde-free color fixing agent, reduces the water solubility of the dye, has good color fixing effect, easily obtained raw materials and controllable production process, and is suitable for industrial production.
Drawings
FIG. 1 is an IR spectrum of example 1 of the present invention;
FIG. 2 is an IR spectrum of example 2 of the present invention;
FIG. 3 is an IR spectrum of example 3 of the present invention.
Detailed Description
The invention is further described by the following detailed description in conjunction with the accompanying drawings.
Example 1:
1. 30g of ethylenediamine and 75g of deionized water were added to a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping funnel; 115g of allyl glycidyl ether are added to the dropping funnel; starting a stirrer to uniformly mix ethylenediamine and water, heating to 50 ℃ under the protection of nitrogen, then dropwise adding allyl glycidyl ether, controlling the dropwise adding speed, keeping the temperature at 50 ℃ for 1 hour after dropwise adding, heating to 70 ℃ and keeping the temperature for 2.5 hours, and obtaining an intermediate L solution after the reaction is finished;
2. 220g of the intermediate L solution synthesized in the step (1), 1350g of a 60 mass percent dimethyldiallylammonium chloride solution (the solvent is water), 30g of anhydrous citric acid and 40g of 30 mass percent hydrochloric acid are added into a four-neck flask provided with an electric stirrer, a reflux condenser, a thermometer and a dropping funnel; dissolving 10g of ammonium persulfate in 100g of deionized water, and placing the dissolved ammonium persulfate solution in a dropping funnel for later use; starting a stirrer, heating to 80 ℃ under the protection of nitrogen to completely dissolve anhydrous citric acid, then dropwise adding an initiator ammonium persulfate solution, controlling the dropwise adding speed, keeping the temperature at 80 ℃ for 1 hour after dropwise adding, heating to 90 ℃ and keeping the temperature for 0.5 hour, and finishing the reaction to obtain the formaldehyde-free color fixing agent;
referring to FIG. 1, which is an infrared spectrum diagram in this example, curve 1 is intermediate L, and curve 2 is a fixing agent; curve 1 is 3089cm-1、922cm-1The two peaks appeared in the position are respectively a stretching vibration absorption peak and a swinging vibration absorption peak of ﹦ C-H, and the two absorption peaks in the curve 2 disappear, which indicates that the intermediate L and the dimethyl diallyl ammonium chloride have copolymerization reaction to prepare the formaldehyde-free color fixing agent.
Example 2:
1. 30g of ethylenediamine and 75g of deionized water were added to a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping funnel; 117g of allyl glycidyl ether are added to the dropping funnel; starting a stirrer to uniformly mix ethylenediamine and water, heating to 53 ℃ under the protection of nitrogen, then dropwise adding allyl glycidyl ether, controlling the dropwise adding speed, keeping the temperature at 53 ℃ for 1.5 hours after dropwise adding, heating to 72 ℃, keeping the temperature for 2.8 hours, and obtaining an intermediate L solution after the reaction is finished;
2. 222g of the intermediate L solution synthesized in the step (1), 1350g of a 60 mass percent dimethyldiallylammonium chloride solution (the solvent is water), 40g of anhydrous citric acid and 50g of 30 mass percent hydrochloric acid were put into a four-necked flask equipped with an electric stirrer, a reflux condenser, a thermometer and a dropping funnel; dissolving 11g of ammonium persulfate in 110g of deionized water, and placing the dissolved ammonium persulfate solution in a dropping funnel for later use; starting a stirrer, heating to 83 ℃ under the protection of nitrogen to completely dissolve the anhydrous citric acid, then dropwise adding an initiator ammonium persulfate solution, controlling the dropwise adding speed, keeping the temperature at 83 ℃ for 1.5 hours after dropwise adding is finished, heating to 92 ℃ and keeping the temperature for 0.5 hour, and finishing the reaction to obtain the formaldehyde-free color fixing agent.
Referring to FIG. 2, which is an infrared spectrum diagram in this example, curve 1 is intermediate L, and curve 2 is a fixing agent; curve 1 is 3083cm-1、924cm-1The two peaks appeared in the position are respectively a stretching vibration absorption peak and a swinging vibration absorption peak of ﹦ C-H, and the two absorption peaks in the curve 2 disappear, which indicates that the intermediate L and the dimethyl diallyl ammonium chloride have copolymerization reaction to prepare the formaldehyde-free color fixing agent.
Example 3:
1. 30g of ethylenediamine and 75g of deionized water were added to a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping funnel; 120g of allyl glycidyl ether are added to the dropping funnel; starting a stirrer to uniformly mix ethylenediamine and water, heating to 55 ℃ under the protection of nitrogen, then dropwise adding allyl glycidyl ether, controlling the dropwise adding speed, keeping the temperature at 55 ℃ for 2.5 hours after dropwise adding, keeping the temperature at 75 ℃ for 3 hours, and heating to 75 ℃ to keep the temperature at the end of reaction to obtain an intermediate L solution;
2. 225g of the intermediate L solution synthesized in the step (1), 1350g of a 60 mass percent dimethyldiallylammonium chloride solution (the solvent is water), 50g of anhydrous citric acid and 60g of 30 mass percent hydrochloric acid were put into a four-necked flask equipped with an electric stirrer, a reflux condenser, a thermometer and a dropping funnel; dissolving 12g of ammonium persulfate in 120g of deionized water, and placing the dissolved ammonium persulfate solution in a dropping funnel for later use; starting a stirrer, heating to 85 ℃ under the protection of nitrogen to completely dissolve the anhydrous citric acid, then dropwise adding an initiator ammonium persulfate solution, controlling the dropwise adding speed, keeping the temperature at 85 ℃ for 2 hours after the dropwise adding is finished, heating to 95 ℃ and keeping the temperature for 0.5 hour, and finishing the reaction to obtain the formaldehyde-free color fixing agent.
Referring to FIG. 3, which is an infrared spectrum diagram in this example, curve 1 is intermediate L, and curve 2 is a fixing agent; curve 1 is 3085cm-1、925cm-1The two absorption peaks appeared are respectively a stretching vibration absorption peak and a swinging vibration absorption peak of ﹦ C-H, and the two absorption peaks in the curve 2 disappear, which indicates that the intermediate L and the dimethyl diallyl ammonium chloride have copolymerization reaction to prepare the formaldehyde-free color fixing agent.
The color fixing process comprises the following steps:
preparing a fixing agent solution (5g/L) → padding pure cotton dyed fabric (one padding and one padding, the padding rate is 85%, the specification of the fabric is 28tex × 28tex and 425 × 228 roots/10 cm, and the fabric is subjected to a fixing performance test with poor-color-fastness red K/S ═ 24.12) → pre-baking (80 ℃,2 minutes) → baking (150 ℃,1 minute) of the fixing agent:
color fastness to rubbing: and (3) carrying out visual evaluation on the color fastness to rubbing of the fabric according to the determination of GB/T3920 plus 2008 < color fastness to rubbing of textiles >, and according to GB/T251 plus 2008 < color fastness to textiles > grey sample card for evaluating staining of the color fastness to rubbing of textiles.
Fastness to soaping: the color fastness to washing of the fabric is visually rated according to GB/T3921-.
As can be seen from the table above, the prepared color fixing agent has obvious effect on improving the fastness to soaping and the fastness to rubbing of the fabric.
Claims (2)
1. The preparation method of the formaldehyde-free color fixing agent is characterized by comprising the following steps:
(1) 60 parts of ethylenediamine and 150 parts of deionized water are added into a reactor provided with a thermometer, a stirrer, a condensation reflux pipe and a dropping funnel; adding 230-240 parts of allyl glycidyl ether into a dropping funnel;
starting stirring to uniformly mix ethylenediamine and water, heating to 50-55 ℃ under the protection of nitrogen, then dropwise adding allyl glycidyl ether, controlling the dropwise adding speed to completely drip the ethylene diamine in 2-2.5 hours, continuously preserving the heat at 50-55 ℃ for 1-2 hours after the dropwise adding is completed, then heating to 70-75 ℃ and preserving the heat for 2.5-3 hours, and obtaining an intermediate L solution after the reaction is completed; the structural formula of the intermediate L is as follows:
(2) adding 440-450 parts of the intermediate L solution synthesized in the step (1), 2700 parts of a dimethyldiallylammonium chloride solution with the mass fraction of 60%, 60-100 parts of anhydrous citric acid and 80-120 parts of hydrochloric acid with the mass fraction of 30% into a reaction container provided with an electric stirrer, a condensation reflux pipe, a thermometer and a dropping funnel; dissolving 20-24 parts of ammonium persulfate in 200-240 parts of deionized water, and placing the dissolved ammonium persulfate solution in a dropping funnel for later use;
starting a stirrer, heating to 80-85 ℃ under the protection of nitrogen to completely dissolve the anhydrous citric acid, then dropwise adding an initiator ammonium persulfate solution, controlling the dropwise adding speed to completely dropwise add the initiator ammonium persulfate solution within 2-3 hours, keeping the temperature at 80-85 ℃ for 1-2 hours after the dropwise adding is finished, heating to 90-95 ℃ and keeping the temperature for 0.5 hour, and finishing the reaction to obtain the formaldehyde-free color fixing agent.
2. The method of claim 1, wherein the formaldehyde-free fixing agent is prepared by: and (3) in the step (2), the dimethyl diallyl ammonium chloride solution with the mass fraction of 60% is prepared, and the solvent is water.
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| JPS6233893A (en) * | 1985-07-31 | 1987-02-13 | 三洋化成工業株式会社 | Dye fixing liquid and its production |
| WO2001031116A1 (en) * | 1999-10-22 | 2001-05-03 | The Procter & Gamble Company | Non-reactive fabric enhancement treatment |
| EP1240382A1 (en) * | 2000-01-18 | 2002-09-18 | The Procter & Gamble Company | Compositions which prevent abrasive color loss from denim fabric |
| CN100350097C (en) * | 2003-03-27 | 2007-11-21 | 三水市金盛精细化工有限公司 | Manufacturing technology of formaldehydeless colour fixing agent |
| CN102887989A (en) * | 2011-07-18 | 2013-01-23 | 杨海翔 | Novel formaldehyde-free fixing agent |
| CN102797170B (en) * | 2012-09-06 | 2014-08-13 | 苏州联胜化学有限公司 | Formaldehyde-free fixing agent and preparation method thereof |
| CN105986493A (en) * | 2015-02-16 | 2016-10-05 | 广东彩格科技有限公司 | Novel formaldehyde-free color-fixing agent |
| CN105421118A (en) * | 2016-01-08 | 2016-03-23 | 湖州市千金丝织厂 | Novel environment-friendly formaldehyde-free dye-fixing agent and preparation method thereof |
| CN105482032A (en) * | 2016-01-20 | 2016-04-13 | 广东溢达纺织有限公司 | Cationic color fixing agent and preparation method and application thereof |
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