CN102797170A - Formaldehyde-free fixing agent and preparation method thereof - Google Patents
Formaldehyde-free fixing agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a formaldehyde-free fixing agent, which comprises the following components in parts by weight: 80 to 120 parts of cationic monomer, 5 to 20 parts of unsaturated high-grade organic amine monomer, 3 to 10 parts of dicyandiamide, 4 to 18 parts of pH regulator, 0.001 to 0.05 part of metal ion chelating agent, 0.5 to 1 part of initiator, 2 to 10 parts of epichlorohydrin and 20 to 50 parts of deionized water. The formaldehyde-free fixing agent provided by the invention does not contain formaldehyde and alkylphenol ethoxylates (APEO); and meanwhile, the film-forming property of the fixing agent is utilized, a meshed film layer can be formed on the surface of the fiber, so that the dye dissolution is reduced, the color fastness of reactive dye dyed fabrics is improved, a fixing effect is good, the formaldehyde-free fixing agent can be applied to fixing colors of the reactive dye dyed fabrics, and the washable color fastness and boiling water soaking fastness of the fabrics are improved.
Description
Technical field
The present invention relates to a kind of printing and dyeing assistant, be specifically related to aldehyde-free colour stabilizer of a kind of direct dyes, cotton fabrics dyed with reactive dyes and preparation method thereof.
Background technology
In recent years, the Along with people's growth in the living standard, the demand of textiles is also more and more, and is also increasingly high to the requirement of textiles, as requires the bright in luster of textiles, and COLOR FASTNESS is good etc.
REACTIVE DYES are as the representative of modern dye industry, advantage such as, process economics complete because of its lovely luster, chromatogram, simple to operate, good level-dyeing property, price are lower, and enjoy liking of dyeing.But there is the shortcoming be difficult to overcome in REACTIVE DYES self, and when it dyed dark heavy colour, its COLOR FASTNESS was relatively poor relatively, put with color-fixing agent that to improve COLOR FASTNESS be an important measures in order.Although form functional group's covalent bonding between REACTIVE DYES dyestuff and the fiber, if in dyeing hydrolised dye or to key not and dyestuff soap insufficiently, its COLOR FASTNESS is reduced, dyestuff falls down from the wet fiber that has dyeed.The color and luster of fabric own is shoaled, and can stain white or dye the fiber of other color and luster, produce the staining and the phenomenon that cuts marks.In order to address these problems, develop the new dye of high-absorbility and high fixation rate, high fastness energetically, no doubt be valid approach the most, but also answer the novel color-fixing agent of synchronized development.
Generally require color-fixing agent must possess following performance: in water, have fine solubility, to the stability of acid-base condition, to the stability of environment around the temperature etc., with other auxiliary agents, weaving with resin also with property and the security that do not contain hazardous substance etc.; Textiles has through the performance that is possessed after the fixation simultaneously: look diminishes, and keeps original feel and style, crock fastness, washing fastness, light fastness height.
From the document Patent data, the 60's of last century and the 80's are peak times of color-fixing agent research.Requirement along with external piece market and product dyed thereby COLOR FASTNESS and content of formaldehyde increasingly stringent; China strengthens developing and using the formaldehyde-free color fixing agent of novel raising COLOR FASTNESS better performances from the later stage the 80's of eighties of last century; To substitute traditional color-fixing agent that contains not environmental protection of formaldehyde, so the exploitation of efficient formaldehyde-free color fixing agent is present development trend.
At present, the color-fixing agent on the market is very different, and the overwhelming majority has just solved water-fast problem of washing COLOR FASTNESS, but does not also solve the problem that anti-boiling water soaks fastness.Also do not have formal testing standard though anti-boiling water soaks fastness, become another short-cut method of many printing and dyeing enterprise examination COLOR FASTNESS.
Therefore, a kind of environmental protection can solve water-fast aldehyde-free colour stabilizer of washing COLOR FASTNESS and anti-boiling water immersion fastness problem and preparation method thereof simultaneously and demand urgently occurring.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of environmental protection, can solve the water-fast aldehyde-free colour stabilizer of washing COLOR FASTNESS and anti-boiling water immersion fastness problem simultaneously.
For achieving the above object, technical scheme of the present invention is following: a kind of aldehyde-free colour stabilizer, and comprise the component of following weight portion: cationic monomer is 80-120 part; Unsaturated senior organic amine monomer is 5-20 part, and dicyandiamide is 3-10 part, and pH value conditioning agent is 4-18 part; Metal ion chelation agent is 0.001-0.05 part; Initator is 0.5-1 part, and chloropropylene oxide is 2-10 part, and deionized water is 20-50 part.
Preferably, comprise the component of following weight portion: cationic monomer is 90-110 part, and unsaturated senior organic amine monomer is 9-16 part; Dicyandiamide is 4-8 part; PH value conditioning agent is 6-15 part, and metal ion chelation agent is 0.01-0.04 part, and initator is 0.6-0.9 part; Chloropropylene oxide is 3-9 part, and deionized water is 25-45 part.
Preferably, comprise the component of following weight portion: cationic monomer is 95-105 part, and unsaturated senior organic amine monomer is 11-14 part; Dicyandiamide is 5-7 part; PH value conditioning agent is 8-12 part, and metal ion chelation agent is 0.02-0.04 part, and initator is 0.7-0.8 part; Chloropropylene oxide is 4-8 part, and deionized water is 30-40 part.
Preferably, comprise the component of following weight portion: cationic monomer is 100 parts, and unsaturated senior organic amine monomer is 12 parts; Dicyandiamide is 6 parts, and pH value conditioning agent is 10 parts, and metal ion chelation agent is 0.03 part; Initator is 0.75 part, and chloropropylene oxide is 6 parts, and deionized water is 35 parts.
Preferably, said cationic monomer comprises one or both in dimethyl diallyl ammonium chloride, methylacryoyloxyethyl trimethyl ammonium chloride, diethyl diallyl ammonium chloride and the acrylyl oxy-ethyl-trimethyl salmiac.
Preferably, said unsaturated senior organic amine monomer comprises allyl amine, diallylamine or triallylamine.
Preferably, said pH value conditioning agent comprises citric acid, glacial acetic acid or hydrochloric acid.
Preferably, said metal ion chelation agent comprises the sodium salt of ethylenediamine tetra-acetic acid, the sodium salt of ethylenediamine tetramethylene phosphonic acid or the sodium salt of aminotriacetic acid.
Preferably, said initator comprises potassium peroxydisulfate-sodium hydrogensulfite or ammonium persulfate-sodium sulfite.
The present invention also provides a kind of preparation method of aldehyde-free colour stabilizer, specifically comprises the steps:
(1) in the four-hole boiling flask that is connected with nitrogen, reflux condensing tube, thermometer, adds cationic monomer, unsaturated senior organic amine monomer and the dicyandiamide that calculates the weight successively; Open and stir; After treating that raw material stirring evenly, add pH value conditioning agent, the pH value of conditioned reaction system is 3-8;
(2) metering weighing metal ion chelation agent is mixed with the aqueous solution with the deionized water dissolving of 20 times of weight again and joins in the aforesaid reaction vessel;
(3) use the deionized water dissolving initator of 10 times of weight again, it is subsequent use to be mixed with the aqueous solution;
(4) reacting by heating still when the temperature in the four-hole boiling flask rises to 40 ℃, drips the initiator solution of above-mentioned 1/3 weight for preparing simultaneously; After dripping, agitated reactor is warming up to 40-50 ℃ of back flow reaction, when temperature is reduced to 50 ℃; Slowly drip the initiator solution of residue 2/3 weight simultaneously, the dropping time is 1-2 hour, after dripping; At 50 ℃, continue isothermal reaction 1-3 hour, promptly get cationic monomer and amine copolymer;
(5) above-mentioned copolymer is warmed up to 70 ℃, drips the chloropropylene oxide that calculates the weight, isothermal reaction 1-3 hour, add a certain amount of deionized water subsequently, promptly obtain the quaternary ammonium salt cationic aldehyde-free colour stabilizer.
Through technique scheme, the beneficial effect of technical scheme of the present invention is: a kind of aldehyde-free colour stabilizer, and comprise the component of following weight portion: cationic monomer is 80-120 part; Unsaturated senior organic amine monomer is 5-20 part, and dicyandiamide is 3-10 part, and pH value conditioning agent is 4-18 part; Metal ion chelation agent is 0.001-0.05 part; Initator is 0.5-1 part, and chloropropylene oxide is 2-10 part, and deionized water is 20-50 part; Adopt aldehyde-free colour stabilizer provided by the invention not contain formaldehyde and APEO; Can carry out static through cation group in the color-fixing agent molecule and dyestuff anionic group combines; Form insoluble color lake at fabric face; And then the water soluble group of sealing dyestuff, make the water-soluble decline of dyestuff, thereby improve the wet colour fastness of DYED FABRICS; Utilize the filming performance of color-fixing agent simultaneously; Can form the netted film of one deck at fiber surface; What make dyestuff dissolves minimizing, has improved each item COLOR FASTNESS of reactive dyeing fabric, and colour fixation is good; Can be applicable to the fixation treatment of Dyeing of Cotton Fabric with Reactive Dyes fabric, can improve the water-fast COLOR FASTNESS and the boiling water immersion fastness of washing of fabric.
The specific embodiment
To combine the accompanying drawing in the embodiment of the invention below, the technical scheme in the embodiment of the invention is carried out clear, intactly description, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills are not making the every other embodiment that is obtained under the creative work prerequisite, all belong to the scope of the present invention's protection.
The invention provides a kind of environmental protection, can solve the water-fast aldehyde-free colour stabilizer of washing COLOR FASTNESS and anti-boiling water immersion fastness problem simultaneously.
Embodiment 1,
A kind of aldehyde-free colour stabilizer, comprise the component of following weight portion: cationic monomer is 80 parts, and unsaturated senior organic amine monomer is 5 parts; Dicyandiamide is 3 parts, and pH value conditioning agent is 4 parts, and metal ion chelation agent is 0.001 part; Initator is 0.5 part, and chloropropylene oxide is 2 parts, and deionized water is 20 parts.
Said cationic monomer comprises one or both in dimethyl diallyl ammonium chloride, methylacryoyloxyethyl trimethyl ammonium chloride, diethyl diallyl ammonium chloride and the acrylyl oxy-ethyl-trimethyl salmiac.
Said unsaturated senior organic amine monomer comprises allyl amine, diallylamine or triallylamine.
Said pH value conditioning agent comprises citric acid, glacial acetic acid or hydrochloric acid.
Said metal ion chelation agent comprises the sodium salt of ethylenediamine tetra-acetic acid, the sodium salt of ethylenediamine tetramethylene phosphonic acid or the sodium salt of aminotriacetic acid.
Said initator comprises potassium peroxydisulfate-sodium hydrogensulfite or ammonium persulfate-sodium sulfite.
The present invention also provides a kind of preparation method of aldehyde-free colour stabilizer, specifically comprises the steps:
(1) in the four-hole boiling flask that is connected with nitrogen, reflux condensing tube, thermometer, adds cationic monomer, unsaturated senior organic amine monomer and the dicyandiamide that calculates the weight successively; Open and stir; After treating that raw material stirring evenly, add pH value conditioning agent, the pH value of conditioned reaction system is 3-8;
(2) metering weighing metal ion chelation agent is mixed with the aqueous solution with the deionized water dissolving of 20 times of weight again and joins in the aforesaid reaction vessel;
(3) use the deionized water dissolving initator of 10 times of weight again, it is subsequent use to be mixed with the aqueous solution;
(4) reacting by heating still when the temperature in the four-hole boiling flask rises to 40 ℃, drips the initiator solution of above-mentioned 1/3 weight for preparing simultaneously; After dripping, agitated reactor is warming up to 40 ℃ of-50 ℃ of back flow reaction, when temperature is reduced to 50 ℃; Slowly drip the initiator solution of residue 2/3 weight simultaneously, the dropping time is 1 hour, after dripping; At 50 ℃, continue isothermal reaction 1 hour, promptly get cationic monomer and amine copolymer;
(5) above-mentioned copolymer is warmed up to 70 ℃, drips the chloropropylene oxide that calculates the weight, isothermal reaction 1 hour adds a certain amount of deionized water subsequently, promptly obtains the quaternary ammonium salt cationic aldehyde-free colour stabilizer.
In technique scheme, the primosome that the present invention adopts is a redox initiation system, can be under lower temperature initiated polymerization, can reach requirements of saving energy to a certain extent.The present invention is directed to the deficiency of existing not environmental protection of color-fixing agent (containing formaldehyde or APEO) and formaldehyde-free color fixing agent colour fixation simultaneously; With cationic monomer, unsaturated senior organic amine monomer, dicyandiamide is raw material; Use redox initiation system, the good environmental type color-fixing agent of a kind of colour fixation has been synthesized in copolymerization.
The above-mentioned color-fixing agent that makes is the quaternary ammonium salt cationic color-fixing agent; Can carry out static through cation group in the color-fixing agent molecule and dyestuff anionic group combines; Form insoluble color lake at fabric face; And then the water soluble group of sealing dyestuff, make the water-soluble decline of dyestuff, thereby improve the wet colour fastness of DYED FABRICS; Utilize the filming performance of color-fixing agent simultaneously, can form the netted film of one deck at fiber surface, what make dyestuff dissolves minimizing, has improved each item COLOR FASTNESS of reactive dyeing fabric.
The purposes of the above-mentioned aldehyde-free colour stabilizer that makes is direct dyes or REACTIVE DYES deep colour dyeing cloth specimen to be impregnated in contain 2% color-fixing agent, and in the fixation liquid of pH=5-6,50 ℃, bath raio is 1:15, dipping 20min; Perhaps, the fixation working solution of preparation 10-20g/L, the cloth specimen two that will dye soaks two and rolls, and at 90-100 ℃ of preliminary drying 2-2.5min, bakes 30s at 150-160 ℃ then.
CATION aldehyde-free colour stabilizer provided by the present invention does not contain formaldehyde and APEO; And colour fixation performance and colour fixation are good; Be a kind of environmental protection aldehyde-free colour stabilizer, reach preferable colour fixation, use the COLOR FASTNESS of anti-dry friction of the REACTIVE DYES deep colour dyeing fabric of this color-fixing agent processing to be the 4-5 level by cation group and filming function; The moisture-proof colorfastness to rubbing is 3 grades; The calico staining fastness is the 4-5 level, and it is 5 grades (it is water white transparency that the boiling water of DYED FABRICS after fixation soaks residual night) that anti-boiling water soaks fastness, and the coloured light of the fabric after fixation does not change basically; Described cationic fixing agent meets the requirement of ecological textile, and each item index is better than traditional color-fixing agent.
Embodiment 2,
All the other are same as the previously described embodiments, and difference is, a kind of aldehyde-free colour stabilizer; The component that comprises following weight portion: cationic monomer is 120 parts, and unsaturated senior organic amine monomer is 20 parts, and dicyandiamide is 10 parts; PH value conditioning agent is 18 parts, and metal ion chelation agent is 0.05 part, and initator is 1 part; Chloropropylene oxide is 10 parts, and deionized water is 50 parts.
Embodiment 3,
All the other are same as the previously described embodiments, and difference is, a kind of aldehyde-free colour stabilizer; The component that comprises following weight portion: cationic monomer is 90 parts, and unsaturated senior organic amine monomer is 9 parts, and dicyandiamide is 4 parts; PH value conditioning agent is 6 parts, and metal ion chelation agent is 0.01 part, and initator is 0.6 part; Chloropropylene oxide is 3 parts, and deionized water is 25 parts.
Embodiment 4,
All the other are same as the previously described embodiments, and difference is, a kind of aldehyde-free colour stabilizer; The component that comprises following weight portion: cationic monomer is 110 parts, and unsaturated senior organic amine monomer is 16 parts, and dicyandiamide is 8 parts; PH value conditioning agent is 15 parts, and metal ion chelation agent is 0.04 part, and initator is 0.9 part; Chloropropylene oxide is 9 parts, and deionized water is 45 parts.
Embodiment 5,
All the other are same as the previously described embodiments, and difference is, a kind of aldehyde-free colour stabilizer; The component that comprises following weight portion: cationic monomer is 95 parts, and unsaturated senior organic amine monomer is 11 parts, and dicyandiamide is 5 parts; PH value conditioning agent is 8 parts, and metal ion chelation agent is 0.0 part, and initator is 0.7 part; Chloropropylene oxide is 4 parts, and deionized water is 30 parts.
Embodiment 6,
All the other are same as the previously described embodiments, and difference is, a kind of aldehyde-free colour stabilizer; The component that comprises following weight portion: cationic monomer is 105 parts, and unsaturated senior organic amine monomer is 14 parts, and dicyandiamide is 7 parts; PH value conditioning agent is 12 parts, and metal ion chelation agent is 0.04 part, and initator is 0.8 part; Chloropropylene oxide is 8 parts, and deionized water is 40 parts.
Embodiment 7,
All the other are same as the previously described embodiments, and difference is, a kind of aldehyde-free colour stabilizer; The component that comprises following weight portion: cationic monomer is 100 parts, and unsaturated senior organic amine monomer is 12 parts, and dicyandiamide is 6 parts; PH value conditioning agent is 10 parts, and metal ion chelation agent is 0.03 part, and initator is 0.75 part; Chloropropylene oxide is 6 parts, and deionized water is 35 parts.
Embodiment 8,
All the other are same as the previously described embodiments, and difference is that the step for preparing said aldehyde-free colour stabilizer is specific as follows:
(1) feeds nitrogen,, copolyreaction is reacted in the atmosphere of inert gas to get rid of the air in the reaction system;
Get allyl amine 8 gram, methylacryoyloxyethyl trimethyl ammonium chloride 100 grams, dicyandiamide 5 grams add in the four-hole boiling flask successively, open and stir, treat that raw material stirring evenly after, using the pH value of glacial acetic acid conditioned reaction system is 5.
(2) water that the metal ion chelation agent tetrasodium ethylenediamine tetraacetate of getting 0.1 gram adds 20 times of weight is mixed with the aqueous solution, therefrom gets 2 milliliters, adds in the four-hole boiling flask.
(3) get 0.7 gram ammonium persulfate and 0.35 gram anhydrous sodium niter cake, it is subsequent use to be mixed with the aqueous solution with the water of 10 times of weight respectively.
(4) the reacting by heating temperature of charge is to 40-50 ℃; When reactor temperature rose to 40 ℃, beginning added the ammonium persulfate and the solution of sodium bisulfite of 1/3 weight simultaneously, after dripping; Agitated reactor is warming up to 40-50 ℃ of back flow reaction, when temperature is reduced to 50 ℃, slowly drips the ammonium persulfate and the solution of sodium bisulfite of residue 2/3 weight simultaneously; The dropping time is 1-2 hour; After dripping,, continue isothermal reaction 2 hours at 50 ℃.
(5) agitated reactor is warmed up to 70 ℃, drips 10 gram chloropropylene oxides,, add the deionized water of 30 gram weight subsequently, promptly obtain the CATION aldehyde-free colour stabilizer 70 ℃ of isothermal reactions 2 hours.
Embodiment 9,
All the other are same as the previously described embodiments, and difference is that the step for preparing said aldehyde-free colour stabilizer is specific as follows:
(1) feeds nitrogen,, copolyreaction is reacted in the atmosphere of inert gas to get rid of the air in the reaction system;
Get diallylamine 5 gram, diethyl diallyl ammonium chloride 90 grams, dicyandiamide 7 grams add in the four-hole boiling flask successively, open and stir, treat that raw material stirring evenly after, using the pH value of citric acid conditioned reaction system is 4.
(2) water that the metal ion chelation agent disodium ethylene diamine tetraacetate of getting 0.1 gram adds 20 times of weight is mixed with the aqueous solution, therefrom gets 2 milliliters, adds in the four-hole boiling flask.
(3) get 0.7 gram potassium peroxydisulfate and 0.35 gram anhydrous sodium niter cake, it is subsequent use to be mixed with the aqueous solution with the water of 10 times of weight respectively.
(4) the reacting by heating temperature of charge is to 40-50 ℃; When reactor temperature rose to 40 ℃, beginning added the ammonium persulfate and the solution of sodium bisulfite of 1/3 weight simultaneously, after dripping; Agitated reactor is warming up to 40-50 ℃ of back flow reaction, when temperature is reduced to 50 ℃, slowly drips the ammonium persulfate and the solution of sodium bisulfite of residue 2/3 weight simultaneously; The dropping time is 1-2 hour; After dripping,, continue isothermal reaction 2 hours at 50 ℃.
(5) agitated reactor is warmed up to 70 ℃, drips 8 gram chloropropylene oxides,, add the deionized water of 30 gram weight subsequently, promptly obtain the CATION aldehyde-free colour stabilizer 70 ℃ of insulation reaction 2 hours.
To the color-fixing agent that the foregoing description provided, all be used to handle REACTIVE DYES deep colour dyeing fabric, drawing the COLOR FASTNESS of anti-the dry friction is the 4-5 level, and the moisture-proof colorfastness to rubbing is 3 grades, and the calico staining fastness is the 4-5 level, and it is the 4-5 level that anti-boiling water soaks fastness; Wherein, to the dependence test result of said embodiment 8 and embodiment 9, as shown in table 1:
Colour fixation after embodiment puts in order the reactive scarlet DYED FABRICS
Annotate:
1, color fastness to washing: press GB/T3921-2008 " textile color stability test: fastness to soaping " method and measure.
2, colour fastness to rubbing: press GB/T3920-2008 " textile color stability test: colour fastness to rubbing " method and measure.
3, GB/T250-2008 variable color gray scale and GB/T251-2008 staining gray scale are used in rating respectively.Colour difference Δ CC: survey color matching appearance Gretag Macbeth Color-EYER 3100 with computer and measure sample L*, a*, b* presses CIELAB aberration formula then and calculates.
4, anti-boiling water soaks fastness: with the cloth specimen after the fixation, by bath raio 1:20, in 100 ℃ boiling water, soak 5-10min, take out cloth specimen then, see the pin water depth that fades at residual night.Pin water color is dark more, and progression is low more.5 grades of water white transparencies, best, 1 grade is that color is dark, by that analogy.
Data in the foregoing description can also be other numerical value, and the specific embodiment is determined on a case-by-case basis, and at this, the present invention does not do any qualification, are main can realize the object of the invention.
Through technique scheme, the beneficial effect of technical scheme of the present invention is: a kind of aldehyde-free colour stabilizer, and comprise the component of following weight portion: cationic monomer is 80-120 part; Unsaturated senior organic amine monomer is 5-20 part, and dicyandiamide is 3-10 part, and pH value conditioning agent is 4-18 part; Metal ion chelation agent is 0.001-0.05 part; Initator is 0.5-1 part, and chloropropylene oxide is 2-10 part, and deionized water is 20-50 part; Adopt aldehyde-free colour stabilizer provided by the invention not contain formaldehyde and APEO; Can carry out static through cation group in the color-fixing agent molecule and dyestuff anionic group combines; Form insoluble color lake at fabric face; And then the water soluble group of sealing dyestuff, make the water-soluble decline of dyestuff, thereby improve the wet colour fastness of DYED FABRICS; Utilize the filming performance of color-fixing agent simultaneously; Can form the netted film of one deck at fiber surface; What make dyestuff dissolves minimizing, has improved each item COLOR FASTNESS of reactive dyeing fabric, and colour fixation is good; Can be applicable to the fixation treatment of Dyeing of Cotton Fabric with Reactive Dyes fabric, can improve the water-fast COLOR FASTNESS and the boiling water immersion fastness of washing of fabric.
Above-described only is preferred implementation of the present invention, should be pointed out that for the person of ordinary skill of the art, under the prerequisite that does not break away from the invention design, can also make some distortion and improvement, and these all belong to protection scope of the present invention.
Claims (10)
1. an aldehyde-free colour stabilizer is characterized in that, comprises the component of following weight portion: cationic monomer is 80-120 part; Unsaturated senior organic amine monomer is 5-20 part, and dicyandiamide is 3-10 part, and pH value conditioning agent is 4-18 part; Metal ion chelation agent is 0.001-0.05 part; Initator is 0.5-1 part, and chloropropylene oxide is 2-10 part, and deionized water is 20-50 part.
2. aldehyde-free colour stabilizer according to claim 1 is characterized in that, comprises the component of following weight portion: cationic monomer is 90-110 part; Unsaturated senior organic amine monomer is 9-16 part, and dicyandiamide is 4-8 part, and pH value conditioning agent is 6-15 part; Metal ion chelation agent is 0.01-0.04 part; Initator is 0.6-0.9 part, and chloropropylene oxide is 3-9 part, and deionized water is 25-45 part.
3. aldehyde-free colour stabilizer according to claim 2 is characterized in that, comprises the component of following weight portion: cationic monomer is 95-105 part; Unsaturated senior organic amine monomer is 11-14 part, and dicyandiamide is 5-7 part, and pH value conditioning agent is 8-12 part; Metal ion chelation agent is 0.02-0.04 part; Initator is 0.7-0.8 part, and chloropropylene oxide is 4-8 part, and deionized water is 30-40 part.
4. aldehyde-free colour stabilizer according to claim 3 is characterized in that, comprises the component of following weight portion: cationic monomer is 100 parts; Unsaturated senior organic amine monomer is 12 parts, and dicyandiamide is 6 parts, and pH value conditioning agent is 10 parts; Metal ion chelation agent is 0.03 part; Initator is 0.75 part, and chloropropylene oxide is 6 parts, and deionized water is 35 parts.
5. aldehyde-free colour stabilizer according to claim 4; It is characterized in that said cationic monomer comprises one or both in dimethyl diallyl ammonium chloride, methylacryoyloxyethyl trimethyl ammonium chloride, diethyl diallyl ammonium chloride and the acrylyl oxy-ethyl-trimethyl salmiac.
6. according to claim 4 or 5 described aldehyde-free colour stabilizers, it is characterized in that said unsaturated senior organic amine monomer comprises allyl amine, diallylamine or triallylamine.
7. aldehyde-free colour stabilizer according to claim 6 is characterized in that, said pH value conditioning agent comprises citric acid, glacial acetic acid or hydrochloric acid.
8. aldehyde-free colour stabilizer according to claim 7 is characterized in that, said metal ion chelation agent comprises the sodium salt of ethylenediamine tetra-acetic acid, the sodium salt of ethylenediamine tetramethylene phosphonic acid or the sodium salt of aminotriacetic acid.
9. aldehyde-free colour stabilizer according to claim 8 is characterized in that said initator comprises potassium peroxydisulfate-sodium hydrogensulfite or ammonium persulfate-sodium sulfite.
10. the preparation method of an aldehyde-free colour stabilizer is characterized in that, specifically comprises the steps:
(1) in the four-hole boiling flask that is connected with nitrogen, reflux condensing tube, thermometer, adds cationic monomer, unsaturated senior organic amine monomer and the dicyandiamide that calculates the weight successively; Open and stir; After treating that raw material stirring evenly, add pH value conditioning agent, the pH value of conditioned reaction system is 3-8;
(2) metering weighing metal ion chelation agent is mixed with the aqueous solution with the deionized water dissolving of 20 times of weight again and joins in the aforesaid reaction vessel;
(3) use the deionized water dissolving initator of 10 times of weight again, it is subsequent use to be mixed with the aqueous solution;
(4) reacting by heating still when the temperature in the four-hole boiling flask rises to 40 ℃, drips the initiator solution of above-mentioned 1/3 weight for preparing simultaneously; After dripping, agitated reactor is warming up to 40-50 ℃ of back flow reaction, when temperature is reduced to 50 ℃; Slowly drip the initiator solution of residue 2/3 weight simultaneously, the dropping time is 1-2 hour, after dripping; At 50 ℃, continue isothermal reaction 1-3 hour, promptly get cationic monomer and amine copolymer;
(5) above-mentioned copolymer is warmed up to 70 ℃, drips the chloropropylene oxide that calculates the weight, isothermal reaction 1-3 hour, add a certain amount of deionized water subsequently, promptly obtain the quaternary ammonium salt cationic aldehyde-free colour stabilizer.
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| CN103711011A (en) * | 2013-12-27 | 2014-04-09 | 福建清源科技有限公司 | Micro-crosslinking type poly(methacryloxyethyltrimethyl ammonium chloride) modified color fixing agent and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH062288A (en) * | 1992-06-17 | 1994-01-11 | Nikka Chem Co Ltd | Dye-fixing agent |
| CN102409568A (en) * | 2011-11-17 | 2012-04-11 | 烟台大学 | Preparation method of hydrophilic cationic formaldehyde-free fixing agent |
| CN102493232A (en) * | 2010-06-30 | 2012-06-13 | 苏州大学 | Formaldehyde-free fixing agent for active dye |
-
2012
- 2012-09-06 CN CN201210326852.0A patent/CN102797170B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH062288A (en) * | 1992-06-17 | 1994-01-11 | Nikka Chem Co Ltd | Dye-fixing agent |
| CN102493232A (en) * | 2010-06-30 | 2012-06-13 | 苏州大学 | Formaldehyde-free fixing agent for active dye |
| CN102409568A (en) * | 2011-11-17 | 2012-04-11 | 烟台大学 | Preparation method of hydrophilic cationic formaldehyde-free fixing agent |
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