CN100529249C - Super-branching reactive dye salt-free dyeing auxiliary - Google Patents
Super-branching reactive dye salt-free dyeing auxiliary Download PDFInfo
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- CN100529249C CN100529249C CNB2007100207948A CN200710020794A CN100529249C CN 100529249 C CN100529249 C CN 100529249C CN B2007100207948 A CNB2007100207948 A CN B2007100207948A CN 200710020794 A CN200710020794 A CN 200710020794A CN 100529249 C CN100529249 C CN 100529249C
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Abstract
This invention discloses a super branch active dyer assist without salt, which belongs to the textile dyeing technology area. The ingredient of it is end amidocyanogen super branch compound, cross-link agent, catalyzer. Because the end amidocyamogen is different from the small branch compound and the traditional high molecular compound, the amidocyamogen and imine base on the surface of fibre are abundance and equal adopting this assist to process the yarn and textile. So there is no need to add salt into the active dyer to guarantee the equality of dying, at the same time, the depth of the dying and color firm and other index is good as or better than the traditional technology. The application of the assist can be added on the washing processor after the bleach or polishing of the textile, and it is simple and can reduce the content of inorganic salt, and it is good at the protection of the environment and simplifies the technology of traditional dying. This assist is suitable to the directly application to acid color and directly color processor.
Description
Technical field
The present invention relates to a kind of auxiliary agent that can be used for super-branching reactive dye salt-free dyeing, belong to textile auxiliary's technical field.
Background technology
REACTIVE DYES is in dyeing course, and dyestuff becomes the chemical bond combination with fiber, thereby coloured fibre demonstrates good moisture resistant fastness, liked by the consumer.In traditional dyeing,, must add a large amount of sodium chloride or sodium sulphate, and consumption reaches 30～150g/l for dye-uptake and the degree of fixation that improves REACTIVE DYES.A large amount of uses of inorganic salts make REACTIVE DYES unavoidably hydrolysis can take place at dyeing course, cause reactive dyeing cost height; The use of a large amount of inorganic salts can't be degraded and reclaim, and is very big to the negative effect of water quality and soil simultaneously, caused the pollution to environment.Therefore, the salt-free dyeing of REACTIVE DYES research becomes one of hot issue that global dyestuff chemistry man and colourist endeavour to solve.
In order to realize the consumption of salt-free dyeing technology or reduction inorganic salts, it is reported [" reactive dye salt-free Study on Technology of Dyeing progress " weaving Leader, 2005 (7): 78～82], existing research mainly concentrates on three aspects: the cation-modified and salt-free dyeing crosslinking agent of synthesizing new low-salt active dyestuff, cellulose fibre.But the existence of problems such as low uneven, cation-modified cellulose fibre complex process of salt dyestuff chromatogram and uneven dyeing has limited their utilizations in actual production.
Studies show that dendrimer is to have dendriform structure, highly branched monodisperse polymer; And hyperbranched compound is the big molecule with dendriform structure of defective.Because the particularity of their structures and character, caused widely and paid close attention to, lot of documents has reported dendrimer and hyperbranched macromolecular is synthetic and the research of application, and dendrimer and hyperbranched macromolecular are applied at aspects such as surfactant, catalyst, nano composite material, metal nano material, membrane material, liquid crystal, coating material, biomedicine field, photoelectric material, membrane electrode, oil exploitation thinner, adhesives.At present, dendrimer and hyperbranched macromolecular material also there is being report in the textile printing and dyeing Application for Field both at home and abroad, as " The use ofdendrimers to modify the dyeing behaviour of reactive dyes on cotton " [Dyes and Pigments 47 (2000) 259～267], " the low application study of algebraically polyamide-amide dendrimer in cotton fiber dyeing " [printing and dyeing assistant, 2005,22 (7): 20～25] etc. in the research, low algebraically polyamide-amide dendrimer PAMAM is applied to the reactive dyeing technology and the direct dyeing technology of COTTON FABRIC, reached significantly short and dyed effect, can realize salt-free dyeing.But, in actual production, also can't be used widely owing to the synthesis step complexity of low algebraically polyamide-amide dendrimer PAMAM, progressively purify that productive rate is extremely low, production cost is expensive.
The big molecular surface of end amino superbranching has abundant amido and imido grpup, it does not do purifying usually to the intermediate product that generates in synthetic reaction process, polymerizing condition is also strict unlike the PAMAM dendritic macromole, its product molecular structure allows to occur defective, therefore, synthetic convenient, cheap, have practical value.In the Chinese invention patent " end amido water-soluble ultrabranching polyamide and preparing process thereof " [CN 1232567C], disclosing a kind of employing contains two keys and contains carboxyl or the monomer of ester group and polyamino monomer, mol ratio with 1: 100～100: 1, reaction is 1 hour to 10 days under-50～100 ℃ temperature, mixture with above-mentioned gained is warming up to 50～280 ℃ again, decompression continues reaction 30 minutes to 5 days down, makes ultrabranching polyamide, and resulting polymers contains a large amount of end amidos and props up compound.
Utilization end amino superbranching compound synthesis technique is simple, cheap and have the advantages that amido and imido grpup are enriched in the surface, is applied to the textile printing and dyeing field, realizes reactive dye salt-free dyeing, has crucial meaning.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, provide that a kind of technology is simple, level-dyeing property and the good reactive dye salt-free dyeing auxiliary of dyefastness.
Technical scheme of the present invention provides a kind of super-branching reactive dye salt-free dyeing auxiliary, it is characterized in that: the aqueous solution that it is made up of end amino superbranching compound, crosslinking agent, catalyst, in the solute, by mass ratio end amino superbranching compound is 10～80%, crosslinking agent is 10～40%, and catalyst is 10～50%.
Described end amino superbranching compound for by acid anhydrides, contain two keys and contain carboxyl or the monomer of ester group in a kind of and polyamines base monomer, synthetic with 1: 20～20: 1 mol ratios; Described acid anhydrides, contain two keys and contain carboxyl or the monomer of ester group comprises succinic anhydride, phthalic anhydride, ring butyric anhydride, methyl acrylate (MA), ethyl acrylate (EA), methyl methacrylate (MMA), acrylic acid (AA), methacrylic acid (MAA); Described polyamines base monomer comprises polyamines based compounds such as ethylenediamine, divinyl triamine, trivinyl tetramine, tetraethylenepentamine, five vinyl hexamines.
Described crosslinking agent is citric acid (CA), maleic anhydride (MA), 1,2,3, a kind of in 4-BTCA (BTCA), tricarballylic acid (PTCA), the glutaraldehyde or their combination.
Described catalyst is a kind of in nitrilotriacetic acid sodium, the inferior sodium phosphate or their combination.
The principle of technical solution of the present invention is: because its architectural feature of end amino superbranching compound both had been different from general micromolecular compound, also be different from conventional linear polymer, good and the surperficial amido of flow of solution, imido grpup are abundant, be applied to the modification of fiber surface is handled, in dye bath, can introduce abundant positive charge to fiber, reduce on the fiber with negative electrical charge, reduce or overcome in the dyeing course on the fiber negative electrical charge the anionic Coulomb force of REACTIVE DYES, impel on the dyestuff and dye, thereby realize real salt-free dyeing.Simultaneously, the adding of crosslinking agent and catalyst can impel between the amido in the end amino superbranching adduct molecule and takes place crosslinkedly with the hydroxyl of fiber surface, improves the set of end amino superbranching compound at fiber surface.Because the carboxyl in partial cross-linked dose is electronegative, these crosslinking agents of too much employing can make the negative charge amount of fiber surface increase, thereby therefore the action effect of influence end amino superbranching compound, the type of choose reasonable crosslinking agent and is controlled its suitable consumption.
Compared with prior art, advantage of the present invention is:
1, because end amino superbranching compound has the advantages that amido and imido grpup are rich in the surface; treated fabric can reduce on the fiber with negative electrical charge, impel on the dyestuff and dye, thereby realize real salt-free dyeing; reduced processing cost, the protection environment to the dyeing waste liquid.
2, the main raw material end amino superbranching compound that is used for reactive dye salt-free dyeing auxiliary, simple, the easily realization of its synthesis technique, therefore, this auxiliary agent cost is low, has the value of suitability for industrialized production and application.
3, the adding of crosslinking agent and catalyst, can impel between the amido in the end amino superbranching adduct molecule and take place crosslinked with the hydroxyl of fiber surface, improve of the set of end amino superbranching compound, can prevent from dyeing course, to come off, combine with dyestuff and form the color lake at fiber surface.
4, end amino superbranching compound is different from linear polymeric, and solution viscosity is little, and is even to the processing of fiber, so the fabric after handling with the reactive dye salt-free dyeing auxiliary that technical solution of the present invention provided, and the uniformity of dyeing and dyefastness are good.
5, hold amido and the imido grpup that the amino superbranching compound contains also can give the fabric good antibacterial performance, dyeing need not be removed after finishing.
Description of drawings
Fig. 1 is the heating curve figure of embodiment of the invention dyeing.
The specific embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment 1:
1, the hyperbranched compound of synthesizing end amino:
52ml divinyl triamine is placed the 250ml there-necked flask, and ice-water bath cooling under the N2 protection, slowly drips the mixed solution of 43ml methyl acrylate and 100ml methyl alcohol with constant pressure funnel, reacts 4h after dropwising at normal temperatures.Move to then in the Rotary Evaporators eggplant type flask, methyl alcohol is removed in decompression, is warming up to 150 ℃ of decompression reaction 4h, stops reaction, obtains the faint yellow end amino superbranching of thickness compound.
2, preparation reactive dye salt-free dyeing auxiliary:
Above-mentioned end amino superbranching compound 6g/l, citric acid 2g/l, inferior sodium phosphate 3g/l are dissolved in the water, and are mixed with reactive dye salt-free dyeing auxiliary, and it is standby to place 12h.
3, textile dyeing pre-treatment
The textile bleached cotton fabric COTTON FABRIC of 13tex * 13tex 133 * 72 are carried out two with the reactive dye salt-free dyeing auxiliary that has been prepared into soak two and roll processing, control pick-up 100% is to dry 5min under 10 ℃ the condition in temperature, and hot water boils 5min then, waits to dye.
4, reactive dye salt-free dyeing
Prescription: reactive scarlet A-EH 2% (heavy) to fabric
Na
2CO
3(A) 20g/l
Bath raio is 50: 1
The dyeing heating curve is referring to Fig. 1.
5, washing post processing
Add the soap flakes of 3g/l, boiled under 95 ℃ temperature 5 minutes, washing back airing obtains sample.
Embodiment 2:
1, end amino superbranching compound is synthetic
52ml trivinyl tetramine is placed the 250ml there-necked flask, and ice-water bath cooling under the N2 protection, slowly drips the mixed solution of 43ml methyl acrylate and 100ml methyl alcohol with constant pressure funnel, reacts 4h after dropwising at normal temperatures.Move to then in the Rotary Evaporators eggplant type flask, methyl alcohol is removed in decompression, is warming up to 150 ℃ of decompression reaction 4h, stops reaction, obtains the faint yellow end amino superbranching of thickness compound.
2, the preparation of reactive dye salt-free dyeing auxiliary
Be mixed with salt-free dyeing auxiliary by above-mentioned end amino superbranching compound 4g/l, citric acid 2g/l, inferior sodium phosphate 3g/l, directly use.
3, textile dyeing pre-treatment
13tex * 13tex 133 * 72 textile bleached cotton fabric COTTON FABRIC two are soaked two roll, 100%, 80 ℃ of oven dry of control pick-up 3min, 180 ℃ bake 2min, and hot water boils 5min then, waits to dye.
4, salt free dyeing with reactive dye
Prescription: reactive scarlet A-EH 2% (heavy) to fabric
Na
2CO
3(A) 20g/l
Bath raio 50: 1
The dyeing heating curve is identical with embodiment 1.
5, washing post processing:
Add the soap flakes of 3g/l, boiled under 95 ℃ temperature 5 minutes, washing back airing obtains sample.
Table one is with normal dyeing technology (NaCl 50g/l) sample and the sample that is dyeed again after auxiliary agent provided by the invention carries out pre-treatment by embodiment 1,2, and the test result list wherein, is pressed GB/T 3920-97 and measured colour fastness to rubbing; Press GB/T 3921-97 and measure color fastness to washing; Survey the color matching instrument with the Ultrascan-XE computer and measure the k/s value.The result shows by table one, and textile dyeing effect after reactive dye salt-free dyeing auxiliary provided by the invention is used and normal dyeing technology quite or better can realize the salt-free dyeing of REACTIVE DYES.
Table one:
Claims (1)
1. super-branching reactive dye salt-free dyeing auxiliary, it is characterized in that: it wherein, is 10～80% by mass ratio end amino superbranching compound by the aqueous solution that end amino superbranching compound, crosslinking agent, catalyst are formed, crosslinking agent is 10～40%, and catalyst is 10～50%; Described end amino superbranching compound for by acid anhydrides, contain two keys and contain carboxyl or the monomer of ester group in a kind of and polyamines base monomer, synthetic with 1: 20～20: 1 mol ratios; Described acid anhydrides, contain two keys and contain carboxyl or the monomer of ester group comprises succinic anhydride, phthalic anhydride, ring butyric anhydride, methyl acrylate, ethyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid; Described polyamines base monomer comprises ethylenediamine, divinyl triamine, trivinyl tetramine, tetraethylenepentamine, five vinyl hexamines; Described crosslinking agent is citric acid, maleic anhydride, 1,2,3, a kind of in 4-BTCA, tricarballylic acid, the glutaraldehyde or their combination; Described catalyst is a kind of in nitrilotriacetic acid sodium, the inferior sodium phosphate or their combination.
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| CNB2007100207948A CN100529249C (en) | 2007-04-02 | 2007-04-02 | Super-branching reactive dye salt-free dyeing auxiliary |
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| CNB2007100207948A CN100529249C (en) | 2007-04-02 | 2007-04-02 | Super-branching reactive dye salt-free dyeing auxiliary |
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| CN100529249C true CN100529249C (en) | 2009-08-19 |
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Families Citing this family (10)
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| CN101200544B (en) * | 2007-12-18 | 2011-05-04 | 苏州大学 | Amine-terminated hyperbranced compound quaternary ammonium salt and preparation method thereof |
| CN101818457B (en) * | 2010-03-03 | 2012-12-26 | 广东德美精细化工股份有限公司 | Rare earth accelerating agent for active dyeing and preparation method and application thereof |
| CN102619105A (en) * | 2012-04-13 | 2012-08-01 | 杭州永光纺织助剂有限公司 | Special emission-reducing deep dye agent for fiber dyeing |
| CN102747569B (en) * | 2012-06-21 | 2014-02-05 | 广东德美精细化工股份有限公司 | Pad dyeing method for reactive dyes |
| CN104927064B (en) * | 2015-05-28 | 2017-06-23 | 齐鲁工业大学 | A kind of preparation method of the high molecular dye based on hyperbranched polyurethane |
| CN106012081B (en) * | 2016-05-27 | 2018-06-08 | 江南大学 | Hyperbranched compound is modified the preparation method that can contaminate polyimide fiber |
| CN106749946B (en) * | 2016-12-02 | 2019-01-18 | 上海雅运新材料有限公司 | Resistance to bubble fastness color fixing agent of reactive dye and its preparation method and application |
| CN110952350A (en) * | 2019-12-19 | 2020-04-03 | 山东天成化工有限公司 | Special cationic assistant for printing and dyeing natural fiber fabric and preparation method thereof |
| CN112111970B (en) * | 2020-09-29 | 2021-05-07 | 绍兴迈宝科技有限公司 | Preparation method of environment-friendly surface modified cotton fiber |
| CN113684688A (en) * | 2021-09-14 | 2021-11-23 | 佛山市海邦纺织有限公司 | Preparation method of moisture-absorbing quick-drying antibacterial cotton fabric |
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Assignee: Jiangsu Xinfang Textile Group Co., Ltd. Assignor: Soochow University Contract record no.: 2010320000875 Denomination of invention: Super-branching reactive dye salt-free dyeing auxiliary Granted publication date: 20090819 License type: Exclusive License Open date: 20071128 Record date: 20100706 |
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