CN102174748B - Salt-free dyeing method of vinyl sulphone type reactive dye for cotton fiber - Google Patents
Salt-free dyeing method of vinyl sulphone type reactive dye for cotton fiber Download PDFInfo
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Abstract
The invention relates to a salt-free dyeing method of vinyl sulphone type reactive dye for cotton fiber, mainly comprising the steps of modifying cotton fiber, dyeing the cotton fiber and the like. The modifying treatment is realized by the steps of: soaking and rolling the cotton fiber by a solution containing acrylamide respectively for two times, and then soaking in a sodium hypochlorite solution to perform Hoffman degradation. The modified cotton fiber is dyed by the vinyl sulphone type reactive dye under a salt-free condition; and therefore, the dyeing rate and the color fixing rate of the dye are improved. By use of the salt-free dyeing method, the content of inorganic salts in dyeing wastewater is reduced, benefit is brought for environment protection, a cotton fiber modifying process can be combined with a chlorine blanching process, the production process is simple and the application prospect is wide.
Description
Technical field
The invention belongs to reactive dye salt-free dyeing field, particularly relate to the method for vinyl-sulfone reactive dyes salt-free dyeing.
Background technology
REACTIVE DYES with bright in colour, chromatogram is complete, application is easy, fastness is excellent, function admirable and being celebrated; Add and to replace forbidding dyestuff and other types dyestuff; And suitable new type natural fiber; Develop into natural fabric at present and used most important dye class, become the dye kind that world's dye industry is given priority to and paid close attention to.Present in the middle of the commodity REACTIVE DYES that occur on the international dyestuff market, most REACTIVE DYES kinds, its active group part all is to be made up of halo s-triazine or two kinds of structures of beta-hydroxyethyl sulfone sulfate; Has good wet colour fastness in order to ensure REACTIVE DYES; Therefore when the molecular structure of design REACTIVE DYES; People usually adopt has molecular structure than low-affinity as dye matrix to fabric, is easy to eccysis from the fabric with the REACTIVE DYES of guarantee to dye unreacted REACTIVE DYES in back and hydrolysis.Just because of dyestuff fabric is had lower affinity, therefore in dyeing course, for make REACTIVE DYES can on dye on the fabric and obtain higher dye-uptake, adopt a large amount of salt or glauber salt to help dye usually.But the use of these inorganic salts can produce a large amount of waste water, causes serious environmental to pollute, and therefore, how to realize that less salt and salt-free dyeing are the problems that people are concerned about always, have made number of research projects to this Chinese scholars.
Up to the present, mainly contain following several kinds of approach:
(1) development new reactive dyes: REACTIVE DYES are since 1956 develop successfully, and the dyestuff chemistry man is just carrying out unremitting effort to this problem always both at home and abroad.Look back the development course of REACTIVE DYES, mainly experienced the three generations, the first generation is from about 1956 to nineteen sixty-eight, invents the REACTIVE DYES of dissimilar single-activity bases; The second generation be from the nineteen sixty-eight to the nineteen ninety about, emphasis is through introducing the utilization rate that two active groups improve dyestuff, thereby realizes low salt dyeing.The development of double-active radical dye successfully has obvious effect to the raising of the utilization rate of REACTIVE DYES; The third generation is to play about 2010 from nineteen ninety; Emphasis is the improvement through active group, parent dyestuff and concatenating group; Substantivity through improving the parent dyestuff and further improve two active groups and dispose fixation rate and the COLOR FASTNESS that improves REACTIVE DYES; Make the more economical environmental protection of application of REACTIVE DYES, fastness is better.
(2) new dyeing auxiliary agent: i.e. salt-free dyeing crosslinking agent, crosslinking agent and dyestuff and fiber form crosslinked covalent bond in the process of dyeing.The crosslinking agent that tradition is used is to contain benzaldehyde compound; People have synthesized a series of non-aldehyde cross-linking agents in recent years; Contain reactivity or active group in its molecular structure; Mainly contain N, N-methylene diacrylamine, epoxy compounds, active vinyl-compound, polyisocyanates, Cyanuric Chloride and derivative thereof etc.Except adopting salt-free crosslinking agent, relevant scholar also begins one's study and replaces inorganic salts to be used for the dyeing of REACTIVE DYES with organic salt at present.
(3) adopt low salt dyeing technology: the substantivity of dyestuff is relevant with dyeing temperature and bath raio, and the low more substantivity of dyeing temperature is high more, needs the salt consumption also just few more.Can reduce the solubility and the dyeing rate of dyestuff but temperature is too low, thereby must select for use proper assistant to improve the dissolving and the dispersiveness of dyestuff, dye and fixation speed on the quickening dyestuff.Bath raio is more little, and the dyestuff substantivity is high more, and the salt consumption is also few more.China authorizes publication number CN101532259A just to disclose a kind of salt-free dyeing technology.
(4) cotton fiber modification: mainly be cationic compound (mainly being nitrogen-containing compound) to be anchored on the cotton fiber through chemical bond or physical absorption; Improve the affinity between dyestuff and the fiber; Thereby improve the degree of exhaustion and the degree of fixation of dyestuff; In dyeing course, reduce and even do not use inorganic salts, thereby reduce the discharging of dyeing waste-water widely.The most frequently used in recent years modifying agent can with fiber with covalent bonds; Promptly in amine salt or quaternary ammonium salt, introduce can with the epoxy radicals of hydroxyl reaction in the fiber, have permanent cationic through the cellulose fibre of this modification, dyeability is more stable; Compound as with triethanolamine comes modification; Or come modification with the hydrochloride of chloroethyl ethylenediamine, and generating DEAE, this fiber is very strong to the reactivity of REACTIVE DYES; With 2-chloroethyl amine hydrochloride or 2-amino-ethyl sulfuric ester or aziridine cotton fiber is carried out modification according to bibliographical information and all can obtain aminoethyl cellulose; After cellulose fibre connected the amine alkyl generally, not only the reactivity to REACTIVE DYES strengthened greatly, and in acid medium, can form the ammonium salt cation, can locate the absorbing dye anion.But up to the present also there are problems in the modified technique of cotton fiber, the for example obvious decline of the wearability of DYED FABRICS (breathing freely, pass through wet and tearing brute force), and cost of material is too high; The technology more complicated; Cost is higher, and toxicity is bigger, and commercial Application is difficulty or the like relatively.
Summary of the invention
The present invention utilizes vinyl-sulfone reactive dyes to be far longer than with the alcoholic extract hydroxyl group of fatty alcohol and the characteristics of the reactivity between hydroxyl in the amino reactivity with fatty amine under the reaction condition about pH=5～10; Through cotton fiber being carried out the aminoethyl modification, the suitable aminoethyl cellulose fiber of preparation content.Vinyl-sulfone reactive dyes can combine with stable covalent with the amino on the cellulose fibre under alkali condition, and vinyl-sulfone reactive dyes is dyed on the cellulose fibre faster, thereby improves the utilization rate of vinyl-sulfone reactive dyes greatly.
The technical scheme of implementing this invention comprises two parts, and first is that cotton fiber modification is handled, and its principle is seen shown in the accompanying drawing 1:
The first step steps the gram addition reaction.The aqueous solution of preparation acrylamide and NaOH adds micro-natrium nitrosum as polymerization inhibitor: cotton two soaks two and rolls in above-mentioned solution, and pick-up is 95%～105%; Put into 70 ℃～125 ℃ constant temperature of insulating box; Taking-up is cooled to room temperature, and washing is dried to neutral.
Second step, hoffman degradation reaction.Above-mentioned modification cotton is put into 40 ℃ of clorox and sodium hydrate aqueous solution soaks 1h.Take out washing to neutral, put into pH value and be 4.5 acetum and soak 30min, washing is dried to neutrality naturally.Obtain final modification cotton.
Second portion is dyeing: adopt vinyl-sulfone reactive dyes dyeing.Room temperature dyeing 30min under salt-free condition, 60 ℃ add the alkali fixation.
Cotton fiber after modification and vinyl-sulfone reactive dyes affinity are good, can under salt-free condition, improve the substantivity and the through-dyeing of dyestuff and fiber, thereby make dye-uptake and the degree of fixation of REACTIVE DYES on cotton fiber significantly improve, and realize salt-free dyeing.
The modified technique that the present invention adopts is not seen bibliographical information as yet, steps the gram addition reaction and adopts and roll baking process and cotton fiber is carried out amination modified, can well adapt to the existing equipment of printing and dyeing mill; Hofmann degradation technology can combine with destarch, kiering, the chlorine bleaching process in the printing and dyeing, does not increase existing dyeing process basically; And the reaction reagent that adopts can use economic environmental protection repeatedly.
Description of drawings
Fig. 1 is an embodiment of the invention technical scheme cotton fiber modification principle schematic.
Wherein: 1 is the cotton fiber structure formula; 2 for stepping the carbamyl ethylization fibre structure formula that obtains after the gram addition reaction; 3 is the aminoethyl cellulose fibre structure formula that obtains behind the hoffman degradation reaction.
The specific embodiment
Embodiment 1
(1) cotton fiber modification route
Two soak two rolls, and pick-up is 100%, pads the aqueous solution that solutions employed is acrylamide and NaOH; Solution composition is: acrylamide 20% (mass percent, down together), NaOH 1.65%; Natrium nitrosum 1 ‰, the cotton fiber that will pad are put into 70 ℃ of constant temperature 2h of insulating box, take out to be cooled to room temperature; Washing is to neutral, and above-mentioned cotton fiber is put into 40 ℃ of clorox and sodium hydrate aqueous solution soaks 1h, and bath raio is 1: 30; Clorox and sodium hydrate aqueous solution are formed: effective chlorine is 0.9%, and the pH value is 12.Take out washing to neutral, put into pH value and be 4.5 acetum and soak 30min, washing is to neutrality.
(2) dyeing route and prescription
Reactive black KN-B or Reactive Brilliant Blue KN-R, consumption are 4% (mass percent, heavy to cotton fiber), 25 ℃ of dyeing temperatures; bath raio 1: 30, and dyeing time 30min is warming up to 60 ℃ then, adds sodium carbonate 15～20g/L; fixation time 60min, washing, (95 ℃; soap flakes are the 3g/L) 10min that soaps dries after the washing.
(3) unmodified cotton fiber dye technology route and prescription
Reactive black KN-B or Reactive Brilliant Blue KN-R, consumption are 4% (mass percent, heavy to cotton fiber), and unmodified cotton fiber adopts normal dyeing technology; 25 ℃ of dyeing temperatures, bath raio 1: 30 adds sodium chloride 50g/L, dyeing time 30min; Be warming up to 60 ℃ then, add sodium carbonate 20g/L, fixation time 60min, washing; (95 ℃, soap flakes the are 3g/L) 10min that soaps dries after the washing.
Through test, its salt-free dyeing of the cotton fiber result who adopts the present embodiment technical scheme to handle is superior to unmodified cotton fiber the salt dyeing effect being arranged, and can realize salt-free dyeing.The result is referring to table 1.
(1) cotton fiber modification route
Two soak two rolls, and pick-up is 105%, pads the aqueous solution that solutions employed is acrylamide and NaOH; Solution composition is: acrylamide 20% (mass percent, down together), NaOH 1.65%; Natrium nitrosum 1 ‰, the cotton fiber that will pad are put into 70 ℃ of constant temperature 2h of insulating box, take out to be cooled to room temperature; Washing is to neutral, and above-mentioned cotton fiber is put into 40 ℃ of clorox and sodium hydrate aqueous solution soaks 1h, and bath raio is 1: 30; Clorox and sodium hydrate aqueous solution are formed: effective chlorine is 0.9%, and pH value is 12.Take out washing to neutral, put into pH value and be 4.5 acetum and soak 30min, washing is to neutrality.
(2) dyeing route and prescription
Blue or green B133% of section China primitive element or the plain dark blue GG of China of section or the plain active yellow 3 R S of China of section or the plain reactive red 3BSN of section China, consumption are 4% (mass percent, heavy to cotton fiber), 25 ℃ of dyeing temperatures; bath raio 1: 30, and dyeing time 30 minutes is warming up to 60 ℃ then; add sodium carbonate 15～20g/L, fixation time 60min, washing; (95 ℃, soap flakes the are 3g/L) 10min that soaps is dried after the washing.
(3) unmodified cotton fiber dye technology route and prescription
Blue or green B133% of section China primitive element or the plain dark blue GG of China of section or the plain active yellow 3 R S of China of section or the plain reactive red 3BSN of section China, consumption are 4% (mass percent, heavy to cotton fiber), and unmodified cotton fiber adopts normal dyeing technology; 25 ℃ of dyeing temperatures, bath raio 1: 30 adds sodium chloride 50g/L, dyeing time 30min; Be warming up to 60 ℃ then, add sodium carbonate 20g/L, fixation time 60min, washing; (95 ℃, soap flakes the are 3g/L) 10min that soaps dries after the washing.
Through test, its salt-free dyeing of the cotton fiber result who adopts the present embodiment technical scheme to handle is superior to unmodified cotton fiber the salt dyeing effect being arranged or being equal to basically with it, can realize salt-free dyeing.The result is referring to table 1.
Table 1 is to adopt vinyl-sulfone reactive dyes that cotton fiber is had salt dyeing technology by routine and degree of fixation that the aminoethyl modified cotton fiber is recorded respectively by salt-free dyeing technology and the K/S value table of comparisons as a result.Wherein dye-uptake, degree of fixation are calculated as follows:
In the formula, E is a dye-uptake, and F is a degree of fixation, A
0, A
1, A
2Be respectively λ
MaxBefore and after the following dyeing with soap after the dye liquor absorbance.Measure the K/S value with konica minolta CM-2500d spectrophotometric color measurement instrument.
Table 1: vinyl sulfone dyestuff has salt dyeing, salt-free dyeing result contrast
Claims (1)
1. the method for a vinyl-sulfone reactive dyes salt-free dyeing comprises modification processing, dyeing process step to cotton fiber, comprises the following steps:
(1) cotton fiber two being soaked two rolls; Pad the aqueous solution that solutions employed is acrylamide, NaOH and natrium nitrosum; Wherein the mass percent of acrylamide is 6%～40%, and the mass percent of NaOH is 1.65%, and the mass percent of natrium nitrosum is 1 ‰; Pick-up is 95%～105%, and is extremely neutral through 70 ℃～125 ℃ oven dry, washing then;
(2) above-mentioned cotton fiber being immersed 40 ℃, effective chlorine is 1h among 0.9% the liquor natrii hypochloritis, in pH is 4.5 acetum, soaks 0.5h then, takes out washing to neutral;
(3) cotton fiber after modification carries out salt-free dyeing with vinyl-sulfone reactive dyes; It is characterized in that described salt-free dyeing method is at 10～30 ℃ of dyeing 30min; Be warming up to 60 ℃, the sodium carbonate that adds 15g/L～20g/L carries out fixation 1h, washing; 95 ℃ of 10min that soap of the soap flakes aqueous solution with 3g/L dry after the washing; Described vinyl-sulfone reactive dyes is reactive black KN-B, Reactive Brilliant Blue KN-R, the blue or green B 133% of section China primitive element, the plain dark blue GG of section China, the plain active yellow 3 R S of section China, the plain reactive brilliant red 3BSN of section China.
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| CN102391682B (en) * | 2011-09-29 | 2014-05-14 | 浙江山川轻纺科技有限公司 | Pure cotton textile dyeing and printing dye and production technology of same |
| CN102391685B (en) * | 2011-09-29 | 2014-05-14 | 浙江山川轻纺科技有限公司 | Coloring agent for pure cotton fabric dyeing and printing and production process thereof |
| CN102899929A (en) * | 2012-10-30 | 2013-01-30 | 东华大学 | Processing method of salt-free dyeing through activated dye |
| CN103243584B (en) * | 2013-05-22 | 2015-12-09 | 东华大学 | A kind of reactive dye salt-free colouring method |
| CN103276611B (en) * | 2013-06-09 | 2015-07-08 | 东华大学 | Dyeing method adopting activated dye with high fixation rate |
| CN103590267B (en) * | 2013-11-22 | 2015-12-02 | 东华大学 | A kind of salt-free non-alkali dyeing method of non-water of vinylsulfone reactive dyes |
| FR3016363B1 (en) * | 2014-01-15 | 2017-05-26 | Snf Sas | AQUEOUS SOLUTION OF ACRYLAMIDE-DERIVED CATIONIC COPOLYMERS, PROCESS FOR PREPARATION AND USE |
| CN108166258A (en) * | 2017-12-29 | 2018-06-15 | 罗莱生活科技股份有限公司 | A kind of salt-free dyeing method of cation-modified cotton fabric |
| CN110055776A (en) * | 2019-05-20 | 2019-07-26 | 上海帛阳纺织科技有限公司 | A kind of dyeing fabric method of energy-saving and emission-reduction |
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