CN102587159A - Rare earth type accelerating agent for reactive dyeing - Google Patents
Rare earth type accelerating agent for reactive dyeing Download PDFInfo
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Abstract
The invention relates to a rare earth type accelerating agent for reactive dyeing. The rare earth type accelerating agent is prepared by mixing rear-earth salts and organic acid for compounding an aqueous solution with the concentration of 20-30% and then adding a product conditioning agent and a PH conditioning agent to the aqueous solution; the PH of the prepared rare earth type accelerating agent for reactive dyeing is 5-11; the aqueous solution is prepared by mixing a mole fraction of rare-earth salts and 3.5-10 mole fraction of organic acid; and the weight percentage of the product condition agent accounting for the aqueous solution is 5%-25%. The rare earth accelerating agent disclosed by the invention plays a role in accelerating in the reactive dyeing process by using an original dyeing device. The using amount of the traditional inorganic salts is reduced by 60% under the condition that the dyeing effect remains unchanged. The load of environments is reduced due to the reduction of the using amount of the inorganic salts; and the cost of dyeing wastewater treatment is reduced under the condition that the dyeing cost is not increased.
Description
Technical field
The present invention relates to the textile printing and dyeing field, be specifically related to a kind of rare earth accelerating agent for active dyeing.Belong to technical field of chemical products.
Background technology
In recent years, China's amount of cotton every year about about 1,100 ten thousand tons, accounted for 40% of world's amount of cotton greatly, was mainly used in clothes and home textile product.The above printing and dyeing enterprise dyeing cloth of scale output reached 49,400,000,000 meters in 2008, and wherein textile and cotton blending dyeing cloth accounts for more than 60%.As the dyeing and finishing processing status of the COTTON FABRIC of natural fabric and sustainable development from now on-directly receive much attention.
The REACTIVE DYES chromatogram is complete, bright in colour, technique for applying is simple, is the used most important dye of cotton fiber dyeing.The domestic total output of REACTIVE DYES was estimated to reach about 180,000 tons in 2009, and output is only second to DISPERSE DYES.Reactive dyeing will consume a large amount of inorganic salts urgees to dye, and according to 180,000 tons of calculating of REACTIVE DYES annual consumption, the annual emissions of inorganic salts can reach ten thousand tons of 450-500.These inorganic salts also remain in the waste water when participating in dyeing; The discharging of high salinity dyeing waste water has directly changed the water quality of rivers and lakes; Destroyed the ecological environment of water, and the high osmosis of salinity will cause rivers and lakes soil property salinization of soil on every side, reduce the output of crops.The textile waste discharge capacity accounts for 9.6% of national discharged volume of industrial waste water.High concentration inorganic salts in the waste water can suppress microbial growth in the water, cause traditional biological effluent treatment powerless for high salt dyeing waste water, and therefore high salt dyeing waste water treatment difficulty is far above the improvement of common organic pollutant wastewater.How to reduce the inorganic salt content in the cotton fiber vital staining waste water, reduce environmental pollution, become a research focus.
Three kinds of methods can reduce the inorganic salts consumption in the dyeing course.
1) structure of optimization REACTIVE DYES
Through the structure of adjustment optimization dye molecule, dyestuff is accomplished dyeing to the dependence of inorganic salts in the reduction vital staining process in the presence of salt-free or small amounts of inorganic salt.Like Ciba company in the Cibacron LS of nineteen ninety-five exploitation series low-salt active dyestuff.Couple together through the dyestuff of special connection base with two identical or different structures, become bridge formation type REACTIVE DYES, molecular weight is big, and flatness is fine, and the three-dimensional effect that connects base and active group is very little, so fiber is had very high substantivity.Such dyestuff is few with the salt amount, has only the 1/2-1/3 of traditional REACTIVE DYES.But, cause uneven and difficult removal of dyeing back loose colour of dyeing easily along with the raising of dyestuff to fiber affinity.
2) cotton fiber is cation-modified
Through cotton fiber is carried out quaternary ammoniated or amination modifying, give cotton fiber with cation group, reach the purpose of salt-free dyeing, but the level-dyeing property of dyestuff is poor, technology is numerous and diverse.
In addition, use crosslinking agent to handle cotton fiber and also can reach same effect, but crosslinking agent can reduce the solubility of dyestuff, the dye-uptake of dyestuff is reduced with tertiary amine or quaternary amine base.
3) substitute of traditional inorganic salt
Sodium chloride and glauber salt impel people to seek a kind of inorganic salts substitute with same function with the environmental hazard that a large amount of dischargings of dyeing waste-water bring.H Gurumallesh Prabu. etc. are at " Coloration Technology " (2002; 118:131-134) publish an article on the periodical; Point out to use natrium citricum can replace traditional inorganic salt in vital staining, to bring into play the short effect of dying, the Color of cotton fiber is not weaker than the short effect of dying of inorganic salts.But inorganic salts such as natrium citricum and the glauber salt market price differs bigger, does not still possess the comprehensive advantage of cost performance.(2005,65:221-225 and 2007 72:57-65) has delivered about the EDTA sodium salt and dye the article of effect with inorganic salts substitute performance is short, but EDTA has potential harm to environment to Nahed S.E etc. at " dyes and pigments ".
Summary of the invention
First purpose of the present invention is to overcome the problems referred to above, and a kind of rare earth accelerating agent for active dyeing is provided.This rare earth accelerating agent can make traditional inorganic salt (sodium chloride or glauber salt) consumption reduce by 60% in cellulose fibre vital staining process, and simultaneously, the short effect of dying of Color and traditional inorganic salt is suitable.Adopt the dyeing cost and the traditional inorganic salt of rare earth accelerating agent suitable, can reduce of the pollution of high salinity dyeing waste-water effectively, reduce the cost of waste water treatment water and soil resources in the environment.
Second purpose of the present invention is for a kind of preparation method of rare earth accelerating agent for active dyeing is provided.
The 3rd purpose of the present invention is for a kind of purposes of rare earth accelerating agent for active dyeing is provided.
First purpose of the present invention reaches through following measure:
A kind of rare earth accelerating agent for active dyeing is characterized in that: by rare-earth salts, organic acid mix be made into the aqueous solution of 20%～30% concentration after, add product conditioning agent and PH conditioning agent and process; The PH that makes rare earth accelerating agent for active dyeing is 5～11; The said aqueous solution comprises that the rare-earth salts of 1 molfraction mixes with the organic acid of 3.5～10 molfractions; The percentage by weight that said product conditioning agent accounts for the aqueous solution is 5%～25%.
Second purpose of the present invention reaches through following measure:
1, a kind of preparation method of rare earth accelerating agent for active dyeing is characterized in that carrying out according to the following steps successively:
1) rare-earth salts with 1 molfraction mixes with the organic acid of 3.5～10 molfractions, is made into the aqueous solution of 20%～30% concentration, reacts 0.5～48 hour down in 20～100 ℃, obtains intermediate A;
2) add that to account for the intermediate A percentage by weight be 5%～25% product conditioning agent, mix down, reacted 0.5～2 hour at 20～50 ℃;
3) afterwards, under 20～50 ℃, add the PH conditioning agent, the PH of control product is 5～11, promptly makes rare earth accelerating agent for active dyeing.
Second purpose of the present invention can also reach through taking following measure:
A kind of embodiment of realizing the present invention's second purpose is: the rare-earth salts described in the step 1) is a kind of in the hydrochloride that contains lanthanum, cerium, samarium, yttrium, neodymium rare earth element, nitrate, oxalates, the carbonate or more than one combination.
A kind of embodiment of realizing the present invention's second purpose is: the organic acid described in the step 1) is a kind of in monocarboxylic acid, polybasic carboxylic acid, hydroxycarboxylic acid, amino carboxylic acid, sulfonic acid, amino acid, the organic phospho acid or more than one combination.
A kind of embodiment of realizing the present invention's second purpose is: the organic acid described in the step 1) is a kind of in citric acid, formic acid, acetate, oxalic acid, propionic acid, tartaric acid, polyacrylic acid, maleic acid, ethylenediamine tetra-acetic acid, benzene sulfonic acid, the polyphosphoric acid or more than one combination.
A kind of embodiment of realizing the present invention's second purpose is: the product conditioning agent step 2) is an amphiprotic substance, and it is amphoteric surfactant or amino acid, or amphoteric surfactant and amino acid combination between the two.
A kind of embodiment of realizing the present invention's second purpose is: described amphoteric surfactant is one or more the combination in betaine type, amino acid pattern, imidazoline type, the amine oxide type surfactant.
A kind of embodiment of realizing the present invention's second purpose is: described amino acid is one or more the combination in glycine, aspartic acid, asparagine, serine, threonine, cysteine, histidine, arginine, glutamic acid, the lysine.
The 3rd purpose of the present invention reaches through following measure:
A kind of purposes of rare earth accelerating agent for active dyeing is characterized in that carrying out according to the following steps successively:
1) according to preparation dye bath in 1: 15, adds REACTIVE DYES under the room temperature, put into the cellulose base fiber fabric after scouringing and bleaching, move 10 minutes;
2) add sodium chloride or glauber salt, add the rare earth accelerating agent for active dyeing that adopts the described preparation method's preparation of first order, move 10 minutes;
3) heating up also, temperature control is incubated 10～60 minutes at 30～90 ℃;
4) add sodium carbonate, be incubated 30～90 minutes;
5) lower the temperature afterwards, soap, dry.
The 3rd purpose of the present invention can also reach through taking following measure:
A kind of embodiment of realizing the present invention's the 3rd purpose is: dyestuff described in the step 1) is low temperature, high temperature or middle temperature REACTIVE DYES; Described cellulose fibre is cotton, fiber crops or viscose.
The invention has the beneficial effects as follows:
Rare earth accelerating agent for active dyeing and methods for making and using same thereof are disclosed among the present invention.This accelerant can make traditional inorganic salt (sodium chloride or glauber salt) consumption reduce by 60% in cellulose fibre vital staining process, and simultaneously, the short effect of dying of Color and traditional inorganic salt is suitable.Adopt the dyeing cost and the traditional inorganic salt of rare earth accelerating agent suitable, reduced of the pollution of high salinity dyeing waste-water effectively, reduced the cost of waste water treatment water and soil resources in the environment.
The specific embodiment
Below in conjunction with embodiment content of the present invention is described further.
Specific embodiment 1:
The described rare earth accelerating agent for active dyeing of present embodiment comprises rare-earth salts, organic acid, product conditioning agent and PH conditioning agent.Rare-earth salts is the nucleus of product, the main short effect of dying of performance.Organic acid can form complex with rare-earth salts, and dyes fiber on the auxiliary dyestuff, product conditioning agent tunable product and the interfibrous interaction of dye well, and the PH conditioning agent is used for adjusting the Acidity of Aikalinity of product.
In the present embodiment, described rare-earth salts is seven water cerium chlorides, and described organic acid is a Citric Acid Mono, and said product conditioning agent is cocamidopropyl betaine (CAB-35), and described PH conditioning agent is a NaOH.
The preparation method of the described rare earth accelerating agent for active dyeing of present embodiment, carry out successively according to the following steps:
1) in the 198.552g deionized water, add 73.55g Citric Acid Mono and 37.258g seven water cerium chlorides, 40 ℃ of following stirring reactions 2 hours obtain the 309.36g intermediate A;
2) under 40 ℃, add 15.468g cocamidopropyl betaine (CAB-35), stirring reaction 0.5 hour;
3) afterwards, under 40 ℃, add NaOH, the PH of regulation system is neutral, promptly makes rare earth accelerating agent for active dyeing.For the ease of difference, abbreviate " accelerant I " here as.
Specific embodiment 2:
The described rare earth accelerating agent for active dyeing of present embodiment comprises rare-earth salts, organic acid, product conditioning agent and PH conditioning agent.Described rare-earth salts is seven water cerium chlorides, and described organic acid is a Citric Acid Mono, and said product conditioning agent is cocamidopropyl betaine (CAB-35), and described PH conditioning agent is a NaOH.
The preparation method of the described rare earth accelerating agent for active dyeing of present embodiment, carry out successively according to the following steps:
1) in the 899.592g deionized water, add 210.14g Citric Acid Mono and 37.258g seven water cerium chlorides, 40 ℃ of following stirring reactions 2 hours obtain the 1146.99g intermediate A;
2) under 40 ℃, add 286.7475g cocamidopropyl betaine (CAB-35), stirring reaction 0.5 hour;
3) afterwards, under 40 ℃, add NaOH, the PH of regulation system is neutral, promptly makes rare earth accelerating agent for active dyeing.For the ease of difference, abbreviate " accelerant II " here as.
Specific embodiment 3:
The described rare earth accelerating agent for active dyeing of present embodiment comprises rare-earth salts, organic acid, product conditioning agent and PH conditioning agent.Described rare-earth salts is six water lanthanum chlorides, and described organic acid is a glacial acetic acid, and said product conditioning agent is a glycine, and described PH conditioning agent is a NaOH.
The preparation method of the described rare earth accelerating agent for active dyeing of present embodiment, carry out successively according to the following steps:
1) in the 95.4915g deionized water, add 21.0175g glacial acetic acid and 35.336g six water lanthanum chlorides, 30 ℃ of following stirring reactions 1 hour obtain the 151.845g intermediate A;
2) under 30 ℃, add the 7.59225g glycine, stirring reaction 0.5 hour;
3) afterwards, under 30 ℃, add NaOH, the PH of regulation system is neutral, promptly makes rare earth accelerating agent for active dyeing.For the ease of difference, abbreviate " accelerant III " here as.
Specific embodiment 4:
The described rare earth accelerating agent for active dyeing of present embodiment comprises rare-earth salts, organic acid, product conditioning agent and PH conditioning agent.Described rare-earth salts is six water lanthanum chlorides, and described organic acid is a glacial acetic acid, and said product conditioning agent is a glycine, and described PH conditioning agent is a NaOH.
The preparation method of the described rare earth accelerating agent for active dyeing of present embodiment, carry out successively according to the following steps:
1) in the 327.544g deionized water, add 60.05g glacial acetic acid and 35.336g six water lanthanum chlorides, 30 ℃ of following stirring reactions 1 hour obtain the 422.93g intermediate A;
2) under 30 ℃, add the 105.7325g glycine, stirring reaction 0.5 hour;
3) afterwards, under 30 ℃, add NaOH, the PH of regulation system is neutral, promptly makes rare earth accelerating agent for active dyeing.For the ease of difference, abbreviate " accelerant IV " here as.
Other embodiment:
Rare-earth salts of the present invention is a kind of in the hydrochloride that contains lanthanum, cerium, samarium, yttrium, neodymium rare earth element, nitrate, oxalates, the carbonate or more than one combination.
Organic acid of the present invention is a kind of in monocarboxylic acid, polybasic carboxylic acid, hydroxycarboxylic acid, amino carboxylic acid, sulfonic acid, amino acid, the organic phospho acid or more than one combination.Described organic acid is a kind of in citric acid, formic acid, acetate, oxalic acid, propionic acid, tartaric acid, polyacrylic acid, maleic acid, ethylenediamine tetra-acetic acid, benzene sulfonic acid, the polyphosphoric acid or more than one combination.
Product conditioning agent of the present invention is an amphiprotic substance, and it is amphoteric surfactant or amino acid, or amphoteric surfactant and amino acid combination between the two.Amphoteric surfactant is one or more the combination in betaine type, amino acid pattern, imidazoline type, the amine oxide type surfactant.Described amino acid is one or more the combination in glycine, aspartic acid, asparagine, serine, threonine, cysteine, histidine, arginine, glutamic acid, the lysine.
The application process of said rare earth accelerating agent for active dyeing below is detailed for example.
Concrete application example 1:
A kind of application process of rare earth accelerating agent for active dyeing, carry out successively according to the following steps:
1) according to preparation dye bath in 1: 15, (2%, owf), adding pure cotton knitting half-bleached shirting moves 10 minutes to add Reactive Brilliant Blue KN-R under the room temperature;
2) add 20g/L glauber salt and 7g/L " accelerant I " respectively, move 10 minutes;
3) heating up also, temperature control is incubated 30 minutes at 60 ℃;
4) add sodium carbonate 20g/L, be incubated 45 minutes;
5) lower the temperature afterwards, soap, dry.
Concrete application example 2:
A kind of application process of rare earth accelerating agent for active dyeing, carry out successively according to the following steps:
1) according to preparation dye bath in 1: 15, (2%, owf), adding pure cotton knitting half-bleached shirting moves 10 minutes to add Reactive Brilliant Blue KN-R under the room temperature;
2) add 20g/L glauber salt and 7g/L " accelerant II " respectively, move 10 minutes;
3) heating up also, temperature control is incubated 30 minutes at 60 ℃;
4) add sodium carbonate 20g/L, be incubated 45 minutes;
5) lower the temperature afterwards, soap, dry.
Concrete application example 3:
A kind of application process of rare earth accelerating agent for active dyeing, carry out successively according to the following steps:
1) according to preparation dye bath in 1: 15, (2%, owf), adding pure cotton knitting half-bleached shirting moves 10 minutes to add Reactive Brilliant Blue KN-R under the room temperature;
2) add 20g/L glauber salt and 7g/L " accelerant III " respectively, move 10 minutes;
3) heating up also, temperature control is incubated 30 minutes at 60 ℃;
4) add sodium carbonate 20g/L, be incubated 45 minutes;
5) lower the temperature afterwards, soap, dry.
Concrete application example 4:
A kind of application process of rare earth accelerating agent for active dyeing, carry out successively according to the following steps:
1) according to preparation dye bath in 1: 15, (2%, owf), adding pure cotton knitting half-bleached shirting moves 10 minutes to add Reactive Brilliant Blue KN-R under the room temperature;
2) add 20g/L glauber salt and 7g/L " accelerant IV " respectively, move 10 minutes;
3) heating up also, temperature control is incubated 30 minutes at 60 ℃;
4) add sodium carbonate 20g/L, be incubated 45 minutes;
5) lower the temperature afterwards, soap, dry.
The short of rare earth accelerating agent dyed effect and urgees to dye this:
According to dying cotton fiber on concrete application example 1～4 said dyeing, according to the cost of material of specific embodiment 1～4 preparation method's counting yield, the gained result sees table 1.
Table 1 rare earth accelerating agent and glauber salt are short to be dyed effect and urgees to dye this comparison
In the table 1, the dyeing cost refers under the identical condition of other conditions (comprising amount of dye, alkali consumption, the water yield, energy resource consumption, labour cost etc.), only comprise the cost of material of glauber salt and rare earth accelerating agent.
Data show in the table 1, and the adding of rare earth accelerating agent makes the glauber salt consumption reduce by 60%, alleviates working strength of workers, raises labour efficiency.Simultaneously, reduced discharging 60% inorganic salts amount, the processing cost of waste water is greatly reduced to environment.
Claims (7)
1. rare earth accelerating agent for active dyeing is characterized in that: by rare-earth salts, organic acid mix be made into the aqueous solution of 20%～30% concentration after, add product conditioning agent and PH conditioning agent and process; The PH that makes rare earth accelerating agent for active dyeing is 5～11; The said aqueous solution comprises that the rare-earth salts of 1 molfraction mixes with the organic acid of 3.5～10 molfractions; The percentage by weight that said product conditioning agent accounts for the aqueous solution is 5%～25%.
2. a kind of rare earth accelerating agent for active dyeing as claimed in claim 1 is characterized in that: described rare-earth salts is a kind of in the hydrochloride that contains lanthanum, cerium, samarium, yttrium, neodymium rare earth element, nitrate, oxalates, the carbonate or more than one combination.
3. a kind of rare earth accelerating agent for active dyeing as claimed in claim 1 is characterized in that: described organic acid is a kind of in monocarboxylic acid, polybasic carboxylic acid, hydroxycarboxylic acid, amino carboxylic acid, sulfonic acid, amino acid, the organic phospho acid or more than one combination.
4. a kind of rare earth accelerating agent for active dyeing as claimed in claim 1 is characterized in that: described organic acid is a kind of in citric acid, formic acid, acetate, oxalic acid, propionic acid, tartaric acid, polyacrylic acid, maleic acid, ethylenediamine tetra-acetic acid, benzene sulfonic acid, the polyphosphoric acid or more than one combination.
5. a kind of rare earth accelerating agent for active dyeing as claimed in claim 1 is characterized in that: described product conditioning agent is an amphiprotic substance, and it is amphoteric surfactant or amino acid, or amphoteric surfactant and amino acid combination between the two.
6. a kind of rare earth accelerating agent for active dyeing as claimed in claim 5 is characterized in that: described amphoteric surfactant is one or more the combination in betaine type, amino acid pattern, imidazoline type, the amine oxide type surfactant.
7. a kind of rare earth accelerating agent for active dyeing as claimed in claim 5 is characterized in that described amino acid is one or more the combination in glycine, aspartic acid, asparagine, serine, threonine, cysteine, histidine, arginine, glutamic acid, the lysine.
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| CN103479549A (en) * | 2013-09-17 | 2014-01-01 | 常州大学 | Chestnut shell hair colorant and method for coloring hair |
| CN103726358A (en) * | 2013-12-31 | 2014-04-16 | 江苏中新资源集团有限公司 | Fabric dyeing accelerant |
| CN103757944A (en) * | 2014-01-14 | 2014-04-30 | 傅科杰 | Composite printing and dyeing auxiliary as well as preparation method and application of auxiliary |
| CN105332296A (en) * | 2015-12-10 | 2016-02-17 | 缪琼华 | Accelerating agent for dyeing of reactive dyes |
| CN105442349A (en) * | 2015-12-10 | 2016-03-30 | 缪琼华 | Preparation method of dyeing accelerant for reactive dyeing |
| CN106368008A (en) * | 2016-08-31 | 2017-02-01 | 浙江正宇纺织印染基地有限公司 | Dyeing accelerant for printing and dyeing of silk-cotton blended fabric and preparation method thereof |
| CN108049215A (en) * | 2017-12-08 | 2018-05-18 | 巢湖市翔宇渔具有限公司 | A kind of fishing net colouring method |
| CN108890826A (en) * | 2018-08-06 | 2018-11-27 | 安徽三和工艺品有限公司 | A kind of dyeing auxiliaries improving bamboo handicraft article dye-uptake |
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|---|---|---|---|---|
| CN103479549A (en) * | 2013-09-17 | 2014-01-01 | 常州大学 | Chestnut shell hair colorant and method for coloring hair |
| CN103479549B (en) * | 2013-09-17 | 2016-04-06 | 常州大学 | Chestnut shell hair colorant and hair colouring methods thereof |
| CN103726358A (en) * | 2013-12-31 | 2014-04-16 | 江苏中新资源集团有限公司 | Fabric dyeing accelerant |
| CN103726358B (en) * | 2013-12-31 | 2015-12-30 | 江苏中新资源集团有限公司 | A kind of fabric accelerant |
| CN103757944A (en) * | 2014-01-14 | 2014-04-30 | 傅科杰 | Composite printing and dyeing auxiliary as well as preparation method and application of auxiliary |
| CN105332296A (en) * | 2015-12-10 | 2016-02-17 | 缪琼华 | Accelerating agent for dyeing of reactive dyes |
| CN105442349A (en) * | 2015-12-10 | 2016-03-30 | 缪琼华 | Preparation method of dyeing accelerant for reactive dyeing |
| CN106368008A (en) * | 2016-08-31 | 2017-02-01 | 浙江正宇纺织印染基地有限公司 | Dyeing accelerant for printing and dyeing of silk-cotton blended fabric and preparation method thereof |
| CN108049215A (en) * | 2017-12-08 | 2018-05-18 | 巢湖市翔宇渔具有限公司 | A kind of fishing net colouring method |
| CN108890826A (en) * | 2018-08-06 | 2018-11-27 | 安徽三和工艺品有限公司 | A kind of dyeing auxiliaries improving bamboo handicraft article dye-uptake |
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