CN102587159B - 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 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 greatly about 1,100 ten thousand tons of left and right, accounted for 40% of world's amount of cotton every year, was mainly used in clothes and home textile product.Within 2008, the above printing and dyeing enterprise dyeing cloth of scale output reaches 49,400,000,000 meters, 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.
REACTIVE DYES chromatogram is complete, bright in colour, technique for applying is simple, is cotton fiber dyeing most important dye used.Within 2009, the domestic total output of REACTIVE DYES is estimated to reach approximately 180,000 tons, 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 waste water when participating in dyeing, the discharge 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 around, reduce the output of crops.Textile waste discharge capacity accounts for 9.6% of national discharged volume of industrial waste water.High concentration inorganic salts in waste water can suppress microbial growth in water, cause traditional biological effluent treatment helpless 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 cotton fiber vital staining waste water, reduce environmental pollution, become a study hotspot.
Three kinds of methods can reduce the inorganic salts consumption in dyeing course.
1) optimize the structure of REACTIVE DYES
By adjustment, optimize the structure of dye molecule, reduce the dependence of dyestuff to inorganic salts in vital staining process, under the existence of salt-free or a small amount of inorganic salts, complete dyeing.If Ciba company is in the Cibacron LS of nineteen ninety-five exploitation series low-salt reactive dyes.By special connection base, the dyestuff of two identical or different structures is coupled together, become bridge-type REACTIVE DYES, molecular weight is large, and flatness is fine, and the three-dimensional effect that connects base and active group is very little, so fiber is had to very high substantivity.Such dyestuff is few by salt amount, only has the 1/2-1/3 of traditional REACTIVE DYES.But along with the raising of dyestuff to fiber affinity, easily cause difficult removal of the rear loose colour of dyeing inequality and dyeing.
2) cotton fiber is cation-modified
By cotton fiber is carried out to quaternary ammoniated or amination modifying, give cotton fiber with cation group, reach the object of salt-free dyeing, but the level-dyeing property of dyestuff is poor, technique is numerous and diverse.
In addition, use the crosslinking agent processing cotton fiber with tertiary amine or quaternary amine base also can reach same effect, but crosslinking agent can reduce the solubility of dyestuff, and the dye-uptake of dyestuff is reduced.
3) substitute of traditional inorganic salt
The environmental hazard that sodium chloride and glauber salt bring with a large amount of discharges of dyeing waste-water impels people to find a kind of inorganic salts substitute with same function.H Gurumallesh Prabu. etc. are at < < Coloration Technology > > (2002,118:131-134) on periodical, publish an article, 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 the inorganic salts such as natrium citricum and the glauber salt market price differs larger, does not still possess the comprehensive advantage of cost performance.Nahed S.E etc. are at < < dyes and pigments > > (2005,65:221-225 and 2007,72:57-65) delivered about the short article that dyes effect of inorganic salts substitute performance for EDETATE SODIUM salt, but EDTA has potential harm to environment.
Summary of the invention
First object 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 meanwhile, the short effect of dying of Color and traditional inorganic salt is suitable.Adopt dyeing cost and the traditional inorganic salt of rare earth accelerating agent suitable, can effectively reduce the pollution of high salinity dyeing waste-water to water and soil resources in environment, reduce the cost of waste water treatment.
Second object of the present invention is for a kind of preparation method of rare earth accelerating agent for active dyeing is provided.
The 3rd object of the present invention is for a kind of purposes of rare earth accelerating agent for active dyeing is provided.
First object of the present invention reaches by following measures:
A rare earth accelerating agent for active dyeing, is characterized in that: by rare-earth salts, organic acid, mixed and be made into after the aqueous solution of 20%～30% concentration, add product conditioning agent and PH conditioning agent and make; The PH that makes rare earth accelerating agent for active dyeing is 5～11; The described 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 described product conditioning agent accounts for the aqueous solution is 5%～25%.
Second object of the present invention reaches by following measures:
1, a preparation method for rare earth accelerating agent for active dyeing, is characterized in that carrying out according to the following steps successively:
1) rare-earth salts of 1 molfraction is mixed with the organic acid of 3.5～10 molfractions, be made into the aqueous solution of 20%～30% concentration, at 20～100 ℃, react 0.5～48 hour, obtain intermediate A;
2) add that to account for intermediate A percentage by weight be 5%～25% product conditioning agent, at 20～50 ℃, mix, react 0.5～2 hour;
3) afterwards, at 20～50 ℃, add PH conditioning agent, the PH that controls product is 5～11, makes rare earth accelerating agent for active dyeing.
Second object of the present invention can also be by taking following measure to reach:
A kind of embodiment of realizing the present invention's the second object is: the rare-earth salts step 1) is a kind of in the hydrochloride containing lanthanum, cerium, samarium, yttrium, neodymium rare earth element, nitrate, oxalates, carbonate or more than one combination.
A kind of embodiment of realizing the present invention's the second object is: the organic acid step 1) is a kind of in monocarboxylic acid, polybasic carboxylic acid, hydroxycarboxylic acid, amino carboxylic acid, sulfonic acid, amino acid, organic phospho acid or more than one combination.
A kind of embodiment of realizing the present invention's the second object is: the organic acid step 1) is a kind of in citric acid, formic acid, acetic acid, oxalic acid, propionic acid, tartaric acid, polyacrylic acid, maleic acid, ethylenediamine tetra-acetic acid, benzene sulfonic acid, polyphosphoric acid or more than one combination.
A kind of embodiment of realizing the present invention's the second object is: the product conditioning agent step 2) is 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 the second object is: described amphoteric surfactant is one or more the combination in betaine type, amino acid pattern, imidazoline type, amine oxide type surfactant.
A kind of embodiment of realizing the present invention's the second object is: described amino acid is one or more the combination in glycine, aspartic acid, asparagine, serine, threonine, cysteine, histidine, arginine, glutamic acid, lysine.
The 3rd object of the present invention reaches by following measures:
A purposes for 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, under room temperature, add REACTIVE DYES, 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 preparation method described in first order to prepare, move 10 minutes;
3) intensification temperature control, at 30～90 ℃, are incubated 10～60 minutes;
4) add sodium carbonate, be incubated 30～90 minutes;
5) lower the temperature afterwards, soap, dry.
The 3rd object of the present invention can also be by taking following measure to reach:
A kind of embodiment of realizing the present invention's the 3rd object is: dyestuff 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 in 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 meanwhile, the short effect of dying of Color and traditional inorganic salt is suitable.Adopt dyeing cost and the traditional inorganic salt of rare earth accelerating agent suitable, effectively reduced the pollution of high salinity dyeing waste-water to water and soil resources in environment, reduced the cost of waste water treatment.
The specific embodiment
Below in conjunction with embodiment, content of the present invention is described further.
Specific embodiment 1:
Rare earth accelerating agent for active dyeing described in the 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 auxiliary dyestuff, product conditioning agent tunable product and the interfibrous interaction of dye well, and PH conditioning agent is used for adjusting the Acidity of Aikalinity of product.
In the present embodiment, described rare-earth salts is seven water chlorination Cerium, and described organic acid is Citric Acid Mono, and described product conditioning agent is cocamidopropyl betaine (CAB-35), and described PH conditioning agent is NaOH.
The preparation method of the rare earth accelerating agent for active dyeing described in the present embodiment, carries out successively according to the following steps:
1) in 198.552g deionized water, add 73.55g Citric Acid Mono and 37.258g seven water chlorination Cerium, stirring reaction is 2 hours at 40 ℃, obtains 309.36g intermediate A; .
2), at 40 ℃, add 15.468g cocamidopropyl betaine (CAB-35), stirring reaction 0.5 hour;
3) afterwards, at 40 ℃, add NaOH, the PH of regulation system is neutral, makes rare earth accelerating agent for active dyeing.For the ease of difference, herein referred to as " accelerant I ".
Specific embodiment 2:
Rare earth accelerating agent for active dyeing described in the present embodiment comprises rare-earth salts, organic acid, product conditioning agent and PH conditioning agent.Described rare-earth salts is seven water chlorination Cerium, and described organic acid is Citric Acid Mono, and described product conditioning agent is cocamidopropyl betaine (CAB-35), and described PH conditioning agent is NaOH.
The preparation method of the rare earth accelerating agent for active dyeing described in the present embodiment, carries out successively according to the following steps:
1) in 899.592g deionized water, add 210.14g Citric Acid Mono and 37.258g seven water chlorination Cerium, stirring reaction is 2 hours at 40 ℃, obtains 1146.99g intermediate A;
2), at 40 ℃, add 286.7475g cocamidopropyl betaine (CAB-35), stirring reaction 0.5 hour;
3) afterwards, at 40 ℃, add NaOH, the PH of regulation system is neutral, makes rare earth accelerating agent for active dyeing.For the ease of difference, herein referred to as " accelerant II ".
Specific embodiment 3:
Rare earth accelerating agent for active dyeing described in the 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 glacial acetic acid, and described product conditioning agent is glycine, and described PH conditioning agent is NaOH.
The preparation method of the rare earth accelerating agent for active dyeing described in the present embodiment, carries out successively according to the following steps:
1) in 95.4915g deionized water, add 21.0175g glacial acetic acid and 35.336g six water lanthanum chlorides, stirring reaction is 1 hour at 30 ℃, obtains 151.845g intermediate A;
2), at 30 ℃, add 7.59225g glycine, stirring reaction 0.5 hour;
3) afterwards, at 30 ℃, add NaOH, the PH of regulation system is neutral, makes rare earth accelerating agent for active dyeing.For the ease of difference, herein referred to as " accelerant III ".
Specific embodiment 4:
Rare earth accelerating agent for active dyeing described in the 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 glacial acetic acid, and described product conditioning agent is glycine, and described PH conditioning agent is NaOH.
The preparation method of the rare earth accelerating agent for active dyeing described in the present embodiment, carries out successively according to the following steps:
1) in 327.544g deionized water, add 60.05g glacial acetic acid and 35.336g six water lanthanum chlorides, stirring reaction is 1 hour at 30 ℃, obtains 422.93g intermediate A;
2), at 30 ℃, add 105.7325g glycine, stirring reaction 0.5 hour;
3) afterwards, at 30 ℃, add NaOH, the PH of regulation system is neutral, makes rare earth accelerating agent for active dyeing.For the ease of difference, herein referred to as " accelerant IV ".
Other embodiment:
Rare-earth salts of the present invention is a kind of in the hydrochloride containing lanthanum, cerium, samarium, yttrium, neodymium rare earth element, nitrate, oxalates, 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, organic phospho acid or more than one combination.Described organic acid is a kind of in citric acid, formic acid, acetic acid, oxalic acid, propionic acid, tartaric acid, polyacrylic acid, maleic acid, ethylenediamine tetra-acetic acid, benzene sulfonic acid, polyphosphoric acid or more than one combination.
Product conditioning agent of the present invention is 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, 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, lysine.
The application process of described rare earth accelerating agent for active dyeing is below described in detail in detail for example.
Concrete application example 1:
An application process for rare earth accelerating agent for active dyeing, carries out successively according to the following steps:
1) according to 1: 15 preparation dye bath, under room temperature, add Reactive Brilliant Blue KN-R (2%, owf), add pure cotton knitting half-bleached shirting, move 10 minutes;
2) add respectively 20g/L glauber salt and 7g/L " accelerant I ", move 10 minutes;
3) intensification temperature control, at 60 ℃, are incubated 30 minutes;
4) add sodium carbonate 20g/L, be incubated 45 minutes;
5) lower the temperature afterwards, soap, dry.
Concrete application example 2:
An application process for rare earth accelerating agent for active dyeing, carries out successively according to the following steps:
1) according to 1: 15 preparation dye bath, under room temperature, add Reactive Brilliant Blue KN-R (2%, owf), add pure cotton knitting half-bleached shirting, move 10 minutes;
2) add respectively 20g/L glauber salt and 7g/L " accelerant II ", move 10 minutes;
3) intensification temperature control, at 60 ℃, are incubated 30 minutes;
4) add sodium carbonate 20g/L, be incubated 45 minutes;
5) lower the temperature afterwards, soap, dry.
Concrete application example 3:
An application process for rare earth accelerating agent for active dyeing, carries out successively according to the following steps:
1) according to 1: 15 preparation dye bath, under room temperature, add Reactive Brilliant Blue KN-R (2%, owf), add pure cotton knitting half-bleached shirting, move 10 minutes;
2) add respectively 20g/L glauber salt and 7g/L " accelerant III ", move 10 minutes;
3) intensification temperature control, at 60 ℃, are incubated 30 minutes;
4) add sodium carbonate 20g/L, be incubated 45 minutes;
5) lower the temperature afterwards, soap, dry.
Concrete application example 4:
An application process for rare earth accelerating agent for active dyeing, carries out successively according to the following steps:
1) according to 1: 15 preparation dye bath, under room temperature, add Reactive Brilliant Blue KN-R (2%, owf), add pure cotton knitting half-bleached shirting, move 10 minutes;
2) add respectively 20g/L glauber salt and 7g/L " accelerant IV ", move 10 minutes;
3) intensification temperature control, at 60 ℃, are incubated 30 minutes;
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 dyeing described in concrete application example 1～4, according to the cost of material of specific embodiment 1～4 preparation method's counting yield, acquired results is in Table 1.
Short effect and the short cost compare that dyes of dying of table 1 rare earth accelerating agent and glauber salt
In table 1, dyeing cost refers to, 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.
In table 1, data show, adding of rare earth accelerating agent makes glauber salt consumption reduce by 60%, alleviates workman's labour intensity, raises labour efficiency.Meanwhile, to environment, reduced discharging 60% inorganic salts amount, the processing cost of waste water is greatly reduced.
Claims (6)
1. a rare earth accelerating agent for active dyeing, is characterized in that: by rare-earth salts, organic acid, mixed and be made into after the aqueous solution of 20%～30% concentration, add product conditioning agent and pH adjusting agent and make; The pH that makes rare earth accelerating agent for active dyeing is 5～11; The described 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 described product conditioning agent accounts for the aqueous solution is 5%～25%; Described product conditioning agent is amphiprotic substance, and it is amphoteric surfactant or amino acid, or amphoteric surfactant and amino acid combination between the two.
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 containing lanthanum, cerium, samarium, yttrium, neodymium rare earth element, nitrate, oxalates, 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, 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, acetic acid, oxalic acid, propionic acid, tartaric acid, polyacrylic acid, maleic acid, ethylenediamine tetra-acetic acid, benzene sulfonic acid, 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 amphoteric surfactant is one or more the combination in betaine type, amino acid pattern, imidazoline type, amine oxide type surfactant.
6. a kind of rare earth accelerating agent for active dyeing as claimed in claim 1, 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, lysine.
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| 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 |
| CN103757944B (en) * | 2014-01-14 | 2015-07-01 | 傅科杰 | Composite printing and dyeing auxiliary as well as preparation method and application of auxiliary |
| CN105442349A (en) * | 2015-12-10 | 2016-03-30 | 缪琼华 | Preparation method of dyeing accelerant for reactive dyeing |
| CN105332296A (en) * | 2015-12-10 | 2016-02-17 | 缪琼华 | Accelerating agent for dyeing of reactive dyes |
| 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 |
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Effective date of registration: 20160411 Address after: Jinjiang Economic Development Zone in Fujian province 362261 (five yuan) Hin Yangxin Road No. 33 Patentee after: Fujian Province Jinjiang Dymatic Chemical Co., Ltd. Address before: 528305, Shunde hi tech Zone, Shunde District, Guangdong, Foshan Patentee before: Guangdong Demei Fine Chemical Co., Ltd. |