CN101922108A - Method for activated bleaching by using 1,4,7-triazacyclononane complexes - Google Patents
Method for activated bleaching by using 1,4,7-triazacyclononane complexes Download PDFInfo
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- CN101922108A CN101922108A CN2010102798499A CN201010279849A CN101922108A CN 101922108 A CN101922108 A CN 101922108A CN 2010102798499 A CN2010102798499 A CN 2010102798499A CN 201010279849 A CN201010279849 A CN 201010279849A CN 101922108 A CN101922108 A CN 101922108A
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- triazacyclononane
- bleaching
- metal complex
- low
- temperature activated
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Abstract
The invention relates to a method for low-temperature activated bleaching by using 1,4,7-triazacyclononane metal complexes, belonging to the field of methods for low-temperature activated bleaching. The method comprises the following steps: (1) taking the 1,4,7-triazacyclononane metal complexes, H2O2, penetrating agents and stabilizing agents and then mixing the substances to obtain bleaching operating fluid with pH value of 7-11; (2) padding the fabrics in the bleaching operating fluid; and (3) carrying out cold pad-batch or steaming on the padded fabrics and then washing the fabrics with water. The method is simple, low in cost, high in production efficiency, environment-friendly, energy-saving and suitable for industrialization and reduces the bleaching temperature, shortens the stacking time and reduces the fabrics damage under the premise of achieving good bleaching effect.
Description
Technical field
The invention belongs to the method field of low-temperature activated bleaching, particularly relate to a kind of use 1,4, the method for the low-temperature activated bleaching of 7-7-triazacyclononane complexes.
Background technology
Hydrogen peroxide bleaching is an important process in the textiles pre-treatment, and the whiteness height of BLEACHED FABRIC, not yellowing, environmental pollution are little, therefore is widely used in the pre-treatment bleaching process of various fabrics.
Conventional hydrogen peroxide bleaching comprises: high-temperature bleaching and the bleaching of cold rolling heap.
The technological process of high-temperature bleaching is: pad bleaching liquor → decatize → washing.
The bleaching liquid prescription is: H
2O
2(100%) 2～15g/L regulates pH value to 10.5～10.8 with caustic soda, and adding stabilizing agent and wetting agent are an amount of, pad bleaching liquor when room temperature, and 95～100 ℃ of decatize 45～60min wash out cloth then.
The shortcoming that high-temperature bleaching technology exists is a process energy consumption height, and fiber strength reduces, and it is coarse to handle the back fabric feeling.
The technological process of conventional cold rolling heap bleaching is: pad bleaching liquor → bank up → wash.
The bleaching liquid prescription is: H
2O
2(100%) be 18-20g/L, the alkali consumption is 50-60g/L, and adding stabilizing agent and wetting agent are an amount of, pad bleaching liquor when room temperature, and the 24h that banks up washes out cloth.
The shortcoming of conventional cold rolling heap bleaching is that technological temperature is low, alkali concn is high, the infiltration difficulty, and the present cold-pad-batch preparation time, about 24h, production efficiency was lower mostly.
For temperature that reduces the hydrogen peroxide high-temperature bleaching or the time that shortens conventional cold rolling heap bleaching, can in the hydrogen peroxide bleaching working solution, add the hydrogen peroxide activator, promote the decomposition rate of hydrogen peroxide at cryogenic conditions.
At present the hydrogen peroxide activator system of research and development mainly comprises: assorted how structure compounds of alkanoyl compounds, amide groups compounds, oxidation and organo-manganese compound etc.The product of industrialization mainly is (tetra-acetylated) ethylenediamine (TAED) and pelargonyl group benzene sulfonic acid sodium salt (NOBS) on the market; this two compounds has obtained using widely in American-European Betengent product, but is not very ripe all the time in the application in the pre-treatment of textiles hydrogen peroxide bleaching.
Summary of the invention
Technical problem to be solved by this invention provides a kind of use 1,4, the method for the low-temperature activated bleaching of 7-7-triazacyclononane complexes, and this method is simple, and cost is low, the production efficiency height, environmental protection and energy saving are suitable for industrialization and use; Reaching under the prerequisite of good bleaching effect, reducing bleaching temperature, shortening and bank up the time, reducing fabric damage.
Of the present invention a kind of 1,4, the application of the metal complex of 7-7-triazacyclononane in the textiles low-temperature activated bleaching.
The method of low-temperature activated bleaching comprises:
(1) preparation bleaching working solution
1,4, metal complex consumption 0.01～1000 μ mol/L of 7-7-triazacyclononane, H
2O
2Consumption 5～50g/L, bleeding agent consumption 1～5g/L, stabilizing agent dosage 0.1～10g/L, then described material is mixed the working solution of pH 7～11, preferred pH 9;
(2) pad
Textiles is put into above-mentioned bleaching working solution to be padded;
(3) textiles after will padding carries out cold dome or decatize, afterwards washing.
In the described step (1) 1,4, metal complex consumption 0.5～50 μ mol/L of 7-7-triazacyclononane.
In the described step (1) 1,4, the metal complex consumption of 7-7-triazacyclononane is preferably 1～20 μ mol/L.
Padding in the described step (2) is two to soak two and roll liquid carrying rate 50%～120%.
Textiles in the described step (2) is woven, knitted fabric or nonwoven textiles.
Cold batching process in the described step (3) is: 20～60 ℃ of the temperature of banking up, time 1～24h.
Decatize technology in the described step (3) is: 60～85 ℃ of steam temperatures, time 0.1～4h.
Washing in the described step (3) comprises hot water wash and cold wash.
In the described step (1) 1,4, the structural formula of the metal complex of 7-7-triazacyclononane is:
Described M is a kind of metal, is selected from a kind of among Mn (II)-(III)-(IV)-(V), Fe (II)-(III), Cu (I)-(II), Ti (II)-(III)-(IV), V (II)-(III)-(IV)-(V), the Co (I)-(II)-(III);
Described R
1, R
2, R
3Be selected from hydrogen, alkyl, a kind of in aryl, carboxyl, sulfonic group, hydroxyl, the pyridine radicals, R
1, R
2And R
3Can be identical or different;
X is the coordination material, be selected from any anion with 1,2 or 3 electric charge or any can be with the mode of 1,2 or 3 dentate neutral molecule, preferably from Cl to metal-complexing
-, Br
-, OH
-1, O
2 2-, H
2O, ROH and RCN;
Y is the counter ion of any non-coordination, preferably from Cl
-, Br
-, ClO
4 -And PF
6 -
A is the integer of 1-10;
K is the integer of 1-10;
N is the integer of 1-10;
M is 0 or the integer of 1-20;
Among the present invention preferred use 1,4,7-7-triazacyclononane metal complex bleach-activating comprises Mn
IV 2-(u-O)
3-(1,4,7-trimethyl-1,4,7-7-triazacyclononane)-(PF
6)
2, Mn
III 2-(u-O)-(u-OAc)
2-(1,4,7-trimethyl-1,4,7-7-triazacyclononane)-(ClO
4)
2, Mn
IV-(u-OCH
3)
3-(1,4,7-trimethyl-1,4,7-7-triazacyclononane)-(PF
6), Fe
2-(1,4,7-trimethyl-1,4,7-7-triazacyclononane)-Cl
2And the mixture of above-mentioned complex.
In the activation cold bleaching working solution of the present invention, can also comprise various auxiliary elements, as stabilizing agent and bleeding agent.The use of stabilizing agent mainly is the resolution ratio of control hydrogen peroxide, and it is evenly decomposed effectively, avoids fiber to suffer violent damage, improves the bleaching effect of hydrogen peroxide.Used stabilizing agent is generally the maleic acid acrylic copolymer, as: MA-AA.Adding bleeding agent among the present invention, is in order to strengthen bleaching liquid wetting to fabric, to help absorption and the diffusion of bleaching agent to fabric.Used bleeding agent is generally non-ionic surface active agent, as JFC.
Beneficial effect
The present invention uses 1,4, and 7-7-triazacyclononane metal complex makes up hydrogen peroxide/activator bleach system as bleach-activating, adopts the processing method of cold dome and/or decatize, reaches the effect to textile bleaching; Compare with the conventional high-temperature hydrogen peroxide bleaching process, reaching under the prerequisite of good bleaching effect, bleaching temperature is reduced to below 85 ℃ from 100 ℃, and working solution pH is controlled in 7 to 11 the scope preferred 9; Compare with conventional cold-pad-batch process, shorten cold dome and bank up the time, and will reduce working solution pH, thereby to the ecological, environmental protective of dyeing industry, energy-saving and cost-reducingly have a remarkable meaning.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
(1) preparation of working solution: in the 1000ml container, add each auxiliary agent successively.Penetrating agent JFC consumption: 2g/L; Stabilizing agent MA-AA consumption: 1g/L; Activator Fe
2-(1,4,7-trimethyl-1,4,7-7-triazacyclononane)-Cl
2Consumption is: 3 μ mol/L; 30%H
2O
2Consumption is: 30g/L; Regulate working solution pH=8, the processing fabric stirs.
(2) pad processing: textile half-bleached shirting two is soaked two and rolls on evenness calender with the working solution of above-mentioned (1) preparation, and liquid carrying rate is 95%.
(3) steaming step: 80 ℃ of steam temperatures, steaming time 1h.
(4) washing:, fully wash with cold water again with the hot wash twice of the COTTON FABRIC after the above-mentioned decatize with 50 ℃-80 ℃.
Embodiment 2
(1) preparation of working solution: in the 1000ml container, add each auxiliary agent successively.Penetrating agent JFC consumption: 2g/L; Stabilizing agent MA-AA consumption: 1g/L; Activator Fe
2-(1,4,7-trimethyl-1,4,7-7-triazacyclononane)-Cl
2Consumption is: 15 μ mol/L; 30%H
2O
2Consumption is: 30g/L; Regulating working solution pH is 9.5, and the processing fabric stirs.
(2) pad processing: textile half-bleached shirting two is soaked two and rolls on evenness calender with the working solution of above-mentioned (1) preparation, and liquid carrying rate is 95%.
(3) steaming step: 80 ℃ of steam temperatures, steaming time 1h.
(4) washing:, fully wash with cold water again with the hot wash twice of the COTTON FABRIC after the above-mentioned decatize with 50 ℃-80 ℃.
Embodiment 3
(1) preparation of working solution: in the 1000ml container, add each auxiliary agent successively.Penetrating agent JFC consumption: 2g/L; Stabilizing agent MA-AA consumption: 0.5g/L; Activator Fe
2-(1,4,7-trimethyl-1,4,7-7-triazacyclononane)-Cl
2Consumption is: 9 μ mol/L; 30%H
2O
2Consumption is: 30g/L; Regulating working solution pH is 9, and the processing fabric stirs.
(2) pad processing: textile half-bleached shirting two is soaked two and rolls on evenness calender with the working solution of above-mentioned (1) preparation, and liquid carrying rate is 95%.
(3) steaming step: 80 ℃ of steam temperatures, steaming time 1h.
(4) washing:, fully wash with cold water again with the hot wash twice of the COTTON FABRIC after the above-mentioned decatize with 50 ℃-80 ℃.
Embodiment 4
(1) preparation of working solution: in the 1000ml container, add each auxiliary agent successively.Penetrating agent JFC consumption: 2g/L; Stabilizing agent MA-AA consumption: 2g/L; Activator Fe
2-(1,4,7-trimethyl-1,4,7-7-triazacyclononane)-Cl
2Consumption is: 18 μ mol/L; 30%H
2O
2Consumption is: 30g/L; Transfer working solution pH to 9, the processing fabric stirs.
(2) pad step: the working solution of textile half-bleached shirting with above-mentioned (1) preparation soaked two at evenness calender two and roll, and liquid carrying rate is 95%.
(3) cold dome step: 40 ℃ of cold dome temperature, cold dome time 6h.
(4) washing:, fully wash with cold water with the hot wash twice of the COTTON FABRIC after the above-mentioned processing with 50 ℃-80 ℃.
Implementation result of the present invention
Processing fabric and each the contrast sample of above-mentioned example 1-4 are carried out whiteness and powerful contrast test analysis, the results are shown in table 1.
The whiteness test of fabric: adopt the U.S. moral tower color Datacolor of company 650 type color measurement and color match instrument that fabric whiteness is tested, according to the assessment method of GB 8425-87 textiles instrument whiteness, folding 4 layers of sample, twill towards outside, longitude and latitude is respectively surveyed three times.
The brute force of fabric is measured: utilize the H5K-S universal testing machine that the tensile strength and the breaking ductility of composite membrane are tested.Adopt the cloth method to test according to GB.
Table 1 bleaching effect of the present invention
Claims (10)
1. one kind is used 1,4, and the method for the low-temperature activated bleaching of the metal complex of 7-7-triazacyclononane comprises:
(1) bleaching working solution: 1,4, metal complex consumption 0.01～1000 μ mol/L of 7-7-triazacyclononane, H
2O
2Consumption 5～50g/L, bleeding agent consumption 1～5g/L, stabilizing agent dosage 0.1～10g/L, then described material is mixed the bleaching working solution of pH7～11;
(2) textiles being put into above-mentioned bleaching working solution pads;
(3) textiles after will padding carries out cold dome or decatize, afterwards washing.
2. a kind of use 1,4 according to claim 1, the method for the low-temperature activated bleaching of the metal complex of 7-7-triazacyclononane is characterized in that: 1,4 in the described step (1), metal complex consumption 1～20 μ mol/L of 7-7-triazacyclononane.
3. a kind of use 1,4 according to claim 1, the method for the low-temperature activated bleaching of the metal complex of 7-7-triazacyclononane is characterized in that: the pH in the described step (1) is 9.
4. a kind of use 1,4 according to claim 1, the method for the low-temperature activated bleaching of the metal complex of 7-7-triazacyclononane is characterized in that: padding in the described step (2) is two to soak two and roll liquid carrying rate 50%～120%.
5. a kind of use 1,4 according to claim 1, the method for the low-temperature activated bleaching of the metal complex of 7-7-triazacyclononane is characterized in that: the textiles in the described step (2) is woven, knitted fabric or nonwoven textiles.
6. a kind of use 1,4 according to claim 1, the method for the low-temperature activated bleaching of the metal complex of 7-7-triazacyclononane is characterized in that: the cold batching process in the described step (3) is 20～60 ℃ of the temperature of banking up, time 1～24h.
7. a kind of use 1,4 according to claim 1, the method for the low-temperature activated bleaching of the metal complex of 7-7-triazacyclononane is characterized in that: the decatize technology in the described step (3) is 60～85 ℃ of steam temperatures, time 0.1～4h.
8. a kind of use 1,4 according to claim 1, the method for the low-temperature activated bleaching of the metal complex of 7-7-triazacyclononane is characterized in that: the washing in the described step (3) is hot water wash and cold wash.
9. a kind of use 1,4 according to claim 1, the method for the low-temperature activated bleaching of the metal complex of 7-7-triazacyclononane is characterized in that, 1,4 in the step (1), the structural formula of the metal complex of 7-7-triazacyclononane is:
Described M is a kind of metal, is selected from a kind of among Mn (II)-(III)-(IV)-(V), Fe (II)-(III), Cu (I)-(II), Ti (II)-(III)-(IV), V (II)-(III)-(IV)-(V), the Co (I)-(II)-(III);
Described R1, R2, R3 are selected from hydrogen, alkyl, and be a kind of in aryl, carboxyl, sulfonic group, hydroxyl, the pyridine radicals, and R1, R2 are identical with R3 or different;
X is the coordination material, be selected from any anion with 1,2 or 3 electric charge or any can be with the mode of 1,2 or 3 dentate neutral molecule to metal-complexing;
Y is the counter ion of any non-coordination;
A is the integer of 1-10;
K is the integer of 1-10;
N is the integer of 1-10;
M is 0 or the integer of 1-20;
Described X is selected from Cl-, Br-, OH
-1, O
2 2-, H
2O, ROH, RCN;
Described Y is selected from Cl-, Br-, ClO
4-, PF
6-.
10. according to each described a kind of use 1,4 among the claim 1-9, the method for the low-temperature activated bleaching of the metal complex of 7-7-triazacyclononane is characterized in that: described 1,4, the metal complex of 7-7-triazacyclononane is Mn
IV 2-(u-O)
3-(1,4,7-trimethyl-1,4,7-7-triazacyclononane)-(PF
6)
2, Mn
III 2-(u-O)-(u-OAc)
2-(1,4,7-trimethyl-1,4,7-7-triazacyclononane)-(ClO
4)
2, Mn
IV-(u-OCH
3)
3-(1,4,7-trimethyl-1,4,7-7-triazacyclononane)-(PF
6), Fe
2-(1,4,7-trimethyl-1,4,7-7-triazacyclononane)-Cl
2In one or more mixture.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102493186A (en) * | 2011-11-24 | 2012-06-13 | 东华大学 | Low-temperature scouring and bleaching aid for textiles as well as preparation method and application of low-temperature scouring and bleaching aid |
| CN103174006A (en) * | 2011-11-24 | 2013-06-26 | 东华大学 | Application of bipyridyl pyrimidine metal complex to low-temperature scouring and bleaching auxiliary for textiles |
| CN103174010A (en) * | 2011-11-24 | 2013-06-26 | 东华大学 | Application of macrocyclic polyamine bridged metal complex to low-temperature scouring and bleaching auxiliary for textiles |
| CN103174011A (en) * | 2011-11-24 | 2013-06-26 | 东华大学 | Application of tetranitrogen bicyclotetradecane metal complex to low-temperature scouring and bleaching auxiliary for textiles |
| WO2018141237A1 (en) * | 2017-02-03 | 2018-08-09 | Rhodia Operations | Bleach or detergent composition |
| WO2021073554A1 (en) * | 2019-10-17 | 2021-04-22 | Rhodia Operations | Metal complex and use thereof |
| CN116084156A (en) * | 2022-12-12 | 2023-05-09 | 上海尚贤新材料有限公司 | Efficient rinsing liquid and application thereof in jean fabric rinsing process |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102493186A (en) * | 2011-11-24 | 2012-06-13 | 东华大学 | Low-temperature scouring and bleaching aid for textiles as well as preparation method and application of low-temperature scouring and bleaching aid |
| CN103174006A (en) * | 2011-11-24 | 2013-06-26 | 东华大学 | Application of bipyridyl pyrimidine metal complex to low-temperature scouring and bleaching auxiliary for textiles |
| CN103174010A (en) * | 2011-11-24 | 2013-06-26 | 东华大学 | Application of macrocyclic polyamine bridged metal complex to low-temperature scouring and bleaching auxiliary for textiles |
| CN103174011A (en) * | 2011-11-24 | 2013-06-26 | 东华大学 | Application of tetranitrogen bicyclotetradecane metal complex to low-temperature scouring and bleaching auxiliary for textiles |
| CN102493186B (en) * | 2011-11-24 | 2013-06-26 | 东华大学 | Low-temperature scouring and bleaching aid for textiles as well as preparation method and application of low-temperature scouring and bleaching aid |
| WO2018141237A1 (en) * | 2017-02-03 | 2018-08-09 | Rhodia Operations | Bleach or detergent composition |
| WO2021073554A1 (en) * | 2019-10-17 | 2021-04-22 | Rhodia Operations | Metal complex and use thereof |
| CN116084156A (en) * | 2022-12-12 | 2023-05-09 | 上海尚贤新材料有限公司 | Efficient rinsing liquid and application thereof in jean fabric rinsing process |
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