CN1986647A - Antiseptic active cationic dye and its preparing method - Google Patents
Antiseptic active cationic dye and its preparing method Download PDFInfo
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- CN1986647A CN1986647A CN 200610147558 CN200610147558A CN1986647A CN 1986647 A CN1986647 A CN 1986647A CN 200610147558 CN200610147558 CN 200610147558 CN 200610147558 A CN200610147558 A CN 200610147558A CN 1986647 A CN1986647 A CN 1986647A
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Abstract
The present invention relates to one kind of antiseptic active cationic dye and its preparation process. The dye has matrix in anthraquinone structure, active group of sym-triazine monochloride or sym-triazine monofluoride, water soluble group of long carbon chain quaternary ammonium salt structure and the chemical structure as shown. The dye may be used in dyeing and antiseptic finishing of various kinds of fiber and has high antiseptic effect, high color fastness and lasting antiseptic performance. It is prepared through the following steps: dissolving anthraquinone A and sym-triazine trichloride or sym-triazine trifluoride in nitrobenzene solvent, heating, cooling and filtering to obtain intermediate B; dissolving the intermediate B in DMF solvent, adding tertiary amine, heating to react, evaporating DMF and vacuum drying to obtain intermediate D; dissolving the intermediate D in DMF solvent, adding alkyl halide, heating to react, washing with ethyl ether, re-crystallizing and drying.
Description
Technical field
The invention belongs to dyestuff synthetic and textile dyeing and finishing field, particularly relate to antibacterial cation reactive dye and preparation method thereof.
Background technology
The dyeing of textiles is two important wet courses of processing with arrangement, and traditional textile dyeing and arrangement are separately carried out, and exists the shortcoming of expensive, high energy consumption and large amount of sewage discharging.With the dyeing and finishing processing technology that dyeing and functional treatment are finished in bathes, for reducing production costs, save energy reduces discharge of wastewater, preserves the ecological environment etc. to have great importance.Therefore, many experts both domestic and external have carried out many researchs in the field, aspect dyeing and antistatic, fire-retardant, antiultraviolet, shrinkproof and research that wrinkle proofing is finished in a bath, have obtained certain achievement.Yet, as a rule, because dyeing different with the finishing technique condition, need under the alkaline condition fixation to finish usually as reactive dyeing, and the resin wrinkle proofing needs an acidic catalyst, makes the use of this technology have bigger limitation.Antibacterial dye belongs to a kind of of functional dyestuff, and in recent years, because its weather resistance, simple for process and ecological, environmental protective etc. are paid close attention in the antibacterial finish of textiles more, therefore, such dyestuff has caused that people more and more pay attention to.
The antibacterial finish of textiles at present exists many shortcomings, as poor durability; Adopt resin or tackiness agent can make fabric feeling descend color change; The fabric Long contact time of human body and process antibacterial finish can form dermatitis; The relief liquor of antibacterial finish is as dealing with improperly in the factory, can destroy the probiotics in the environment and causes ecological problem etc.
The functional dyestuff that has good dyefastness on textiles is a kind of ideal antibacterial finishing agent, both at home and abroad to this report and few.The foreign scholar adopts aminoanthraquinone as dye matrix, and quaternary ammonium salt has synthesized a series of cationic antimicrobial dyestuffs as antibacterial components, and nylon and acrylic fabric have been carried out successfully dyeing, has obtained better anti-bacterial effect.But this dyestuff lacks avidity to cotton fibre, and owing to quaternary ammonium moiety in the molecule combines by amido linkage with dye matrix, hydrolysis easily, and make dyestuff lose anti-microbial property.
Antibacterial cation reactive dye (chemically-reactive dyes) is mainly used in cellulosic fibre, also can be used for protein fibre, tynex, polyacrylonitrile fibre and cationic dyeable polyester fiber.Antibiotic part in the dyestuff adopts quaternary ammonium salt structure, mainly is based on quaternary ammonium salt to human body safety, has broad spectrum antibacterial, can not cause mutation and the resistance of bacterium, the most important thing is and can combine with dye matrix, forms to have water miscible cationic dyestuff.
Summary of the invention
The objective of the invention is based on reactive dyestuffs the excellent dyeing behavior of cotton fibre and the sterilization mechanism of quaternary ammonium salt, reactive dyestuffs and quaternary ammonium salt bactericide group are combined, antibacterial cation reactive dye and preparation method thereof is provided, can dye and antibacterial finish to other fibers commonly used of cellulose fiber peacekeeping, have high antibacterial effect, make dyeing with antibacterial finish once finish and dyefastness good, antibiotic durable.
The molecular structure that antibacterial cation activity of the present invention is dyed is by the anthraquinone dye parent, the s-triazine active group is formed with the quaternary ammonium moiety with long carbochain, it is characterized in that such dyestuff is mainly used in the dyeing and the antibacterial finish of cellulosic fibre, short the dying that does not need neutral electrolyte (as sodium-chlor and sodium sulfate) when being used for cellulose dyeing, also can be used for protein fibre (as wool, silk etc.), tynex is (as nylon 66, nylon 6), acrylic fibers, the dyeing of fibers such as cation dyeable polyester and antibacterial finish, such dyestuff has very high anti-microbial property in solution or on the fiber, such dyestuff has very high avidity (absorption property) to above fiber, and has good every dyeing colour fastness.Chemical structure is as follows:
R
1, R
2, R
3Structure see Table 1
The preparation method that antibacterial cation activity of the present invention is dyed comprises the steps:
A. aminoanthraquinone A and trichlorine or trifluoro s-triazine are dissolved in the oil of mirbane organic solvent, with mixture heating up to 90 ℃, after 1 hour temperature is risen to 120 ℃, continuing stirring about 1 hour under this temperature, be cooled to 25-30 ℃, filter dyestuff intermediate B, methanol wash, dry in the vacuum drying device;
B. the dyestuff intermediate B with step a preparation is dissolved in DMF (N, the dinethylformamide) organic solvent, adds tertiary amines intermediate C in this mixture, in 55 ℃ of reactions 3-4 hour, reaction finished, and boils off solvent DMF in vacuum-evaporator, get dyestuff intermediate D, dry in the vacuum drying device;
C. step b is made to such an extent that dyestuff intermediate D is dissolved in the DMF organic solvent, in this mixture, add haloalkyl E, about reacting by heating mixture to 120 ℃, reacted 4-5 hour, reaction finishes, and boils off solvent DMF in vacuum-evaporator, the ether washing, ether-alcohol mixed solvent recrystallization gets dyestuff F, vacuum-drying in the vacuum drying oven.
The invention has the beneficial effects as follows: antibacterial cation reactive dye not only can be mainly used in cellulosic fibre, also can be used for the dyeing and the antibacterial finish of protein fibre, tynex, polyacrylonitrile fibre and cationic dyeable polyester fiber, have good dyeing affinity and antibiotic weather resistance, and dyeing and antibacterial finish are once finished, water saving, energy-conservation, ecological, environmental protective.
Embodiment
Provided by the invention have the active cationic dye of antibacterial and the dyeing mechanism that the preparation method has mainly utilized reactive dyestuffs and the antibiotic mechanism of quaternary ammonium salt, and the preparation method is based on the principle of acylations and alkylated reaction.Different with other antibacterial cation dyestuff, antibacterial cation reactive dye provided by the invention is except dyeing to fiber cable fiber and giving the antibacterial, can also finish dyeing and antibacterial finish simultaneously to protein fibre, tynex, polyacrylonitrile fibre and cationic dyeable polyester fiber, improve the range of application of such dyestuff.In addition, owing to have bigger hydrophobic group in such dye molecule, its affinity to bacterial cell membrane is improved, dyestuff antiseptic-germicide molecule combines with bacterial micro-organism easily, be convenient to the cytolemma that long hydrophobic carbochain pierces through bacterium, thereby bacterium is lost activity, and the general quaternary ammonium salt antiseptic of anti-microbial property is improved.
Following illustrative embodiment helps further to understand the present invention.
Embodiment 1
A. be that the 1-aminoanthraquinone of 17g and the trifluoro s-triazine of 20g are dissolved in the 200ml oil of mirbane organic solvent with quality, with mixture heating up to 90 ℃, after 1 hour temperature is risen to 120 ℃, continuing stirring about 1 hour under this temperature, be cooled to 25-30 ℃, filter dyestuff intermediate 1-(4,6-two chloro-2-amino s-triazine) aminoanthraquinone, methanol wash, dry in the vacuum drying device;
B. with the dyestuff intermediate 1-(4 of step a preparation, the amino s-triazine of 6-two chloro-2-) aminoanthraquinone 10g is dissolved in 150mlDMF (N, dinethylformamide) in the organic solvent, be heated to 55 ℃, in 30min, slowly splash into 1-amino-3-dimethylamino butane 5.5g, and afterreaction 2 hours, reaction finishes, in vacuum-evaporator, boil off solvent DMF, get dyestuff intermediate 1-(the amino s-triazine of 4-chloro-6-(1-amino-3-dimethylamino butane) 2-) aminoanthraquinone, dry in the vacuum drying device;
C. the dyestuff intermediate 9g that step b is made is dissolved in the 150ml DMF organic solvent, in this mixture, add the 3g lauryl chloride, about reacting by heating mixture to 120 ℃, reacted 4-5 hour, reaction finishes, and boils off solvent DMF in vacuum-evaporator, the ether washing, ether-alcohol mixed solvent recrystallization gets following structure yellow dyes, vacuum-drying in the vacuum drying oven.
The gained antibacterial cation reactive dye is dissolved in the water, be mixed with the solution of different concns, carry out antibacterial tests according to AATCC standard 100, the result shows that this dyestuff has excellent anti-microbial property to gram prolapse of uterus (E.coli) and gram sun bacterium (Staph.Aureus) in the aqueous solution.
The gained active cationic dye is dyeed to fibers such as cotton, wool, silk, nylon, acrylic fibers.To the cotton fabric dyeing process condition for example: adopt dip method, dye dosage 0.5-3% (owf); bath raio 30: 1; 70 ℃ of dyeing temperatures, time 30min, color fixing temperature is 85 ℃ in soda ash; 1 hour time; flush away not set and the hydrolised dye of finishing that dye, and carries out antibacterial tests according to 100 pairs of fabrics of AATCC standard then, and carries out the wash resistant test according to the AATCC standard.The dyeing temperature of fibers such as wool, silk, nylon, acrylic fibers is 95 ℃, and the time is 1-2 hour, and other conditions are with cotton basic identical.
Embodiment 2-21, the synthetic method of described antibacterial cation reactive dye is substantially the same manner as Example 1, and other condition sees Table 1.
Table 1 embodiment 2-21
Claims (6)
1. antibacterial cation reactive dye, it is characterized in that: dye matrix is an anthraquinone ring, and active group is a chloro-s-triazine or a fluorine s-triazine, and water soluble group is the quaternary ammonium salt structure with long carbochain, and chemical structure is as follows:
2. antibacterial cation reactive dye according to claim 1 is characterized in that: described dyestuff can be used for the dyeing and the antibacterial finish of fibers such as cellulosic fibre, protein fibre, tynex, acrylic fibers, cation dyeable polyester.
3. germ resistance active cationic dye according to claim 1 is characterized in that: when described dyestuff is used for cellulose dyeing, do not need the short of sodium-chlor or sodium sulfate to dye, can obtain high dye uptake.
4. germ resistance active cationic dye according to claim 1 is characterized in that: described dyestuff has the excellent antibiotic performance to gram prolapse of uterus and gram sun bacterium in solution and on the fiber.
5. germ resistance active cationic dye according to claim 1 is characterized in that: described dyestuff has very high avidity to above fiber, and has excellent every colour fastness.
6. the preparation method of germ resistance active cationic dye, it is characterized in that: this method comprises the steps:
A. aminoanthraquinone A and trichlorine or trifluoro s-triazine are dissolved in the oil of mirbane organic solvent, with mixture heating up to 90 ℃, after 1 hour temperature is risen to 120 ℃, continuing stirring about 1 hour under this temperature, be cooled to 25-30 ℃, filter dyestuff intermediate B, methanol wash, dry in the vacuum drying device;
B. the dyestuff intermediate B with step a preparation is dissolved in DMF (N, the dinethylformamide) organic solvent, adds tertiary amines intermediate C in this mixture, in 55 ℃ of reactions 3-4 hour, reaction finished, and boils off solvent DMF in vacuum-evaporator, get dyestuff intermediate D, dry in the vacuum drying device;
C. step b is made to such an extent that dyestuff intermediate D is dissolved in DMF (N, dinethylformamide) in the organic solvent, in this mixture, add haloalkyl E, about reacting by heating mixture to 120 ℃, reacted 4-5 hour, reaction finishes, in vacuum-evaporator, boil off solvent DMF, ether washing, ether-ethyl alcohol recrystallization, get dyestuff F, vacuum-drying in the vacuum drying oven.
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| CN102493222A (en) * | 2011-11-08 | 2012-06-13 | 青岛大学 | Dyeing method of reactive dye containing ionic liquid |
| CN101768372B (en) * | 2010-01-06 | 2013-12-11 | 东华大学 | Antibacterial cation reactive dye and preparation and application thereof |
| CN103725036A (en) * | 2014-01-05 | 2014-04-16 | 盐城纺织职业技术学院 | Orange red positive ion active dye |
| CN104357940A (en) * | 2014-10-28 | 2015-02-18 | 江苏工程职业技术学院 | Method for preparing composite polyamide fibers from antibacterial azo dye |
| CN104419221A (en) * | 2013-08-22 | 2015-03-18 | 盐城工业职业技术学院 | Preparation method and use of salt-free and alkali-free dyeing type activated dye |
| CN104448896A (en) * | 2014-10-28 | 2015-03-25 | 江苏工程职业技术学院 | Preparation method of antibacterial azo dye for polyarmide fibers |
| CN104911847A (en) * | 2014-03-13 | 2015-09-16 | 张家港市金陵纺织有限公司 | Production technology of nano-silver antibiosis pure cotton yarn dyed fabric |
| CN105484064A (en) * | 2015-11-17 | 2016-04-13 | 江南大学 | Novel haloamine antibacterial reactive dye, and preparation method and application thereof |
| CN105585875A (en) * | 2015-11-30 | 2016-05-18 | 南京工业大学 | Di-cationic reactive dye for salt-free dyeing of cotton woven fabrics and preparation method thereof |
| CN105694529A (en) * | 2015-11-30 | 2016-06-22 | 南京工业大学 | Positive ion reactive dye containing polyether amine chain segments and preparation method of positive ion reactive dye |
| CN107353671A (en) * | 2017-07-17 | 2017-11-17 | 南京工业大学 | A kind of azo structure contained active cationic dye and preparation method thereof |
| CN109914125A (en) * | 2019-02-22 | 2019-06-21 | 东华大学 | A kind of normal pressure exhaust process of biology base PTT series polyester textile |
| CN110616575A (en) * | 2019-10-25 | 2019-12-27 | 万得化工科技(上海)有限公司 | Reactive dye for textile and environment-friendly salt-free dyeing process thereof |
| CN114016198A (en) * | 2021-11-09 | 2022-02-08 | 江苏箭鹿毛纺股份有限公司 | Durable elastic woolen sweater made of modified polyester composite filaments and preparation method of durable elastic woolen sweater |
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| CN106987153B (en) * | 2017-04-28 | 2019-01-11 | 江苏迪安化工有限公司 | A kind of salt-free dyeing type yellow cationic reactive dye and its preparation method and application |
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2006
- 2006-12-20 CN CNB2006101475588A patent/CN100560654C/en not_active Expired - Fee Related
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| CN101768372B (en) * | 2010-01-06 | 2013-12-11 | 东华大学 | Antibacterial cation reactive dye and preparation and application thereof |
| CN102493222B (en) * | 2011-11-08 | 2014-01-01 | 青岛大学 | Dyeing method of reactive dye containing ionic liquid |
| CN102493222A (en) * | 2011-11-08 | 2012-06-13 | 青岛大学 | Dyeing method of reactive dye containing ionic liquid |
| CN104419221A (en) * | 2013-08-22 | 2015-03-18 | 盐城工业职业技术学院 | Preparation method and use of salt-free and alkali-free dyeing type activated dye |
| CN104419221B (en) * | 2013-08-22 | 2016-08-17 | 盐城工业职业技术学院 | A kind of salt-free non-alkali dyeing type reactive dye preparation and purposes |
| CN103725036B (en) * | 2014-01-05 | 2015-09-30 | 盐城工业职业技术学院 | A kind of orange red active cationic dye |
| CN103725036A (en) * | 2014-01-05 | 2014-04-16 | 盐城纺织职业技术学院 | Orange red positive ion active dye |
| CN104911847A (en) * | 2014-03-13 | 2015-09-16 | 张家港市金陵纺织有限公司 | Production technology of nano-silver antibiosis pure cotton yarn dyed fabric |
| CN104357940A (en) * | 2014-10-28 | 2015-02-18 | 江苏工程职业技术学院 | Method for preparing composite polyamide fibers from antibacterial azo dye |
| CN104448896A (en) * | 2014-10-28 | 2015-03-25 | 江苏工程职业技术学院 | Preparation method of antibacterial azo dye for polyarmide fibers |
| CN105484064A (en) * | 2015-11-17 | 2016-04-13 | 江南大学 | Novel haloamine antibacterial reactive dye, and preparation method and application thereof |
| CN105694529A (en) * | 2015-11-30 | 2016-06-22 | 南京工业大学 | Positive ion reactive dye containing polyether amine chain segments and preparation method of positive ion reactive dye |
| CN105585875A (en) * | 2015-11-30 | 2016-05-18 | 南京工业大学 | Di-cationic reactive dye for salt-free dyeing of cotton woven fabrics and preparation method thereof |
| CN105694529B (en) * | 2015-11-30 | 2017-06-23 | 南京工业大学 | The active cationic dye of one class containing polyetheramine segment and preparation method thereof |
| CN107353671A (en) * | 2017-07-17 | 2017-11-17 | 南京工业大学 | A kind of azo structure contained active cationic dye and preparation method thereof |
| CN109914125A (en) * | 2019-02-22 | 2019-06-21 | 东华大学 | A kind of normal pressure exhaust process of biology base PTT series polyester textile |
| CN109914125B (en) * | 2019-02-22 | 2021-07-20 | 东华大学 | Normal-pressure dip dyeing process of bio-based PTT series polyester fabric |
| CN110616575A (en) * | 2019-10-25 | 2019-12-27 | 万得化工科技(上海)有限公司 | Reactive dye for textile and environment-friendly salt-free dyeing process thereof |
| CN114016198A (en) * | 2021-11-09 | 2022-02-08 | 江苏箭鹿毛纺股份有限公司 | Durable elastic woolen sweater made of modified polyester composite filaments and preparation method of durable elastic woolen sweater |
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Assignee: Fujian province Changle City homologous Dyeing Co. Ltd. Assignor: Donghua University Contract record no.: 2010350000170 Denomination of invention: Antiseptic active cationic dye and its preparing method Granted publication date: 20091118 License type: Exclusive License Open date: 20070627 Record date: 20100719 |
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