CN104357940B - A kind of antibiotic azo dye prepares the method for composite polyamide fiber - Google Patents
A kind of antibiotic azo dye prepares the method for composite polyamide fiber Download PDFInfo
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Abstract
The invention discloses a kind of method that antibiotic azo dye prepares composite polyamide fiber.Antibacterial composite fibers of the present invention is obtained by the interior method that is mixed into.First based on 4-bromo-1,8-naphthalene acid anhydride prepares dyestuff colour base, then carry out the coupling of antibacterial functions group, prepare the azo dyes with antibacterial effect, above-mentioned antibacterial azo colorants and polyamide are obtained the polyamide compound fibre of durable antibiotic through co-blended spinning.The band look polyamide compound fibre that the method is obtained, the COLOR FASTNESS of fiber is excellent.There is high antibacterial effect simultaneously, Escherichia coli, staphylococcus aureus, hay bacillus, Candida albicans and Gram-negative bacteria are killed or inhibitory action.
Description
Technical field
The invention belongs to composite fibre synthesis field, be specifically related to a kind of method that antibiotic azo dye prepares composite polyamide fiber.
Background technology
Textiles is the fabulous medium of growth of microorganism, and its surface area contributes to microbial growth.At present, the antibacterial research of fiber is just causing increasing concern, the mainly finishing method of antibacterial textile process now, fabric is flooded, pad or applies reason with the solution or resin that contain antiseptic, dry when being accompanied by high temperature thus make fabric obtain anti-microbial property, usually process in dyeing and finishing processing final stage, this method for sorting is easy to process, and alternative antiseptic scope is wide.But there is the shortcoming such as poor durability, energy consumption height.
Adopting in fiber and being mixed into rule is add the serial antibacterial colorant of mixing at polymer melting spinning phase, imparts fiber bactericidal properties.Advantage is that fastness to washing is high, and antibacterial efficacy is lasting, saves mass energy, can not produce a large amount of waste water simultaneously, be conducive to environmental protection.
Summary of the invention
Goal of the invention: in order to solve the deficiencies in the prior art, the invention provides a kind of method that antibiotic azo dye prepares composite polyamide fiber.The composite polyamide fiber adopting the method obtained is compared with antibiotic finish after traditional dyeing, and in energy-conserving and environment-protective, antibacterial fabric persistence, fabric color fastness, the aspects such as solid grain size are significantly improved.Adopt amino dyestuff as dye matrix, preferred antibacterial components adopts the antibacterial colorant of method synthesizing series of diazo coupling, and antibacterial azo colorants and polyamide are obtained the polyamide compound fibre of durable antibiotic through co-blended spinning.Thus solve the problems such as antibacterial fabric persistence difference waits, dyestuff easily gathers.
Technical scheme: a kind of antibiotic azo dye of the present invention prepares the method for composite polyamide fiber, comprises the steps:
(1) dyestuff colour base preparation:
Join in 200ml absolute ethyl alcohol by bromo-for 0.6g-0.8g4-1,8-naphthalene acid anhydride, slowly stir 15 minutes, add amino-pyridine derivatives 0.5-0.7g, reflux 12 hours at temperature 70-80 DEG C, filter, ethanol is washed, suction filtration, obtains midbody compound A; 0.1-1.4g midbody compound A is added in 200ml absolute ethyl alcohol, slowly stir 15 minutes at temperature 65-75 DEG C, drip the cuprous iodide catalyst of 0.0002% of raw material midbody compd A weight, drip 25% ammoniacal liquor 100ml slowly, reflux 12 hours, 50 DEG C of filtrations, filtrate cools, and suction filtration, obtains the crude product of midbody compound B, with absolute ethyl alcohol recrystallization, obtain orange-yellow crystalline intermediate compd B;
(2) prepared by diazol C: slowly joined by natrium nitrosum 12-17g in the 100ml98% concentrated sulfuric acid, 15 minutes are being stirred lower than 5 DEG C of condition lower magnetic forces, finely dispersed composition is heated to 60 DEG C of insulations and magnetic agitation 1 hour, add midbody compound B0.2-0.4mol slowly after being cooled to 5 DEG C and added complete in 50 minutes, magnetic agitation fully reaction in 3 hours, must clarify diazol C;
(3) prepared by coupling agent D: the raw material getting 0.3-0.5mol coupling group is dissolved in 100-150ml36% acetic acid, then sodium acetate is added, the Acetic acid-sodium acetate buffer solution formed after utilizing mixing maintains solution pH value at 4-5, stirs 2 hours, obtain coupling agent D at 10 DEG C of condition lower magnetic forces;
(4) diazol C is joined in coupling agent D fast, hierarchy of control reaction temperature at 10 DEG C, magnetic agitation 3 hours; With 100 DEG C of hot water wash 5 minutes, leach precipitation, at 120 DEG C of temperature vacuumize 1 hour the colorant of antimicrobial form azo composite polyamide stock-dye;
(5) colorant of above-mentioned antimicrobial form azo polyamide fiber dyeing and polyamide are made through blended slice, melt spinning antibacterially contaminate polyamide fiber, wherein in blend, the pigment weight percentage of antimicrobial form azo polyamide fiber dyeing is 2-5%, all the other are polyamide, and spinning temperature is decided to be 200-300 DEG C.
As optimization, described amino-pyridine derivatives described in step (1) is the one in 3-amino-4-methyl-2-Pyridinecarboxylic Acid, 3-amino-4-methylpyridine.
As optimization, the raw material of coupling group described in step (2) is the one in N, N-diethyl-p-tlouidine, N, N-diethyl-3-acetylaminoaniline, N, N-diethyl-m-toluidine or N-ethyl-N hydroxyethyl aniline.
Beneficial effect: the present invention prepares the method for composite polyamide fiber by a kind of antibacterial azo dyes, there is work simplification, dyefastness is good, and there is durable broad spectrum antibacterial, be applied to composite polyamide textile dyeing, after dyeing, polyamide fiber has high antibacterial effect, kills or inhibitory action Escherichia coli, staphylococcus aureus, hay bacillus, Candida albicans and Gram-negative bacteria.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be described in detail.
Specific embodiment 1:
Antibiotic azo dye prepares a method for composite polyamide fiber, comprises the steps:
(1) dyestuff colour base preparation:
Bromo-for 0.6g4-1,8-naphthalene acid anhydride is joined in 200ml absolute ethyl alcohol, slowly stirs 15 minutes at temperature 70 C, add amino-pyridine derivatives 0.5g, reflux 12 hours, filter, ethanol is washed, suction filtration, obtains midbody compound A, course of reaction following graphic shown in:
，
0.1g midbody compound A is added in 200ml absolute ethyl alcohol, slowly stir 15 minutes temperature 65 DEG C, drip the cuprous iodide catalyst of 0.0002% of raw material midbody compd A weight, drip 25% ammoniacal liquor 100ml slowly, reflux 12 hours, 50 DEG C of filtrations, filtrate cools, suction filtration, obtain the crude product of midbody compound B, course of reaction following graphic shown in, with absolute ethyl alcohol recrystallization, obtain orange-yellow crystalline intermediate compd B;
(2) prepared by diazol C: slowly joined by natrium nitrosum 12g in the 100ml98% concentrated sulfuric acid, 15 minutes are being stirred lower than 5 DEG C of condition lower magnetic forces, finely dispersed composition is heated to 60 DEG C of insulations and magnetic agitation 1 hour, add midbody compound B0.2mol slowly after being cooled to 5 DEG C and added complete in 50 minutes, magnetic agitation fully reaction in 3 hours, must clarify diazol C;
(3) prepared by coupling agent D: the N getting 0.3mol coupling group, N-diethyl-p-tlouidine is dissolved in 100ml36% acetic acid, then adds sodium acetate, and the Acetic acid-sodium acetate buffer solution formed after utilizing mixing maintains solution pH value at 4-5, stir 2 hours at 10 DEG C of condition lower magnetic forces, obtain coupling agent D;
(4) diazol C is joined in coupling agent D fast, hierarchy of control reaction temperature at 10 DEG C, magnetic agitation 3 hours; With 100 DEG C of hot water wash 5 minutes, leach precipitation, at 120 DEG C of temperature vacuumize 1 hour the colorant of antimicrobial form azo composite polyamide stock-dye, its molecular formula following graphic shown in;
Wherein R=N, N-diethyl-p-tlouidine
(5) colorant of above-mentioned antimicrobial form azo polyamide fiber dyeing and polyamide are made through blended slice, melt spinning antibacterially contaminate polyamide fiber, wherein in blend, the pigment weight percentage of antimicrobial form azo polyamide fiber dyeing is 2-5%, all the other are polyamide, and spinning temperature is decided to be 250 DEG C.
Specific embodiment 2:
(1) dyestuff colour base preparation:
Join in 200ml absolute ethyl alcohol by bromo-for 0.8g4-1,8-naphthalene acid anhydride, slowly stir 15 minutes, add amino-pyridine derivatives 0.7g, reflux 12 hours temperature 80 DEG C, filter, ethanol is washed, suction filtration, obtains midbody compound A; 1.4g midbody compound A is added in 200ml absolute ethyl alcohol, slowly stir 15 minutes temperature 75 DEG C, drip the cuprous iodide catalyst of 0.0002% of raw material midbody compd A weight, drip 25% ammoniacal liquor 100ml slowly, reflux 12 hours, 50 DEG C of filtrations, filtrate cools, and suction filtration, obtains the crude product of midbody compound B, with absolute ethyl alcohol recrystallization, obtain orange-yellow crystalline intermediate compd B;
(2) prepared by diazol C: slowly joined by natrium nitrosum 17g in the 100ml98% concentrated sulfuric acid, 15 minutes are being stirred lower than 5 DEG C of condition lower magnetic forces, finely dispersed composition is heated to 60 DEG C of insulations and magnetic agitation 1 hour, add midbody compound B0.4mol slowly after being cooled to 5 DEG C and added complete in 50 minutes, magnetic agitation fully reaction in 3 hours, must clarify diazol C;
(3) prepared by coupling agent D: the N getting 0.5mol coupling group, N-diethyl-3-acetylaminoaniline is dissolved in 150ml36% acetic acid, then sodium acetate is added, the Acetic acid-sodium acetate buffer solution formed after utilizing mixing maintains solution pH value at 4-5, stir 2 hours at 10 DEG C of condition lower magnetic forces, obtain coupling agent D;
(4) diazol C is joined in coupling agent D fast, hierarchy of control reaction temperature at 10 DEG C, magnetic agitation 3 hours; With 100 DEG C of hot water wash 5 minutes, leach precipitation, at 120 DEG C of temperature vacuumize 1 hour the colorant of antimicrobial form azo composite polyamide stock-dye, its molecular formula following graphic shown in;
Wherein R=N, N-diethyl-3-acetylaminoaniline
(5) colorant of above-mentioned antimicrobial form azo polyamide fiber dyeing and polyamide are made through blended slice, melt spinning antibacterially contaminate polyamide fiber, wherein in blend, the pigment weight percentage of antimicrobial form azo polyamide fiber dyeing is 2-5%, all the other are polyamide, and spinning temperature is decided to be 250 DEG C.
Specific embodiment 3:
(1) dyestuff colour base preparation:
Join in 200ml absolute ethyl alcohol by bromo-for 0.7g4-1,8-naphthalene acid anhydride, slowly stir 15 minutes, add amino-pyridine derivatives 0.6g, reflux 12 hours temperature 75 DEG C, filter, ethanol is washed, suction filtration, obtains midbody compound A; 0.7g midbody compound A is added in 200ml absolute ethyl alcohol, 15 minutes are slowly stirred at temperature 70 C, drip the cuprous iodide catalyst of 0.0002% of raw material midbody compd A weight, drip 25% ammoniacal liquor 100ml slowly, reflux 12 hours, 50 DEG C of filtrations, filtrate cools, and suction filtration, obtains the crude product of midbody compound B, with absolute ethyl alcohol recrystallization, obtain orange-yellow crystalline intermediate compd B;
(2) prepared by diazol C: slowly joined by natrium nitrosum 14g in the 100ml98% concentrated sulfuric acid, 15 minutes are being stirred lower than 5 DEG C of condition lower magnetic forces, finely dispersed composition is heated to 60 DEG C of insulations and magnetic agitation 1 hour, add midbody compound B0.3mol slowly after being cooled to 5 DEG C and added complete in 50 minutes, magnetic agitation fully reaction in 3 hours, must clarify diazol C;
(3) prepared by coupling agent D: the N-ethyl-N hydroxyethyl aniline getting 0.4mol coupling group is dissolved in 120ml36% acetic acid, then sodium acetate is added, the Acetic acid-sodium acetate buffer solution formed after utilizing mixing maintains solution pH value at 4-5, stirs 2 hours, obtain coupling agent D at 10 DEG C of condition lower magnetic forces;
(4) diazol C is joined in coupling agent D fast, hierarchy of control reaction temperature at 10 DEG C, magnetic agitation 3 hours; With 100 DEG C of hot water wash 5 minutes, leach precipitation, at 120 DEG C of temperature vacuumize 1 hour the colorant of antimicrobial form azo composite polyamide stock-dye, its molecular formula following graphic shown in;
Wherein R=N-ethyl-N hydroxyethyl aniline
(5) colorant of above-mentioned antimicrobial form azo polyamide fiber dyeing and polyamide are made through blended slice, melt spinning antibacterially contaminate polyamide fiber, wherein in blend, the pigment weight percentage of antimicrobial form azo polyamide fiber dyeing is 2-5%, all the other are polyamide, and spinning temperature is decided to be 250 DEG C.
Specific embodiment 4
Antibiotic azo dye prepares a method for composite polyamide fiber, comprises the steps:
(1) dyestuff colour base preparation:
Join in 200ml absolute ethyl alcohol by bromo-for 0.6g4-1,8-naphthalene acid anhydride, slowly stir 15 minutes, add amino-pyridine derivatives 0.6g, reflux 12 hours temperature 75 DEG C, filter, ethanol is washed, suction filtration, obtains midbody compound A; 0.5g midbody compound A is added in 200ml absolute ethyl alcohol, 15 minutes are slowly stirred at temperature 70 C, drip the cuprous iodide catalyst of 0.0002% of raw material midbody compd A weight, drip 25% ammoniacal liquor 100ml slowly, reflux 12 hours, 50 DEG C of filtrations, filtrate cools, and suction filtration, obtains the crude product of midbody compound B, with absolute ethyl alcohol recrystallization, obtain orange-yellow crystalline intermediate compd B;
(2) prepared by diazol C: slowly joined by natrium nitrosum 15g in the 100ml98% concentrated sulfuric acid, 15 minutes are being stirred lower than 5 DEG C of condition lower magnetic forces, finely dispersed composition is heated to 60 DEG C of insulations and magnetic agitation 1 hour, add midbody compound B0.2mol slowly after being cooled to 5 DEG C and added complete in 50 minutes, magnetic agitation fully reaction in 3 hours, must clarify diazol C;
(3) prepared by coupling agent D: the N getting 0.4mol coupling group, N-diethyl-m-toluidine is dissolved in 110ml36% acetic acid, then adds sodium acetate, and the Acetic acid-sodium acetate buffer solution formed after utilizing mixing maintains solution pH value at 4-5, stir 2 hours at 10 DEG C of condition lower magnetic forces, obtain coupling agent D;
(4) diazol C is joined in coupling agent D fast, hierarchy of control reaction temperature at 10 DEG C, magnetic agitation 3 hours; With 100 DEG C of hot water wash 5 minutes, leach precipitation, at 120 DEG C of temperature vacuumize 1 hour the colorant of antimicrobial form azo composite polyamide stock-dye, its molecular formula following graphic shown in;
Wherein R=N, N-diethyl-m-toluidine
(5) colorant of above-mentioned antimicrobial form azo polyamide fiber dyeing and polyamide are made through blended slice, melt spinning antibacterially contaminate polyamide fiber, wherein in blend, the pigment weight percentage of antimicrobial form azo polyamide fiber dyeing is 2-5%, all the other are polyamide, and spinning temperature is decided to be 250 DEG C.
According to above 4 embodiments, by the composite polyamide fiber of gained, carry out antibacterial tests with reference to AATCC standard 100, result shows this composite polyamide fiber has killing action to Escherichia coli, staphylococcus aureus, hay bacillus, Candida albicans.Simultaneously by obtained composite polyamide fiber, after washing 50 times, carry out antibacterial tests according to AATCC standard, result shows this composite polyamide fiber can have killing action to Escherichia coli, staphylococcus aureus, hay bacillus, Candida albicans, and has Durability of antimicrobial effect.
Anti-bacteria test result
Claims (1)
1. prepare a method for composite polyamide fiber with antibiotic azo dye, it is characterized in that: comprise the steps:
(1) dyestuff colour base preparation:
Join in 200mL absolute ethyl alcohol by bromo-for 0.6g-0.8g4-1,8-naphthalene acid anhydride, slowly stir 15 minutes, add amino-pyridine derivatives 0.5-0.7g, reflux 12 hours at temperature 70-80 DEG C, filter, ethanol is washed, suction filtration, obtains midbody compound A; 0.1-1.4g midbody compound A is added in 200mL absolute ethyl alcohol, slowly stir 15 minutes at temperature 65-75 DEG C, drip the cuprous iodide catalyst of 0.0002% of raw material midbody compd A weight, drip 25% ammoniacal liquor 100mL slowly, reflux 12 hours, 50 DEG C of filtrations, filtrate cools, and suction filtration, obtains the crude product of midbody compound B, with absolute ethyl alcohol recrystallization, obtain orange-yellow crystalline intermediate compd B; Described amino-pyridine derivatives is the one in 3-amino-4-methyl-2-Pyridinecarboxylic Acid, 3-amino-4-methylpyridine;
(2) prepared by diazol C: slowly joined by natrium nitrosum 12-17g in the 100mL98% concentrated sulfuric acid, 15 minutes are being stirred lower than 5 DEG C of condition lower magnetic forces, finely dispersed composition is heated to 60 DEG C of insulations and magnetic agitation 1 hour, add midbody compound B0.2-0.4mol slowly after being cooled to 5 DEG C and added complete in 50 minutes, magnetic agitation fully reaction in 3 hours, must clarify diazol C;
(3) prepared by coupling agent D: the raw material getting 0.3-0.5mol coupling group is dissolved in 100-150mL36% acetic acid, then sodium acetate is added, the Acetic acid-sodium acetate buffer solution formed after utilizing mixing maintains solution ph at 4-5, stirs 2 hours, obtain coupling agent D at 10 DEG C of condition lower magnetic forces; The raw material of described coupling group is the one in N, N-diethyl-p-tlouidine, N, N-diethyl-m-toluidine, N, N-diethyl-3-acetylaminoaniline or N-ethyl-N hydroxyethyl aniline;
(4) diazol C is joined in coupling agent D fast, hierarchy of control reaction temperature at 10 DEG C, magnetic agitation 3 hours; With 100 DEG C of hot water wash 5 minutes, leach precipitation, at 120 DEG C of temperature vacuumize 1 hour the colorant of antimicrobial form azo composite polyamide stock-dye;
(5) colorant of above-mentioned antimicrobial form azo polyamide fiber dyeing and polyamide are made through blended slice, melt spinning antibacterially contaminate polyamide fiber, wherein in blend, the pigment weight percentage of antimicrobial form azo polyamide fiber dyeing is 2-5%, all the other are polyamide, and spinning temperature is decided to be 200-300 DEG C.
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