CN103147275A - Method for modifying nylon fabric by magnetic nano ferrous oxide with photocatalytic activity - Google Patents
Method for modifying nylon fabric by magnetic nano ferrous oxide with photocatalytic activity Download PDFInfo
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Abstract
The invention discloses a method for modifying nylon fabric by magnetic nano ferrous oxide with photocatalytic activity. The method comprises the following steps of: firstly, preparing diluted hydrochloric acid solution, etching the nylon fabric by the prepared diluted hydrochloric acid solution, and then, swelling the etched nylon fabric; then, preparing a modifying solution of ferric sulfate, sodium hydroxide, sodium dodecyl benzene sulfonate and chitosan, and placing the pre-treated nylon fabric to the modifying solution for hydrothermal reaction to obtain modified nylon fabric; and finally, preparing a coupler solution, placing the modified nylon fabric to the coupler solution for treatment, and then, curing the modified nylon fabric treated by the coupler solution to obtain the nylon fabric coated with a magnetic nano ferrous trioxide particle thin film having photocatalytic activity. The nylon fabric modified by the method disclosed by the invention has good photocatalytic activity, magnetic property and scourability, and the handfeel and ventilation of the nylon fabric are not affected.
Description
Technical field
The invention belongs to function textile material technical field, relate to a kind of method of modifying of nylon fabric, be specifically related to a kind of method of photocatalytic activity and magnetic Nano di-iron trioxide modified nylon fabric.
Background technology
The nanometer di-iron trioxide has good photocatalytic activity and magnetic property, hardness is high, good weatherability, light resistance and chemical stability, be a kind of important inorganic pigment and fine ceramics raw material, can be used as photocatalysis degradation organic contaminant and magnetic pipe recording material.At present, preparation nanometer di-iron trioxide method can be divided into dry method and wet method generally.Dry method comprises microwave method, flame thermal decomposition, vapour deposition, nonthermal plasma chemistry vapour deposition process and LASER HEAT decomposition method etc.; Wet method comprises hydro-thermal method, forced hydrolysis method, gel-sol method, microemulsion method, the precipitation method and colloid chemistry method etc.Wherein to have the particle purity of preparation high for hydro-thermal method, good dispersion, and good crystalline and size are controlled, easily realize the advantages such as suitability for industrialized production high quality of products.Nylon fabric has excellent intensity and anti-wear performance, not only can be used as the wearing fabrics such as down jackets, anorak, but also be widely used in, decorate and TECHNICAL FABRIC, coat at the nylon fabric fiber surface nanometer ferric oxide particle film that one deck has photocatalytic activity and magnetic, will greatly widen the range of application of nylon fabric, improve added value of product.
Adopt at present hydro-thermal method also not have the correlation technique of nylon fabric clad nano ferric oxide particle film.Existing surface of nylon fabric method of modifying mainly contains two kinds: the one, and the functional fiber that preparation contains nano particle, in spinning process by nanoparticulate dispersed in the chemical fibre raw material, a fibroblast of respinning, its advantage is consistency of performance, and shortcoming is that nano particle and polymeric material compatibility are poor, and nanoparticulate dispersed is inhomogeneous, agglomeration is serious, most of nanoparticles embedded is in fibrous matrix, and seldom, so performance significantly descends the nano particle of fiber surface; The 2nd, use adhesive and auxiliary agent that nano particle is mixed with to dressing liquid, adopt dipping or the techniques such as compregnate, oven dry that nano particle is adhered to fabric face, equally also be faced with the problem of nanoparticle agglomerates, and the fabric wash resistant fastness after arranging is bad, the feel variation, wearability is greatly affected.
Summary of the invention
A kind of method that the purpose of this invention is to provide photocatalytic activity and magnetic Nano di-iron trioxide modified nylon fabric, nylon fabric after modification has good photocatalytic activity, magnetic property and washing durability, and does not affect feel and the gas permeability of nylon fabric.
The technical solution adopted in the present invention is, the method for photocatalytic activity and magnetic Nano di-iron trioxide modified nylon fabric is specifically implemented according to following steps:
Step 1, preparation dilute hydrochloric acid solution, utilize hydrochloric acid solution to carry out etching to nylon fabric, and the nylon fabric after then using DMF solution to etching carries out swelling treatment;
The modified solution of step 2, preparation ferric sulfate, NaOH, neopelex and shitosan, put into modified solution by pretreated nylon fabric and carry out hydro-thermal reaction, obtains the modified nylon fabric;
Step 3, preparation coupling agent solution, the modified nylon fabric is placed in to coupling agent solution to be processed, the modified nylon fabric that to process through coupling agent solution again is cured processing, obtains the nylon fabric that coats photocatalytic activity and magnetic Nano ferric oxide particle film.
Characteristics of the present invention also are,
Step 1 is specifically implemented according to following steps:
1.1) according to the volume ratio 1:4 of hydrochloric acid and water～6, the preparation dilute hydrochloric acid solution, the mass concentration of described hydrochloric acid is 36%;
1.2) take nylon fabric, according to bath raio 1:30～50, the nylon fabric taken is put into to step 1.1) dilute hydrochloric acid solution for preparing, under 50 ℃～70 ℃ conditions, dilute hydrochloric acid solution immersion treatment 20min～40min for nylon fabric by taking, complete the etching processing to nylon fabric;
1.3) by step 1.2) and in nylon fabric after etching processing be immersed in DMF, process 3h～5h under 70 ℃～90 ℃ conditions, then with deionized water, rinse well.
Step 2 is specifically implemented according to following steps:
2.1) quality of nylon fabric after processing according to step 1, measure deionized water with the bath raio of 1:30～50;
2.2) according to total concentration of iron, be 0.01mol/L～0.05mol/L, the mol ratio of ferric ion and hydroxide ion is Fe
3+: OH
-=1:2～1:4, take respectively ferric sulfate and NaOH;
2.3) by step 2.2) and in the ferric sulfate that takes dissolve in step 2.1) in the deionized water that measures, obtain ferrum sulfuricum oxydatum solutum, then add NaOH and fully stir, obtain ferric sulfate and NaOH mixed solution;
2.4) take respectively neopelex and shitosan, add the neopelex and the shitosan that take to step 2.3) in the ferric sulfate and NaOH mixed solution that prepare, constantly stir until neopelex and shitosan are dissolved in ferric sulfate and NaOH mixed solution, form modified solution, wherein in every liter of ferric sulfate and NaOH mixed solution, add the neopelex of 4g～8g, the shitosan of 2g～5g;
2.5) pour the pretreated nylon fabric of step 1 into step 2.4) and in the preparation modified solution in flood, dip time is 5min～10min;
2.6) will be through step 2.5) and nylon fabric after dipping together with modified solution, proceed in reaction cylinder after sealing, the volume of modified solution is no more than 60%～80% of reaction cylinder volume, reaction cylinder after sealing is risen to 120 ℃～140 ℃ with 2～4 ℃/min speed, then with 5～10r/min rotating speed isothermal reaction 3h～5h;
2.7) after question response is complete, cooling, the nylon fabric of taking-up being immersed in to 5min～10min in deionized water, dry 40min～60min under 60 ℃～90 ℃ vacuum conditions, obtain the modified nylon fabric.
The shitosan adopted in step 2 is the shitosan that deacetylation is 90%, molecular weight is less than 1000.
Step 3 is specifically implemented according to following steps:
3.1) according to the quality of nylon fabric, measure ethanolic solution for 1:80～120 in mass ratio;
3.2) according to 3-glycidyl propyl trimethoxy silicane coupling agent and step 3.1) and in the volume ratio of ethanolic solution of preparation be that 0.02～0.05:1 measures 3-glycidyl propyl trimethoxy silicane coupling agent, the 3-glycidyl propyl trimethoxy silicane coupling agent measured slowly is added drop-wise to step 3.1) in the ethanolic solution for preparing, while dripping constantly, stir, 10min～20min dropwises, by solution left standstill 30min～50min, obtain coupling agent solution after dropwising;
3.3) modified nylon textile impregnation that step 2 is obtained is in step 3.2) and in the coupling agent solution for preparing, and make modified nylon fabric and coupling agent solution carry out coupling reaction 4h～8h under 30 ℃～60 ℃ conditions;
3.4) step 3.3) and in coupling reaction after, the positive and negative two sides of the nylon fabric of taking-up is placed in respectively to irradiation 30min～50min under ultraviolet lamp, during irradiation, nylon fabric, apart from ultraviolet lamp 10cm～20cm, completes the curing processing to nylon fabric;
3.5) will be through step 3.4) and solidify nylon fabric after processing soak 5min～10min in acetone after, soak again 5min～10min in absolute ethyl alcohol, again with taking out after washed with de-ionized water nylon fabric 5min～10min, by the nylon fabric that cleans up in 70 ℃～90 ℃ vacuumizes, until dry, obtain coating the nylon fabric of photocatalytic activity and magnetic Nano ferric oxide particle film.
The power of the ultraviolet lamp that in step 3, curing reaction adopts is that 40W, dominant wavelength are 365nm.
Step 3.1) ethanolic solution in is that 1:5～10 are formulated by absolute ethyl alcohol and deionized water according to volume ratio.
The invention has the beneficial effects as follows, adopt hydro-thermal method in the process for preparing photocatalytic activity and magnetic Nano di-iron trioxide crystal, the nanometer di-iron trioxide crystal grain of generation is directly loaded to the nylon fabric fiber surface, coat the nanometer ferric oxide particle film of one deck densification on the nylon fibre surface, give nylon fabric photocatalytic activity and magnetic property; And by regulating the source of iron consumption, reaction temperature and time, the selecting and the technique such as coupling post processing of dispersant, optimization best modification scheme; The inventive method can be saved raw material, easy and simple to handle, and nanometer di-iron trioxide attachment fastness is good.Test result shows, the nylon fabric after the modification of nanometer di-iron trioxide can the photo-catalytic degradation of methyl-orange dyestuff, and after 30 standards washings, fabric still has certain magnetic property.
The accompanying drawing explanation
Fig. 1 is the stereoscan photograph of common nylon fabric;
Fig. 2 is the stereoscan photograph after adopting the inventive method to the modification of nylon fabric clad nano ferric oxide particle;
Fig. 3 is the nanometer ferric oxide particle X-ray diffraction spectrogram that surface of nylon fabric coats;
Fig. 4 is the forward and backward ultraviolet visible ray of the nylon fabric nanometer di-iron trioxide modification spectral curve that diffuses;
Fig. 5 is the B-H loop after adopting the inventive method to the modification of nylon fabric clad nano di-iron trioxide.
The specific embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
The method of photocatalytic activity of the present invention and magnetic Nano di-iron trioxide modified nylon fabric, specifically according to following steps, implement:
Step 1, preparation dilute hydrochloric acid solution, utilize the dilute hydrochloric acid solution of preparation to carry out etching to nylon fabric, and the nylon fabric after then using DMF solution to etching carries out swelling treatment; Specifically according to following steps, implement:
1.1) according to the volume ratio 1:4 of hydrochloric acid and water～6, the preparation dilute hydrochloric acid solution, the mass concentration of described hydrochloric acid is 36%;
1.2) take nylon fabric, according to bath raio 1:30～50, the nylon fabric taken is put into to step 1.1) dilute hydrochloric acid solution for preparing, under 50 ℃～70 ℃ conditions, dilute hydrochloric acid solution immersion treatment 20min～40min for nylon fabric by taking, complete the etching processing to nylon fabric;
1.3) by step 1.2) and in nylon fabric after etching processing be immersed in DMF, process 3h～5h under 70 ℃～90 ℃ conditions, then with deionized water, rinse well.
The modified solution of step 2, preparation ferric sulfate, NaOH, neopelex and shitosan, put into modified solution by pretreated nylon fabric and carry out hydro-thermal reaction, obtains the modified nylon fabric, specifically according to following steps, implements:
2.1) quality of nylon fabric after processing according to step 1, measure deionized water with the bath raio of 1:30～50;
2.2) according to total concentration of iron, be 0.01mol/L～0.05mol/L, the mol ratio of ferric ion and hydroxide ion is Fe
3+: OH
-=1:2～1:4, take respectively ferric sulfate and NaOH;
2.3) by step 2.2) and in the ferric sulfate that takes dissolve in step 2.1) in the deionized water that measures, obtain ferrum sulfuricum oxydatum solutum, then add NaOH and fully stir, obtain ferric sulfate and NaOH mixed solution;
2.4) take respectively neopelex and shitosan, add the neopelex and the shitosan that take to step 2.3) in the ferric sulfate and NaOH mixed solution that prepare, constantly stir until neopelex and shitosan are dissolved in ferric sulfate and NaOH mixed solution, form modified solution, wherein in every liter of ferric sulfate and NaOH mixed solution, add the neopelex of 4g～8g, the shitosan of 2g～5g;
2.5) pour the pretreated nylon fabric of step 1 into step 2.4) and in the preparation modified solution in flood, dip time is 5min～10min;
2.6) will be through step 2.5) and nylon fabric after dipping together with modified solution, proceed in reaction cylinder after sealing, the volume of modified solution is no more than 60%～80% of reaction cylinder volume, reaction cylinder after sealing is risen to 120 ℃～140 ℃ with 2～4 ℃/min speed, then with 5～10r/min rotating speed isothermal reaction 3h～5h;
2.7) after question response is complete, cooling, the nylon fabric of taking-up being immersed in to 5min～10min in deionized water, dry 40min～60min under 60 ℃～90 ℃ vacuum conditions, obtain the modified nylon fabric.
Shitosan wherein is the shitosan that deacetylation is 90%, molecular weight is less than 1000.
Step 3, preparation coupling agent solution, the modified nylon fabric is placed in to coupling agent solution to be processed, the modified nylon fabric that to process through coupling agent solution again is cured processing, obtain the nylon fabric that coats photocatalytic activity and magnetic Nano ferric oxide particle film, specifically implement according to following steps:
3.1) according to the quality of nylon fabric, measuring ethanolic solution for 1:80～120 in mass ratio, ethanolic solution is that 1:5～10 are formulated by absolute ethyl alcohol and deionized water according to volume ratio.
3.2) according to 3-glycidyl propyl trimethoxy silicane coupling agent and step 3.1) and in the volume ratio of ethanolic solution of preparation be that 0.02～0.05:1 measures 3-glycidyl propyl trimethoxy silicane coupling agent, the 3-glycidyl propyl trimethoxy silicane coupling agent measured slowly is added drop-wise to step 3.1) in the ethanolic solution for preparing, while dripping constantly, stir, 10min～20min dropwises, by solution left standstill 30min～50min, obtain coupling agent solution after dropwising;
3.3) modified nylon textile impregnation that step 2 is obtained is in step 3.2) and in the coupling agent solution for preparing, and make modified nylon fabric and coupling agent solution carry out coupling reaction 4h～8h under 30 ℃～60 ℃ conditions;
3.4) step 3.3) and in coupling reaction after, the positive and negative two sides of the nylon fabric of taking-up is placed in respectively to irradiation 30min～50min under ultraviolet lamp, during irradiation, nylon fabric, apart from ultraviolet lamp 10cm～20cm, completes the curing processing to nylon fabric; The power of the ultraviolet lamp that curing reaction adopts is that 40W, dominant wavelength are 365nm.
3.5) will be through step 3.4) and solidify nylon fabric after processing soak 5min～10min in acetone after, soak again 5min～10min in absolute ethyl alcohol, again with taking out after washed with de-ionized water nylon fabric 5min～10min, by the nylon fabric that cleans up in 70 ℃～90 ℃ vacuumizes, until dry, obtain coating the nylon fabric of photocatalytic activity and magnetic Nano ferric oxide particle film.
Fig. 1 is the stereoscan photograph of common nylon fabric, Fig. 2 is the stereoscan photograph of clad nano di-iron trioxide nylon fabric, can find out: common nylon fabric fiber surface is very clean, do not have other materials to adhere to, and the nylon fabric fiber surface after the loaded with nano di-iron trioxide has coated the thicker particulate material of one deck, also be studded with some tiny particles, the high power electromicroscopic photograph shows that this particle clad is comprised of nano-scale particle simultaneously.Fig. 3 is the nanometer ferric oxide particle X-ray diffraction spectrogram that surface of nylon fabric coats, test result shows: the angle of diffraction 2 θ stronger diffraction maximum occurred 24 °, 33 °, 36 °, 41 °, 49 °, 54 °, 62 ° and 64 ° of left and right, consistent with the No.89-0599 in standard diagram JCPDF, respectively corresponding (012) of bloodstone α-di-iron trioxide, (104), (110), (113), (024), (116), (214) and (300) crystal face.Fig. 4 is the forward and backward ultraviolet visible ray of the nylon fabric nanometer di-iron trioxide modification spectral curve that diffuses.Can find out, after nylon fabric clad nano di-iron trioxide, not only ultraviolet radiation absorption significantly be strengthened, and visible ray is also increased to some extent.Fig. 5 is the B-H loop of clad nano di-iron trioxide nylon fabric, and test result shows: the nylon fabric of clad nano di-iron trioxide shows weak magnetic property, and remanent magnetization is 0.00043emug
-1, coercivity is 205.0Oe.
Select methyl orange dye to carry out photocatalytic activity mensuration.By size, be that nylon fabric that 10cm * 10cm quality is about 1.2g is immersed in the methyl orange solution that volume 50mL, mass concentration are 2mg/l, reach adsorption equilibrium after being placed in darkroom 90min, then be placed under quartz ultraviolet lamp and carry out irradiation, the power of ultraviolet lamp is 20W, dominant wavelength is 254nm, light source distance methyl orange liquid level is 10cm, by the forward and backward absorbance at maximum absorption wavelength 464nm place of 7220N type spectrophotometric determination methyl orange solution irradiation 5h, calculate the degradation rate D of methyl orange according to formula (1).
In formula, A
0initial absorbance while for methyl orange solution, reaching adsorption equilibrium, A
1absorbance for the methyl orange solution after ultraviolet irradiation 5h.
According to standard GB/T/T 8629-2001 " textiles is home washings and drying program for test ", clad nano di-iron trioxide nylon fabric is washed and dry (selecting A type washing machine, 4A washing procedure, A type drying program).And measure the hysteresis curve of clad nano di-iron trioxide nylon fabric with VSM multifunction vibration sample magnetometer (U.S. Quantum Design company), calculate remanent magnetization and coercivity.
Beneficial effect of the present invention place is described from the principle aspect:
(1) the present invention is by controlling the concentration of ferric sulfate, the mol ratio of ferric sulfate and NaOH, reaction temperature and time, selecting and consumption of dispersant, the nylon fabric acid etch is processed, and coupling modification post-processing approach, make the nanometer ferric oxide particle that is coated on the nylon fabric fiber surface firm, fine and close, particle is nanoscale, with fibre substrate, is combined well, has certain photocatalytic activity and magnetic property.This is because ferric sulfate concentration, the mol ratio of ferric sulfate and NaOH, reaction temperature and time, dispersant dosage, the nylon fabric acid etch, coupling modification post processing all affects photocatalytic activity, magnetic, purity, crystallization degree, pattern, the particle size of nanometer di-iron trioxide and coats fastness.According to a large amount of experiments, show: when total concentration of iron is 0.01～0.05mol/L, surface of nylon fabric can coat certain thickness nanometer ferric oxide film, can not deposit too many nano particle in solution simultaneously; When being less than 0.01mol/L, in solution, very little, surface of nylon fabric can not form continuous clad to iron ion content, affects photocatalytic activity and magnetic property; When being greater than 0.05mol/L, iron concentration is excessive easily causes waste, and because the nanometer di-iron trioxide is reunited, the nanometer ferric oxide film fastness that makes fabric face coat is bad.
(2) when ferric iron and hydroxyl mol ratio be Fe
3+: OH
-during=1:2～1:4, can make ferric sulfate all transform into the nanometer di-iron trioxide, product purity is high; When mol ratio is less than 1:2 or is greater than 1:4, the bloodstone nanometer di-iron trioxide of generation is fewer, and contains other dephasign compositions.
(3) when reaction temperature is controlled at 120～140 ℃, can generate bloodstone nanometer di-iron trioxide crystal grain, crystallization degree is high; When temperature during lower than 120 ℃, nanometer di-iron trioxide crystal poor growth, crystal formation is bad, almost there is no magnetic; When temperature, during higher than 150 ℃, nylon fabric intensity is subject to major injury, can not use.
(4) reaction time and stirring major effect crystal morphology and the particle size of nanometer di-iron trioxide: when the reaction time is controlled at 3～5h, the nanometer ferric oxide particle generated is little and be evenly distributed, and the nanometer ferric oxide film coated at surface of nylon fabric is complete, fine and close; When being less than 3h, nanometer di-iron trioxide crystal grain ateliosis, poor with the nylon fibre binding strength; When being greater than 5h, the nano ferriferrous oxide granule of generation is reunited obviously, and it is large that particle size becomes, and covered effect is bad, easily comes off, and nylon fabric intensity descends larger.
(5) add neopelex and shitosan, can control preferably the size of nanometer ferric oxide particle: when the neopelex consumption at 4～8g/L, chitosan dosage is when 2～5g/L, and the nanometer ferric oxide particle of generation is nanoscale; When the neopelex consumption is less than 4g/L, when chitosan dosage is less than 2g/L, do not have the effect of controlling nanometer di-iron trioxide crystal size; When the neopelex consumption is greater than 8g/L, when chitosan dosage is greater than 5g/L, affect nanometer ferric oxide coated nylon fabric.
(6) use watery hydrochloric acid to process nylon fabric, can form some micropores and pitting on the nylon fibre surface, improve the coating fastness of nanometer ferric oxide particle: when the volume ratio of hydrochloric acid and water is 1:4～6,50～70 ℃ of temperature, during time 20～40min, can go out more little micropore and pit in the nylon fibre surface etch; When the volume ratio of hydrochloric acid and water is greater than 1:4, temperature is lower than 50 ℃, and the time, while being less than 20min, etching effect was not obvious; When the volume ratio of hydrochloric acid and water is less than 1:4, temperature is higher than 70 ℃, and the time, while being longer than 40min, the nylon fibre etching was serious, and strength damage is larger.
(7) the coupling agent modified processing of 3-glycidyl propyl trimethoxy silicane, can greatly improve the binding strength of nanometer di-iron trioxide and nylon fabric: when the volume ratio of 3-glycidyl propyl trimethoxy silicane and absolute ethyl alcohol is 0.02～0.05:1, absolute ethyl alcohol and deionized water volume ratio are 1:5～10 o'clock, can control well the hydrolysis rate of 3-glycidyl propyl trimethoxy silicane, improve the binding strength of nanometer di-iron trioxide and nylon fibre; When the volume ratio of 3-glycidyl propyl trimethoxy silicane and absolute ethyl alcohol is greater than 0.05:1, when absolute ethyl alcohol and deionized water volume ratio are less than 1:5, slowly, coupling effect extends the hydrolysis of 3-glycidyl propyl trimethoxy silicane; When the volume ratio of 3-glycidyl propyl trimethoxy silicane and absolute ethyl alcohol is less than 0.02:1, when absolute ethyl alcohol and deionized water volume ratio are greater than 1:10, the hydrolysis of 3-glycidyl propyl trimethoxy silicane is accelerated, and loses coupling activity.When reaction temperature, at 40～60 ℃, the reaction time, when 4～8h, can be improved the attachment fastness of nanometer di-iron trioxide; When reaction temperature, during lower than 40 ℃, the hydrolysis of 3-glycidyl propyl trimethoxy silicane slowly; When reaction temperature, during higher than 60 ℃, the hydrolysis of 3-glycidyl propyl trimethoxy silicane is accelerated.When the reaction time is less than 4h, coupling effect is bad; When the reaction time is greater than 8h, lose time.The use ultraviolet ray is cured, can improve between the nanometer ferric oxide particle and and nylon fibre between bond strength.
Embodiment 1
According to hydrochloric acid and water volume ratio 1:6, preparation hydrochloric acid weak solution, take the nylon fabric of 5g, according to bath raio 1:50, nylon fabric is put into to the dilute hydrochloric acid solution of 250mL, process 20min under 50 ℃ of conditions, then by etching, good nylon fabric is immersed in N, in dinethylformamide, under 70 ℃ of conditions, process 3h, clean with deionized water, according to the nylon fabric quality, measure the deionized water of 150mL with bath raio 1:30, according to total concentration of iron, be 0.01mol/L, ferric iron and hydroxyl mol ratio are Fe
3+: OH
-=1:2, take respectively ferric sulfate and NaOH, ferric sulfate is dissolved in deionized water, obtain ferrum sulfuricum oxydatum solutum, then add NaOH and fully stir, obtain ferric sulfate and NaOH mixed solution, the shitosan of the neopelex of 0.6g and 0.3g is added in ferric sulfate and NaOH mixed solution, wherein deacetylating degree of chitosan is 90%, molecular weight is less than 1000, and constantly stir, be mixed with modified solution, pretreated nylon fabric is poured in the modified solution prepared and flooded 5min, then nylon fabric is proceeded in reaction cylinder and seals together with modified solution, the modified solution volume is no more than 60% of reaction cylinder volume, rise to 120 ℃ with 2 ℃/min speed, with 5r/min rotating speed isothermal reaction 5h, the complete taking-up nylon fabric of question response, be immersed in 5min in deionized water, dry 60min under 60 ℃ of vacuum conditions, obtain the modified nylon fabric, according to the nylon fabric quality, with bath raio, 1:80 measures ethanolic solution, and this ethanolic solution is according to volume ratio, to be that 1:5 is formulated by absolute ethyl alcohol and deionized water.Volume ratio according to 3-glycidyl propyl trimethoxy silicane coupling agent and ethanolic solution is that 0.02:1 measures 3-glycidyl propyl trimethoxy silicane coupling agent, and slowly be added drop-wise in ethanolic solution by it, while dripping constantly, stir, 10min dropwises, then standing 30min, obtain coupling agent solution, by the modified nylon textile impregnation in coupling agent solution, carry out coupling reaction 4h under 60 ℃ of conditions, after completion of the reaction by nylon fabric just, anti-two sides is placed in respectively hardening with radiation 30min under ultraviolet lamp, fabric is apart from ultraviolet lamp 10cm, wherein the power of ultraviolet lamp is 40W, dominant wavelength is 365nm, the nylon fabric solidified after processing is immersed in to acetone, each 5min in absolute ethyl alcohol, use again washed with de-ionized water 5min, vacuumize under 70 ℃ of conditions, obtain coating the nylon fabric of photocatalytic activity and magnetic Nano ferric oxide particle film.
Estimating the photocatalytic activity of nanometer di-iron trioxide modified nylon fabric with ultraviolet lamp irradiation methyl orange dye solution, through the ultraviolet irradiation of 5h, is 81% to the degradation rate of methyl orange dye.According to standard GB/T/T 8629-2001 " textiles is home washings and drying program for test ", clad nano di-iron trioxide nylon fabric is washed and dry (selects A type washing machine, the 4A washing procedure, A type drying program), and measure the hysteresis curve of clad nano di-iron trioxide nylon fabric with VSM multifunction vibration sample magnetometer (U.S. Quantum Design company), after 30 standard washings, the remanent magnetization of clad nano di-iron trioxide nylon fabric is 0.00031emug
-1, coercivity is 187Oe.
Embodiment 2
According to hydrochloric acid and water volume ratio 1:4, preparation hydrochloric acid weak solution, take the nylon fabric of 5g, according to bath raio 1:30, nylon fabric is put into to the dilute hydrochloric acid solution of 150mL, process 40min under 70 ℃ of conditions, then by etching, good nylon fabric is immersed in N, in dinethylformamide solution, under 90 ℃ of conditions, process 5h, clean with deionized water, according to the nylon fabric quality, measure the deionized water of 250mL with bath raio 1:50, according to total concentration of iron, be 0.05mol/L, ferric iron and hydroxyl mol ratio are Fe
3+: OH
-=1:4, take respectively ferric sulfate and NaOH, ferric sulfate is dissolved in deionized water, obtain ferrum sulfuricum oxydatum solutum, then add NaOH and fully stir, obtain ferric sulfate and NaOH rufous mixed solution, the shitosan of the neopelex of 2g and 1.25g is added in ferric sulfate and NaOH mixed solution, wherein deacetylating degree of chitosan is 90%, molecular weight is less than 1000, and constantly stir, be mixed with modified solution, pretreated nylon fabric is poured in the modified solution prepared and flooded 10min, then nylon fabric is proceeded in reaction cylinder and seals together with modified solution, the modified solution volume is no more than 80% of reaction cylinder volume, rise to 140 ℃ with 4 ℃/min speed, with 10r/min rotating speed isothermal reaction 3h, the complete taking-up nylon fabric of question response, be immersed in 10min in deionized water, dry 40min under 90 ℃ of vacuum conditions, obtain the modified nylon fabric, according to the nylon fabric quality, with bath raio, 1:120 measures ethanolic solution, and this ethanolic solution is according to volume ratio, to be that 1:10 is formulated by absolute ethyl alcohol and deionized water.Volume ratio according to 3-glycidyl propyl trimethoxy silicane coupling agent and ethanolic solution is that 0.05:1 measures 3-glycidyl propyl trimethoxy silicane coupling agent, and slowly be added drop-wise in absolute ethyl alcohol by it, while dripping constantly, stir, 20min dropwises, then standing 50min, obtain coupling agent solution, by the modified nylon textile impregnation in coupling agent solution, carry out coupling reaction 8h under 30 ℃ of conditions, after completion of the reaction by nylon fabric just, anti-two sides is placed in respectively hardening with radiation 50min under ultraviolet lamp, fabric is apart from ultraviolet lamp 20cm, wherein the power of ultraviolet lamp is 40W, dominant wavelength is 365nm, the nylon fabric solidified after processing is immersed in to acetone successively, each 10min in absolute ethyl alcohol, use again washed with de-ionized water 10min, vacuumize under 90 ℃ of conditions, obtain coating the nylon fabric of photocatalytic activity and magnetic Nano ferric oxide particle film.
Estimating the photocatalytic activity of nanometer di-iron trioxide modified nylon fabric with ultraviolet lamp irradiation methyl orange dye solution, through the ultraviolet irradiation of 5h, is 92% to the degradation rate of methyl orange dye.According to standard GB/T/T 8629-2001 " textiles is home washings and drying program for test ", clad nano di-iron trioxide nylon fabric is washed and dry (selects A type washing machine, the 4A washing procedure, A type drying program), and measure the hysteresis curve of clad nano di-iron trioxide nylon fabric with VSM multifunction vibration sample magnetometer (U.S. Quantum Design company), after 30 standard washings, the remanent magnetization of clad nano di-iron trioxide nylon fabric is 0.00074emug
-1, coercivity is 325Oe.
Embodiment 3
According to hydrochloric acid and water volume ratio 1:5, preparation hydrochloric acid weak solution, take the nylon fabric of 5g, according to bath raio 1:40, nylon fabric is put into to the dilute hydrochloric acid solution of 200mL, process 30min under 60 ℃ of conditions, then by etching, good nylon fabric is immersed in N, in dinethylformamide, under 80 ℃ of conditions, process 4h, clean with deionized water, according to the nylon fabric quality, measure the deionized water of 200mL with bath raio 1:40, according to total concentration of iron, be 0.03mol/L, ferric iron and hydroxyl mol ratio are Fe
3+: OH
-=1:3, take respectively ferric sulfate and NaOH, ferric sulfate is dissolved in deionized water, obtain ferrum sulfuricum oxydatum solutum, then add NaOH and fully stir, obtain ferric sulfate and NaOH mixed solution, the shitosan of the neopelex of 1.2g and 0.6g is added in ferric sulfate and NaOH mixed solution, wherein deacetylating degree of chitosan is 90%, molecular weight is less than 1000, and constantly stir, be mixed with modified solution, pretreated nylon fabric is poured in the modified solution prepared and flooded 8min, then nylon fabric is proceeded in reaction cylinder and seals together with modified solution, the modified solution volume is no more than 70% of reaction cylinder volume, rise to 130 ℃ with 3 ℃/min speed, with 8r/min rotating speed isothermal reaction 4h, the complete taking-up nylon fabric of question response, be immersed in 7min in deionized water, dry 50min under 80 ℃ of vacuum conditions, obtain the modified nylon fabric, according to the nylon fabric quality, with bath raio, 1:100 measures ethanolic solution, and this ethanolic solution is according to volume ratio, to be that 1:8 is formulated by absolute ethyl alcohol and deionized water.Volume ratio according to 3-glycidyl propyl trimethoxy silicane coupling agent and ethanolic solution is that 0.03:1 measures 3-glycidyl propyl trimethoxy silicane coupling agent, and slowly be added drop-wise in absolute ethyl alcohol by it, while dripping constantly, stir, 15min dropwises, then standing 40min, obtain coupling agent solution, by the modified nylon textile impregnation in coupling agent solution, carry out coupling reaction 6h under 40 ℃ of conditions, after completion of the reaction by nylon fabric just, anti-two sides is placed in respectively hardening with radiation 40min under ultraviolet lamp, fabric is apart from ultraviolet lamp 15cm, wherein the power of ultraviolet lamp is 40W, dominant wavelength is 365nm, the nylon fabric solidified after processing is immersed in respectively to acetone, each 7min in absolute ethyl alcohol, use again washed with de-ionized water 7min, vacuumize under 80 ℃ of conditions, obtain coating the nylon fabric of photocatalytic activity and magnetic Nano ferric oxide particle film.
Estimating the photocatalytic activity of nanometer di-iron trioxide modified nylon fabric with ultraviolet lamp irradiation methyl orange dye solution, through the ultraviolet irradiation of 5h, is 86% to the degradation rate of methyl orange dye.According to standard GB/T/T 8629-2001 " textiles is home washings and drying program for test ", clad nano di-iron trioxide nylon fabric is washed and dry (selects A type washing machine, the 4A washing procedure, A type drying program), and measure the hysteresis curve of clad nano di-iron trioxide nylon fabric with VSM multifunction vibration sample magnetometer (U.S. Quantum Design company), after 30 standard washings, the remanent magnetization of clad nano di-iron trioxide nylon fabric is 0.00042emug
-1, coercivity is 214Oe.
Claims (7)
1. the method for photocatalytic activity and magnetic Nano di-iron trioxide modified nylon fabric, is characterized in that, specifically according to following steps, implements:
Step 1, preparation dilute hydrochloric acid solution, utilize the dilute hydrochloric acid solution of preparation to carry out etching to nylon fabric, and the nylon fabric after then using DMF solution to etching carries out swelling treatment;
The modified solution of step 2, preparation ferric sulfate, NaOH, neopelex and shitosan, put into modified solution by pretreated nylon fabric and carry out hydro-thermal reaction, obtains the modified nylon fabric;
Step 3, preparation coupling agent solution, the modified nylon fabric is placed in to coupling agent solution to be processed, the modified nylon fabric that to process through coupling agent solution again is cured processing, obtains the nylon fabric that coats photocatalytic activity and magnetic Nano ferric oxide particle film.
2. the method for photocatalytic activity according to claim 1 and magnetic Nano di-iron trioxide modified nylon fabric, is characterized in that, described step 1 is specifically implemented according to following steps:
1.1) according to the volume ratio 1:4 of hydrochloric acid and water～6, the preparation dilute hydrochloric acid solution, the mass concentration of described hydrochloric acid is 36%;
1.2) take nylon fabric, according to bath raio 1:30～50, the nylon fabric taken is put into to step 1.1) dilute hydrochloric acid solution for preparing, under 50 ℃～70 ℃ conditions, dilute hydrochloric acid solution immersion treatment 20min～40min for nylon fabric by taking, complete the etching processing to nylon fabric;
1.3) by step 1.2) and in nylon fabric after etching processing be immersed in DMF, process 3h～5h under 70 ℃～90 ℃ conditions, then with deionized water, rinse well.
3. the method for photocatalytic activity according to claim 1 and magnetic Nano di-iron trioxide modified nylon fabric, is characterized in that, described step 2 is specifically implemented according to following steps:
2.1) quality of nylon fabric after processing according to step 1, measure deionized water with the bath raio of 1:30～50;
2.2) according to total concentration of iron, be 0.01mol/L～0.05mol/L, the mol ratio of ferric ion and hydroxide ion is Fe
3+: OH
-=1:2～1:4, take respectively ferric sulfate and NaOH;
2.3) by step 2.2) and in the ferric sulfate that takes dissolve in step 2.1) in the deionized water that measures, obtain ferrum sulfuricum oxydatum solutum, then add NaOH and fully stir, obtain ferric sulfate and NaOH mixed solution;
2.4) take respectively neopelex and shitosan, add the neopelex and the shitosan that take to step 2.3) in the ferric sulfate and NaOH mixed solution that prepare, constantly stir until neopelex and shitosan are dissolved in ferric sulfate and NaOH mixed solution, form modified solution, wherein in every liter of ferric sulfate and NaOH mixed solution, add the neopelex of 4g～8g, the shitosan of 2g～5g;
2.5) pour the pretreated nylon fabric of step 1 into step 2.4) and in the preparation modified solution in flood, dip time is 5min～10min;
2.6) will be through step 2.5) and nylon fabric after dipping together with modified solution, proceed in reaction cylinder after sealing, the volume of modified solution is no more than 60%～80% of reaction cylinder volume, reaction cylinder after sealing is risen to 120 ℃～140 ℃ with 2～4 ℃/min speed, then with 5r/min～10r/min rotating speed isothermal reaction 3h～5h;
2.7) after question response is complete, cooling, the nylon fabric of taking-up being immersed in to 5min～10min in deionized water, dry 40min～60min under 60 ℃～90 ℃ vacuum conditions, obtain the modified nylon fabric.
4. according to the method for the described photocatalytic activity of claim 1 or 3 and magnetic Nano di-iron trioxide modified nylon fabric, it is characterized in that, described shitosan is the shitosan that deacetylation is 90%, molecular weight is less than 1000.
5. the method for photocatalytic activity according to claim 1 and magnetic Nano di-iron trioxide modified nylon fabric, is characterized in that, described step 3 is specifically implemented according to following steps:
3.1) according to the quality of nylon fabric, measure ethanolic solution for 1:80～120 in mass ratio;
3.2) according to 3-glycidyl propyl trimethoxy silicane coupling agent and step 3.1) and in the volume ratio of ethanolic solution of preparation be that 0.02～0.05:1 measures 3-glycidyl propyl trimethoxy silicane coupling agent, the 3-glycidyl propyl trimethoxy silicane coupling agent measured is added drop-wise to step 3.1) in the ethanolic solution for preparing, while dripping constantly, stir, 10min～20min dropwises, by solution left standstill 30min～50min, obtain coupling agent solution after dropwising;
3.3) modified nylon textile impregnation that step 2 is obtained is in step 3.2) and in the coupling agent solution for preparing, and make modified nylon fabric and coupling agent solution carry out coupling reaction 4h～8h under 30 ℃～60 ℃ conditions;
3.4) step 3.3) and in coupling reaction after, the positive and negative two sides of the nylon fabric of taking-up is placed in respectively to irradiation 30min～50min under ultraviolet lamp, during irradiation, nylon fabric, apart from ultraviolet lamp 10cm～20cm, completes the curing processing to nylon fabric;
3.5) will be through step 3.4) and solidify nylon fabric after processing soak 5min～10min in acetone after, soak again 5min～10min in absolute ethyl alcohol, again with taking out after washed with de-ionized water nylon fabric 5min～10min, by the nylon fabric that cleans up in 70 ℃～90 ℃ vacuumizes, until dry, obtain coating the nylon fabric of photocatalytic activity and magnetic Nano ferric oxide particle film.
6. the method for a kind of photocatalytic activity according to claim 5 and magnetic Nano di-iron trioxide modified nylon fabric, it is characterized in that described step 3.1) described in ethanolic solution by absolute ethyl alcohol and deionized water, according to volume ratio, be that 1:5～10 are formulated.
7. a kind of method of photocatalytic activity and magnetic Nano di-iron trioxide modified nylon fabric according to claim 1 or 5, is characterized in that, the power of the ultraviolet lamp that in described step 3, curing reaction adopts is that 40W, dominant wavelength are 365nm.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107385892A (en) * | 2017-08-01 | 2017-11-24 | 浙江理工大学 | A kind of method of nylon fibre surface chemistry titanizing |
| CN111809385A (en) * | 2020-07-09 | 2020-10-23 | 吴江福华织造有限公司 | Preparation method of polyamide fabric with lasting antibacterial effect |
| CN112371182A (en) * | 2020-11-30 | 2021-02-19 | 南通大学 | Preparation method of fiber-based bismuth vanadate composite photocatalytic material |
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| CN102277727A (en) * | 2011-06-22 | 2011-12-14 | 西安工程大学 | Method for nanometer ferroferric oxide modification of chinlon fabric via hydrothermal process |
| CN102926187A (en) * | 2012-10-18 | 2013-02-13 | 西安工程大学 | Method for modifying polyester fabric by using magnetic nano iron trioxide |
| CN102943374A (en) * | 2012-11-21 | 2013-02-27 | 武汉爱帝高级服饰有限公司 | Anti-radiation warm-keeping antistatic fabric fiber, preparation method thereof and device |
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| CN102277727A (en) * | 2011-06-22 | 2011-12-14 | 西安工程大学 | Method for nanometer ferroferric oxide modification of chinlon fabric via hydrothermal process |
| CN102926187A (en) * | 2012-10-18 | 2013-02-13 | 西安工程大学 | Method for modifying polyester fabric by using magnetic nano iron trioxide |
| CN102943374A (en) * | 2012-11-21 | 2013-02-27 | 武汉爱帝高级服饰有限公司 | Anti-radiation warm-keeping antistatic fabric fiber, preparation method thereof and device |
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| CN107385892A (en) * | 2017-08-01 | 2017-11-24 | 浙江理工大学 | A kind of method of nylon fibre surface chemistry titanizing |
| CN107385892B (en) * | 2017-08-01 | 2019-07-26 | 浙江理工大学 | A kind of method of nylon fibre surface chemistry titanizing |
| CN111809385A (en) * | 2020-07-09 | 2020-10-23 | 吴江福华织造有限公司 | Preparation method of polyamide fabric with lasting antibacterial effect |
| CN112371182A (en) * | 2020-11-30 | 2021-02-19 | 南通大学 | Preparation method of fiber-based bismuth vanadate composite photocatalytic material |
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