CN109252365A - Anti-electrostatic fire retardant type casein base graphene compound fabric and preparation method thereof - Google Patents
Anti-electrostatic fire retardant type casein base graphene compound fabric and preparation method thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
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Abstract
Present invention relates particularly to a kind of anti-electrostatic fire retardant type casein base graphene compound fabrics and preparation method thereof.Firstly, preparing graphene oxide (GO) using Hummers method is improved, and configuring GO solution keeps its negatively charged；Then, by the modified acid dissolution casein of caprolactam, keep its positively charged；Finally, introducing nanoparticle graphene in casein matrix using LBL self-assembly method to prepare anti-electrostatic fire retardant type casein base GO compound fabric, then use NaBH4Being restored to get final product is anti-electrostatic fire retardant type casein base graphene compound fabric.Anti-electrostatic fire retardant type casein base graphene compound fabric prepared by the present invention, improves the antistatic property and flame retardant property of fabric, and is expected to be applied to the fields such as leather, food, papermaking.
Description
Technical field
The invention belongs to technical field of composite materials, and in particular to a kind of anti-electrostatic fire retardant type casein base graphene is compound to be knitted
Object and preparation method thereof.
Background technique
In recent years, environmental issue is of interest by people always.Casein is as a kind of pure natural protein, due to good life
Biodegradable, compatibility, cost be inexpensive and strand in a variety of reactive groups can synthesize various derivatives, in leather, make
Paper, fabric and medicine and other fields are used widely.But the functionality that casein is applied as coating is lacked there are still some at present
It falls into, if antistatic property and flame retardant property are poor, is limiting its application range to a certain degree.Graphene is a kind of two dimension
The carbon material of honeycomb structure has unique monatomic layer structure and excellent mechanics, thermal property, causes both at home and abroad
The very big concern of researcher[1-3].According to the literature, graphene is introduced in different polymeric matrixs, had centainly to its performance
Promotion.If the good conductance of graphene is forthright and hygroscopicity, substrate surface can be made to form continuous moisture film, to improve indirectly
Surface conductivity[4-6].Also, graphene sheet layer structure be on the whole it is intensive and continuous, it can prevent oxygen from entering material
Depths.In addition, graphene conduction heat is very good, the excessively high heat in part can be transmitted to rapidly its remaining part of material
Point so that heat is able to good dispersion, thus the intensity of a fire be not easy Spreading and diffusion achieve the effect that it is fire-retardant[7-9].However, by mesh
Before, graphene is introduced in casein system, while improving being rarely reported for its flame retardant property and antistatic property.([1]Lan Y,
Liu H,Cao X H,et al.Electrically conductive thermoplastic polyurethane/
polypropylene nanocomposites with selectively distributed grapheme [J]
.Polymer,2016,97:11-19.[2] Ding Y,Zhu J Q,Wang C H,et al.Multifunctional
three-dimensional graphene nanoribbons composite sponge[J].Carbon,2016,104:
133-140.[3] Han N R,Cho J W.Click coupled stitched graphene sheets and their
polymer nanocomposites with enhanced photothermal and mechanical properties
[J] .Composites Part A:Applied Science Manufacturing, 2016,87:78-85. [4] Liu Lin,
Open east graphene/composite conducting polymer material research [J] functional material, 2014,45 (S1): 7-11. [5] Wang
T,Ge H,Zhang K.A novel core-shell silica@graphene straticulate structured
antistatic anticorrosion composite coating[J].Journal of Alloys & Compounds,
The preparation of the brave graphene of 2018. [6] chapters and application [D] East China University of Science modified and in antistatic coating, 2013.
[7] application and the mechanism of action [J] applied chemistry of Chen Nan, Zhong Guilin, Zhang Guofeng the graphene in flame retardance of polymer material,
2018,35 (03): 307-316. [8] Bao C, Guo Y, Yuan B, et al. Functionalized Graphene
Oxide for Fire Safety Applications of Polymers: A Combination of Condensed
Phase Flame Retardant Strategies [ J ] J Mater Chem, 2012,22 (43): 23057-23063.
[9] Wei H, Zhu Z, Sun H, et al. Graphene and Poly (ionic liquid) Modified
Polyurethane Sponges with Enhanced Flame Retardant Properties [ J ] .J Appl Polym
Sci, 2017,134 (44): 45477.).
Summary of the invention
The object of the present invention is to provide a kind of anti-electrostatic fire retardant type casein base graphene compound fabrics and preparation method thereof, should
The compound fabric of method preparation improves the antistatic and flame retardant property of fabric, is expected to be applied to the neck such as leather, food, papermaking
Domain.
The technical scheme adopted by the invention is as follows:
The preparation method of anti-electrostatic fire retardant type casein base graphene compound fabric, comprising the following steps:
Step 1: it improves Hummers method and prepares graphene oxide (GO):
7.5 ~ 7.8mL concentrated sulfuric acid is taken to be added in three-necked flask, by potassium peroxydisulfate and phosphorus pentoxide with the quality of (1:1 ~ 1:3)
Than being slowly added into the concentrated sulfuric acid with vigorous stirring, mixture being warming up to 70 DEG C ~ 90 DEG C；Then, graphite is added and is mixed
In solution, stops heating after stirring 8 ~ 12h, be cooled to room temperature, after reaction wash resulting product, stand, dry；
20 ~ 30ml concentrated sulfuric acid is taken to be added in three-necked flask, then by pretreated graphite and the sodium nitrate (matter of graphite and sodium nitrate
Amount is than being 1:1 ~ 1:3) it is slowly added in the concentrated sulfuric acid after mixing, the reaction temperature of system is maintained at 3 DEG C ~ 4 DEG C；Then, delay
It is slow that potassium permanganate (mass ratio of graphite and potassium permanganate is 1:1 ~ 1:3) is added, react be warming up to after the min of 30min ~ 50 30 DEG C ~
50 DEG C, react 2h；30mL ~ 50mL deionized water is added, is warming up to 80 DEG C ~ 90 DEG C, reacts 10min ~ 20min；Finally, being added
100mL ~ 150mL deionized water terminates reaction, and 8mL ~ 12mL hydrogen peroxide is added, and system is buff from brown stain, is washed with HCl
It washs, later, by reaction product washing, is centrifuged and dries；
Step 2: the preparation of modified Casein lotion (CA):
The acidic aqueous solution that 2 ~ 6g casein is dissolved in 3wt% ~ 5wt% is added in three-necked flask, 150ml distillation is then added
Water, heating water bath simultaneously stir；Then, the modifier solution that mass fraction is 25% is added dropwise with the speed of 1d/2s, then 75
1h is reacted at a temperature of DEG C；
Step 3: the preparation of anti-electrostatic fire retardant type casein base graphene compound fabric:
By cotton fabric in KH550(gamma-aminopropyl-triethoxy-silane) lysate in impregnate 30 min, wash and dry；It connects
, cotton fabric is immersed to 20 min in negatively charged GO aqueous solution (5mg/mL ~ 8mg/mL), is washed and dried；Then, by cotton
Fabric is immersed in the positively charged casein lysate 20min of 3wt% ~ 5wt%, washes and dries；Above procedure is an assembling
Circulation can form a GO/CA bilayer in surface of cotton fabric；Repeat assembling circulation, (GO/CA) can be obtainedn
Fabric samples；
By (GO/CA)nFabric samples are put into three-necked flask, and 300mL distilled water is added, and the carbon of 3wt% ~ 5wt% is then added dropwise
Acid sodium solution adjusts the pH to 9 ~ 10 of reaction system；Heating water bath is carried out after reducing agent is added into three-necked flask, reaction terminates
Product is washed into drying afterwards, can be prepared by the RGO/CA compound fabric of the different assembling numbers of plies.
In the step 1, the temperature and time of drying is respectively 60 DEG C, for 24 hours.
In the step 2, acidic aqueous solution is aqueous acetic acid, aqueous citric acid solution or boric acid aqueous solution.
In the step 2, modifier solution is caprolactam solution, acrylonitrile monomer solution, organic silicon solution or poly-
Urethane solution.
In the step 2, the temperature of heating water bath and reaction time are respectively 65 DEG C, 2h.
In the step 3, the temperature of heating water bath and reaction time are respectively 80 DEG C, 1h.
In the step 3, reducing agent is sodium borohydride (NaBH4), the quality of the dosage of the reducing agent and graphene oxide
Than for 8:1 ~ 6:1.
The invention has the following advantages that
The present invention is to provide a kind of anti-electrostatic fire retardant type casein base graphene compound fabric and preparation method thereof, the present invention is used
Method be LBL self-assembly method, by intermolecular interaction such as electrostatic alternating sorbent, electric charge transfer, successively to replace
The mode of deposition enables layer and layer spontaneously to associate to form the process of the molecule aggregate with certain specific function.The method
Easy to operate, assembling is complete, and raw materials used casein is natural products in experiment, and at low cost, product is degradable, and graphene is
Stratiform two-dimensional structure has excellent performance.The present invention prepares resulting casein base graphene compound fabric, both shows to resist quiet
Electrical property shows flame retardant property again, and the quality and grade of fabric after covering with paint, lacquer, colour wash, etc. is made to increase, and is expected to be applied to leather, food
The fields such as product, papermaking increase its commercial value；Products therefrom stability is good, and it is good to realize that industrialization has been established for product
Basis.
Detailed description of the invention
Fig. 1 is preparation method (LBL self-assembly) mechanism figure of the invention
Fig. 2 is (RGO/CA) of the different assembling numbers of plies prepared by the present inventionnCompound fabric ((a:0 layers b:5 layers c:10 layers) (a ':
0 layer b ': 5 layers c ': 10 layers)) the forward and backward appearance comparison diagram of burning.
Specific embodiment
The present invention will be described in detail With reference to embodiment.
The preparation method of anti-electrostatic fire retardant type casein base graphene compound fabric, comprising the following steps:
Step 1: it improves Hummers method and prepares graphene oxide (GO):
7.5 ~ 7.8mL concentrated sulfuric acid is taken to be added in three-necked flask, by potassium peroxydisulfate and phosphorus pentoxide with the quality of (1:1 ~ 1:3)
Than being slowly added into the concentrated sulfuric acid with vigorous stirring, mixture being warming up to 70 DEG C ~ 90 DEG C；Then, graphite is added and is mixed
In solution, stops heating after stirring 8 ~ 12h, be cooled to room temperature, after reaction wash resulting product, stand, dry；
20 ~ 30ml concentrated sulfuric acid is taken to be added in three-necked flask, then by pretreated graphite and the sodium nitrate (matter of graphite and sodium nitrate
Amount is than being 1:1 ~ 1:3) it is slowly added in the concentrated sulfuric acid after mixing, the reaction temperature of system is maintained at 3 DEG C ~ 4 DEG C；Then, delay
It is slow that potassium permanganate (mass ratio of graphite and potassium permanganate is 1:1 ~ 1:3) is added, react be warming up to after the min of 30min ~ 50 30 DEG C ~
50 DEG C, react 2h；30mL ~ 50mL deionized water is added, is warming up to 80 DEG C ~ 90 DEG C, reacts 10min ~ 20min；Finally, being added
100mL ~ 150mL deionized water terminates reaction, and 8mL ~ 12mL hydrogen peroxide is added, and system is buff from brown stain, is washed with HCl
It washs, later, by reaction product washing, is centrifuged and dries；
Step 2: the preparation of modified Casein lotion (CA):
The acidic aqueous solution that 2 ~ 6g casein is dissolved in 3wt% ~ 5wt% is added in three-necked flask, 150ml distillation is then added
Water, heating water bath simultaneously stir；Then, the modifier solution that mass fraction is 25% is added dropwise with the speed of 1d/2s, then 75
1h is reacted at a temperature of DEG C；
Step 3: the preparation of anti-electrostatic fire retardant type casein base graphene compound fabric:
By cotton fabric in KH550(gamma-aminopropyl-triethoxy-silane) lysate in impregnate 30 min, wash and dry；It connects
, cotton fabric is immersed to 20 min in negatively charged GO aqueous solution (5mg/mL ~ 8mg/mL), is washed and dried；Then, by cotton
Fabric is immersed in the positively charged casein lysate 20min of 3wt% ~ 5wt%, washes and dries；Above procedure is an assembling
Circulation can form a GO/CA bilayer in surface of cotton fabric；Repeat assembling circulation, (GO/CA) can be obtainedn
Fabric samples；
By (GO/CA)nFabric samples are put into three-necked flask, and 300mL distilled water is added, and the carbon of 3wt% ~ 5wt% is then added dropwise
Acid sodium solution adjusts the pH to 9 ~ 10 of reaction system；Heating water bath is carried out after reducing agent is added into three-necked flask, reaction terminates
Product is washed into drying afterwards, can be prepared by the RGO/CA compound fabric of the different assembling numbers of plies.
In the step 1, the temperature and time of drying is respectively 60 DEG C, for 24 hours.
In the step 2, acidic aqueous solution is aqueous acetic acid, aqueous citric acid solution or boric acid aqueous solution.
In the step 2, modifier solution is caprolactam solution, acrylonitrile monomer solution, organic silicon solution or poly-
Urethane solution.
In the step 2, the temperature of heating water bath and reaction time are respectively 65 DEG C, 2h.
In the step 3, the temperature of heating water bath and reaction time are respectively 80 DEG C, 1h.
In the step 3, reducing agent is sodium borohydride, and the mass ratio of the dosage of the reducing agent and graphene oxide is 8:1
~6:1。
Embodiment 1
Step 1: it improves Hummers method and prepares graphene oxide (GO)
It takes the 7.5mL concentrated sulfuric acid to be added in 100mL three-necked flask, with mass ratio is 1:1 by potassium peroxydisulfate and phosphorus pentoxide,
It is slowly added into the concentrated sulfuric acid under strong stirring, phosphorus pentoxide, which is added, exothermic phenomenon, and mixture is warming up to 70 DEG C；Then
Graphite is added, cleans the graphite being stained in bottle wall with 3 ~ 6ml concentrated sulfuric acid, after stirring 8h, stops heating, turns after being cooled to room temperature
It moves on in 500mL beaker, 500mL distilled water is added into beaker, stand for 24 hours etc. to be precipitated, outwell supernatant and suspension, then
500mL distilled water is added, stirs and stands, repeats 4-5 times, filters, wash with distilled water to neutrality, is placed at room temperature for 1h, dries.
It takes the 18ml concentrated sulfuric acid to be added in three-necked flask, pretreated graphite and sodium nitrate (mass ratio 1:1) is mixed
It is slowly added into the concentrated sulfuric acid after uniformly, keeps system temperature at 1 DEG C；By potassium permanganate, (graphite and potassium permanganate mass ratio are again
It 1:1) is slowly added in system, 30 DEG C is warming up to after 0.5h, react 2h；30ml deionized water is added, 85 DEG C of reactions are warming up to
20min；It is eventually adding 100ml deionized water and terminates reaction, 10ml hydrogen peroxide is added, is washed with a small amount of volume 3%HCl, later will
Product is washed with deionized repeatedly, and centrifugation is finally dried for 24 hours in 40 DEG C of baking ovens.
Step 2: the preparation of modified Casein lotion (CA):
2g casein is dissolved in 3wt% acidic aqueous solution to be added in three-necked flask, 150ml distilled water is then added, by the system
It is maintained at 65 DEG C of stirred in water bath 2h；Then 25% caprolactam solution is added dropwise with the speed of 1d/2s, it is anti-at 75 DEG C
Answer 1h；(in step 2, acidic aqueous solution is aqueous acetic acid, aqueous citric acid solution or boric acid aqueous solution.)
Step 3: the preparation of anti-electrostatic fire retardant type casein base graphene compound fabric:
By cotton fabric in KH550(amido functional group silane) lysate in impregnate 30 min, wash and dry, then, by cotton
Fabric impregnates 20 min in the negatively charged GO aqueous solution of 5 mg/mL, washes and dries；Cotton fabric is then immersed in band
Casein lysate (mass fraction 3%) 20min of positive charge, washes and dries；Above procedure is an assembling circulation, in cotton
Fabric surface forms a GO/CA bilayer；Repeat assembling circulation, (GO/CA) can be obtainednFabric sample；
By (GO/CA)nFabric samples are put into three-necked flask, and 300mL distilled water is added, and the sodium carbonate that 3wt% is then added dropwise is molten
Liquid adjusts the pH to 9 of reaction system, and reducing agent sodium borohydride (sodium borohydride and the dilute quality of graphite oxide are added thereto
Than for 8:1)；Heating water bath is carried out again, after reaction by dry (RGO/CA) to get the different assembling numbers of plies of product washingn
Compound fabric carries out combustion experiment to the fabric of the different assembling numbers of plies, and tests its anti-flammability and surface resistivity.
Embodiment 2
Step 1: it improves Hummers method and prepares graphene oxide (GO)
The 7.6mL concentrated sulfuric acid is taken to be added in three-necked flask, by potassium peroxydisulfate and phosphorus pentoxide with the mass ratio of 1:2, strong
It is slowly added into the concentrated sulfuric acid under stirring, phosphorus pentoxide, which is added, exothermic phenomenon, mixture is warming up to 80 DEG C, then by stone
Ink is added in three-necked flask, cleans the graphite being stained in bottle wall with 3 ~ 6ml concentrated sulfuric acid；After stirring 10h, stop heating, it is cooling
It is transferred to after to room temperature in 500mL beaker, 500mL distilled water is added and stands for 24 hours etc. to be precipitated, outwells supernatant and suspension；
Again plus 500mL distilled water, stirring are stood, and are washed 4-5 times, are filtered repeatedly, extremely neutral wash with distilled water, are placed at room temperature for 2h, are dried in the air
It is dry.
The 25ml concentrated sulfuric acid is taken to be added in three-necked flask, then pretreated graphite and sodium nitrate (mass ratio 3:1) is mixed
It is even to be slowly added into the concentrated sulfuric acid, keep system temperature at 3 DEG C；Again by potassium permanganate (graphite and potassium permanganate mass ratio be 1:2)
It is slowly added in system, 40 DEG C is warming up to after half an hour, react 2h；10 DEG C are added, 40ml deionized water is warming up to 85 DEG C instead
15min is answered, 140ml deionized water is eventually adding and terminates reaction, 8ml hydrogen peroxide is added, system is buff from brown stain, is used
A small amount of volume 5%HCl washing, product is washed repeatedly with 500ml deionized water later, is centrifuged, then the drying in 60 DEG C of baking ovens
24h。
Step 2: the preparation of modified Casein lotion (CA)
4g casein is dissolved in 4% acidic aqueous solution to be added in three-necked flask, 150ml distilled water is then added, which is protected
It holds in 65 DEG C of stirred in water bath 2h；Then 25% caprolactam solution is added dropwise with the speed of 1d/2s, is reacted at 75 DEG C
1h；(in step 2, acidic aqueous solution is aqueous acetic acid, aqueous citric acid solution or boric acid aqueous solution.)
Step 3: the preparation of anti-electrostatic fire retardant type casein base graphene (RGO) compound fabric.
By cotton fabric in KH550(gamma-aminopropyl-triethoxy-silane) lysate in impregnate 30 min, clean and do
It is dry, then, cotton fabric is immersed to 20 min in negatively charged GO aqueous solution (6mg/mL), is washed and dried；Then cotton is knitted
Object is immersed in positively charged casein lysate (mass fraction 4%) 20min, washes and dries；Above procedure is an assembling
Circulation forms a GO/CA bilayer in surface of cotton fabric；Repeat assembling circulation, (GO/CA) can be obtainednFabric
Sample；
By (GO/CA)nFabric samples are put into three-necked flask, and 300mL distilled water is added, the sodium carbonate liquor of 4wt% is added dropwise,
Adjust the pH to 9 of reaction system, then, be added reducing agent sodium borohydride (sodium borohydride and the dilute mass ratio of graphite oxide are 7:
1) heating water bath, is carried out, product is washed into drying after reaction, can be prepared by (RGO/CA) of the different assembling numbers of pliesnIt is compound
Fabric carries out combustion experiment to the fabric of the different assembling numbers of plies, and tests its anti-flammability and surface resistivity.
Embodiment 3
Step 1: it improves Hummers method and prepares graphene oxide (GO)
The 7.6mL concentrated sulfuric acid is taken to be added in 100mL three-necked flask, by potassium peroxydisulfate (K2S2O8) and phosphorus pentoxide (P2O5) with
Mass ratio is 1:3, is slowly added into the concentrated sulfuric acid under vigorous stirring, and P2O5, which is added, exothermic phenomenon, and mixture will heat up
To 90 DEG C；, then graphite is added in three-necked flask, cleans the graphite being stained in bottle wall with 3 ~ 6ml concentrated sulfuric acid；Stir 12h
Afterwards, stop heating, be transferred to after being cooled to room temperature in 500mL beaker, 500mL distilled water is added and stands for 24 hours etc. to be precipitated, outwells
Supernatant and suspension, then plus 500mL distilled water, stirring stand, 4-5 time repeatedly, filter, wash with distilled water to neutrality, room
Temperature places 1h, dries.Take the 23ml concentrated sulfuric acid as in three-necked flask, then by pretreated graphite and sodium nitrate (mass ratio 2:
1) it mixes and is slowly added into the concentrated sulfuric acid, keep system temperature at 3-4 DEG C, later again by potassium permanganate (graphite and potassium permanganate matter
Amount is than being 1:3) it is slowly added in system, it is warming up to 35 DEG C after half an hour, reacts 2h, adds 10 DEG C, 40ml deionized water rises
Temperature is eventually adding 140ml deionized water and terminates reaction to 85 DEG C of reaction 15min, is added 10ml hydrogen peroxide, and system is from brown stain
It for buff, is washed with a small amount of volume 5%HCl, later washs product repeatedly with 500ml deionized water, be centrifuged, then at 60 DEG C
It is dried for 24 hours in baking oven.
Step 2: the preparation of modified Casein lotion (CA)
6g casein is dissolved in 5% acidic aqueous solution to be added in three-necked flask, 150ml distilled water is then added, which is protected
It holds in 65 DEG C of stirred in water bath 2h；Then 25% caprolactam solution is added dropwise with the speed of 1d/2s, is reacted at 75 DEG C
(in step 2, acidic aqueous solution is aqueous acetic acid, aqueous citric acid solution or boric acid aqueous solution to 1h..)
Step 3: the preparation of anti-electrostatic fire retardant type casein base graphene compound fabric.
By cotton fabric in KH550(gamma-aminopropyl-triethoxy-silane) lysate in impregnate 30 min, clean and do
It is dry, then, cotton fabric is immersed to 20 min in negatively charged GO aqueous solution (8mg/mL), is washed and dried；Then cotton is knitted
Object is that 5% positively charged casein lysate (mass fraction 5%) impregnates 20min in mass fraction, is washed and dried；The above mistake
Journey is an assembling circulation, forms a GO/CA bilayer in surface of cotton fabric；Repeat assembling circulation, can be obtained
(GO/CA)nFabric sample；
By (GO/CA)nFabric samples are put into three-necked flask, and 300mL distilled water is added, and the sodium carbonate that 5wt% is then added dropwise is molten
Liquid adjusts the pH to 10 of reaction system, and reducing agent sodium borohydride (sodium borohydride and the dilute quality of graphite oxide are added thereto
Than for 6:1)；Heating water bath is carried out again, product is washed into drying after reaction, can be prepared by (the RGO/ of the different assembling numbers of plies
CA)nCompound fabric carries out combustion experiment to the fabric of the different assembling numbers of plies, and tests its anti-flammability and surface resistivity.
The present invention is prepared for anti-electrostatic fire retardant type casein base graphene using the method for LBL self-assembly, to different assembled layers
Several compound fabric carries out combustion experiment, and test its anti-flammability and surface resistivity obtain it is specific now in conjunction with attached drawing to draw a conclusion
Illustrate: it will be seen from figure 1 that preparing composite coating by the method for LBL self-assembly, mechanism is mutual by positive and negative charge
In conjunction with being assembled.It is (RGO/CA) of the different assembling numbers of plies from table 1nThe antistatic property of compound fabric characterizes, this experiment is logical
It crosses BEST-212 resistance meter measurement table resistance rate and determines that (antistatic property is divided into 3 grades to antistatic property；Table resistance rate < 10
^7It is A grades, 10^7~10^10It is B grades, 10^10~10^13It is C grades, > 10^13There is no antistatic property).From Table 2, it can be seen that
The surface resistivity of 1BL is 2.278 × 10^10The surface resistivity of Ω, 5BL are 8.679 × 10^9The surface electricity of Ω, 10BL
1.649 × 10^ of resistance rate9Ω reaches B grades antistatic, to lead to the conclusion that a kind of anti-static inflaming-retarding type casein base RGO is multiple
Condensating fiber coating can assign fabric antistatic property.It can be seen that in Fig. 2, form one layer after the fabric burning by RGO assembling
Continuous protectiveness layer of charcoal, which is able to suppress Mass and heat transfer, improves the flame retardant property of fabric, from the different assembled layers of table 2
Several (RGO/CA)nThe flame retardancy test results of compound fabric can be seen that the increase with the assembling number of plies, and oxygen concentration gradually increases
Greatly, illustrate that the anti-flammability of fabric gradually increases.In conjunction with Fig. 1, table 1, Fig. 2 and table 2 it is found that compound fabric prepared by the present invention is
With antistatic and fire-retardant difunctional fabric.
(RGO/CA) of the different assembling numbers of plies of table 1nThe antistatic property of compound fabric characterizes
(RGO/CA) of the different assembling numbers of plies of table 2nThe flame retardancy test results of compound fabric
Note: 0BL is pure fabric；5BL is 5 layers of fabric of coating；10BL is 10 layers of fabric of coating.
The contents of the present invention are not limited to cited by embodiment, and those of ordinary skill in the art are by reading description of the invention
And to any equivalent transformation that technical solution of the present invention is taken, all are covered by the claims of the invention.
Claims (8)
1. a kind of preparation method of anti-electrostatic fire retardant type casein base graphene compound fabric, which comprises the following steps:
Step 1: it improves Hummers method and prepares graphene oxide (GO):
7.5 ~ 7.8mL concentrated sulfuric acid is taken to be added in three-necked flask, by potassium peroxydisulfate and phosphorus pentoxide with the quality of (1:1 ~ 1:3)
Than being slowly added into the concentrated sulfuric acid with vigorous stirring, mixture being warming up to 70 DEG C ~ 90 DEG C；Then, graphite is added and is mixed
In solution, stops heating after stirring 8 ~ 12h, be cooled to room temperature, after reaction wash resulting product, stand, dry；
20 ~ 30ml concentrated sulfuric acid is taken to be added in three-necked flask, then by pretreated graphite and the sodium nitrate (matter of graphite and sodium nitrate
Amount is than being 1:1 ~ 1:3) it is slowly added in the concentrated sulfuric acid after mixing, the reaction temperature of system is maintained at 3 DEG C ~ 4 DEG C；Then, delay
It is slow that potassium permanganate (mass ratio of graphite and potassium permanganate is 1:1 ~ 1:3) is added, react be warming up to after the min of 30min ~ 50 30 DEG C ~
50 DEG C, react 2h；30mL ~ 50mL deionized water is added, is warming up to 80 DEG C ~ 90 DEG C, reacts 10min ~ 20min；Finally, being added
100mL ~ 150mL deionized water terminates reaction, and 8mL ~ 12mL hydrogen peroxide is added, and system is buff from brown stain, first uses HCl
Washing by reaction product washing, is centrifuged and dries later；
Step 2: the preparation of modified Casein lotion (CA):
The acidic aqueous solution that 2 ~ 6g casein is dissolved in 3wt% ~ 5wt% is added in three-necked flask, 150ml distillation is then added
Water, heating water bath simultaneously stir；Then, the modifier solution that mass fraction is 25% is added dropwise with the speed of 1d/2s, then 75
1h is reacted at a temperature of DEG C；
Step 3: the preparation of anti-electrostatic fire retardant type casein base graphene compound fabric:
By cotton fabric in KH550(gamma-aminopropyl-triethoxy-silane) lysate in impregnate 30 min, wash and dry, connect
, cotton fabric is immersed to 20min in negatively charged GO aqueous solution (5mg/mL ~ 8mg/mL), is washed and dried；Then, by cotton
Fabric is immersed in the positively charged casein lysate 20min of 3wt% ~ 5wt%, washes and dries；Above procedure is an assembling
Circulation can form a GO/CA bilayer in surface of cotton fabric；Repeat assembling circulation, (GO/CA) can be obtainedn
Fabric samples；
By (GO/CA)nFabric samples are put into three-necked flask, and 300mL distilled water is added, and the carbonic acid of 3wt% ~ 5wt% is then added dropwise
Sodium solution adjusts the pH to 9 ~ 10 of reaction system；Heating water bath is carried out after reducing agent is added into three-necked flask, after reaction
Product is washed into drying, can be prepared by (RGO/CA) of the different assembling numbers of pliesnCompound fabric.
2. the preparation method of anti-electrostatic fire retardant type casein base graphene compound fabric according to claim 1, feature exist
In:
In the step 1, the temperature and time of drying is respectively 60 DEG C, for 24 hours.
3. the preparation method of anti-electrostatic fire retardant type casein base graphene compound fabric according to claim 1, feature exist
In:
In the step 2, acidic aqueous solution is aqueous acetic acid, aqueous citric acid solution or boric acid aqueous solution.
4. the preparation method of anti-electrostatic fire retardant type casein base graphene compound fabric according to claim 1, feature exist
In,
In the step 2, modifier solution is caprolactam solution, acrylonitrile monomer solution, organic silicon solution or polyurethane
Solution.
5. the preparation method of anti-electrostatic fire retardant type casein base graphene compound fabric according to claim 1, feature exist
In,
In the step 2, the temperature of heating water bath and reaction time are respectively 65 DEG C, 2h.
6. the preparation method of anti-electrostatic fire retardant type casein base graphene compound fabric according to claim 1, feature exist
In:
In the step 3, the temperature of heating water bath and reaction time are respectively 80 DEG C, 1h.
7. the preparation method of anti-electrostatic fire retardant type casein base graphene compound fabric according to claim 1, feature exist
In:
In the step 3, reducing agent is sodium borohydride, and the mass ratio of the dosage of the reducing agent and graphene oxide is 8:1 ~ 6:
1。
8. anti-electrostatic fire retardant type casein base graphene compound fabric made from preparation method as described in claim 1.
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