CN112876751A - Janus-like graphene/natural latex composite membrane and preparation method thereof - Google Patents
Janus-like graphene/natural latex composite membrane and preparation method thereof Download PDFInfo
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- CN112876751A CN112876751A CN202110055320.7A CN202110055320A CN112876751A CN 112876751 A CN112876751 A CN 112876751A CN 202110055320 A CN202110055320 A CN 202110055320A CN 112876751 A CN112876751 A CN 112876751A
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08J2307/02—Latex
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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Abstract
The invention relates to a natural latex/quasi-dihedral nerve graphene composite film and a preparation method thereof, wherein the water dispersibility provided by a quasi-dihedral nerve graphene hydrophilic part is utilized, and a quasi-dihedral nerve graphene water dispersion liquid is mixed and stirred with natural latex uniformly according to a proportion, so that the stably dispersed natural latex/quasi-dihedral nerve graphene dispersion liquid is obtained, wherein the oxidation degree of the quasi-dihedral nerve graphene is asymmetrically distributed, one end of the quasi-dihedral nerve graphene dispersion liquid is hydrophilic, and the quasi-dihedral nerve graphene composite film has good water dispersibility; the other end is hydrophobic, and the property of graphene is reserved, so that the composite membrane has excellent mechanical property and electrical property.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to a preparation method of a Janus graphene/natural latex composite film, and belongs to the field of preparation of natural latex nano composite aqueous dispersion.
[ background of the invention ]
Graphene is a two-dimensional carbon material with a single atomic thickness, and is commonly used for preparing high-performance natural latex/graphene composite films due to its ultrahigh thermal conductivity, extraordinary electron transport and mechanical properties.
However, due to the strong van der waals force between graphene sheets, the graphene-rubber interface interaction is weak, and unmodified graphene sheets are difficult to uniformly disperse in a natural latex matrix, resulting in poor final properties of the composite material. The surface of the graphene oxide is rich in oxygen-containing functional groups and has excellent water dispersibility, so that the graphene oxide has good compatibility with natural latex, the natural latex/graphene oxide composite membrane is prepared by an emulsion blending method and then is subjected to in-situ reduction, and the obtained natural latex/graphene composite membrane graphene is uniform in dispersion and excellent in performance. However, the preparation of graphene oxide requires a large amount of strong oxidizing reagents such as concentrated sulfuric acid and potassium permanganate, which causes water pollution; in addition, reagents such as hydrazine hydrate, sodium borohydride and hydroiodic acid which are commonly used for reducing graphene oxide are expensive, have high toxicity or production danger, and are not suitable for practical production and application. Finally, the method for soaking the graphene oxide in the film in-situ reduction composite film is not suitable for reducing the graphene oxide in a natural latex thick product or a product needing to be dipped and coated on a fabric, and the problem of uneven reduction or fabric pollution is easily caused.
Based on the above points, it is very meaningful to find a graphene material which can be uniformly dispersed in a natural latex matrix and does not need to be reduced.
[ summary of the invention ]
In the prior art, when the natural latex/graphene composite film is prepared, graphene oxide is used for improving the dispersibility of graphene, the preparation and reduction processes of the graphene oxide are not suitable for practical production and application, and the obtained film is poor in conductivity due to the fact that the graphene oxide is compounded with the natural latex.
In order to solve the problems, the invention aims to provide a natural latex/pseudodihedral graphene composite film and a preparation method thereof, wherein the pseudodihedral graphene aqueous dispersion is mixed with natural latex according to a proportion and uniformly stirred by utilizing water dispersibility provided by a pseudodihedral graphene hydrophilic part, so that the stably dispersed natural latex/pseudodihedral graphene dispersion is obtained;
another object of the present invention is to provide a method for stably and uniformly dispersing graphene in natural latex.
The method comprises the steps of uniformly dispersing the Janus-like graphene aqueous dispersion in a natural latex matrix according to a ratio, mixing and stirring uniformly, carrying out in-situ reduction on oxidized parts of the Janus-like graphene under the action of a compounding agent, an alkaline environment and a post-vulcanization temperature in the natural latex, forming a film, and vulcanizing to obtain the natural latex/Janus-like graphene composite film. The oxidation degree of the Zanthoxylum-like graphene is asymmetrically distributed, and one end of the Zanthoxylum-like graphene is hydrophilic and has good water dispersibility; the other end is hydrophobic, and the property of graphene is reserved, so that the composite membrane has excellent mechanical property and electrical property.
Preferably, the Janus-like graphene aqueous dispersion is uniformly dispersed in a natural latex matrix according to a proportion, the mixture is uniformly stirred, poured into a mold, dried, taken down from the mold, and vulcanized to obtain the natural latex/Janus-like graphene composite film.
Preferably, the vulcanization is heating vulcanization, and the used equipment is one or two of vacuum drying and forced air drying;
preferably, the vulcanization temperature is 80-110 ℃ and the time is 0.5-2 h.
Preferably, the membrane is formed by dipping, casting or suction filtration;
the dipping film forming refers to dipping a dipping die into natural latex-type Shuangshen graphene composite aqueous dispersion, and then pulling to form a film, wherein the pulling speed is 2-10 mm/min;
the casting film forming refers to pouring the natural latex-class Janus graphene composite aqueous dispersion into a mold, and forming a film at the temperature of 25-60 ℃;
the film formation by suction filtration refers to the film formation by vacuum filtration of the natural latex-class Shuangshen graphene composite aqueous dispersion under the condition of a flowing field.
Preferably, the uniform mixing and stirring means that the mixing of the Janus-like graphene aqueous dispersion and the natural latex is carried out under the condition of continuous stirring, the stirring speed is 200-2000r/min, the stirring time is 5-120min, the temperature is 10-40 ℃, and the content of Janus-like graphene in the composite film is controlled to be 0.1-10 wt%.
Preferably, the natural latex is pre-vulcanized natural latex, which comprises fresh natural latex or concentrated natural latex from hevea trees, and is pre-vulcanized by adopting a vulcanization system consisting of a vulcanizing agent, an accelerator and an activating agent, an anti-aging agent and a stabilizing agent;
it is preferable that: the dry rubber solid content of the pre-vulcanized natural rubber latex is 60 wt%;
it is preferable that: the prevulcanized natural latex is prepared from the following raw materials in parts by weight: 100 parts of natural latex; 0.5-1.5 parts of vulcanizing agent sulfur; 0.4-0.6 part of anti-aging agent 2, 6-di-tert-butyl-p-cresol; 0.2-0.6 part of anti-aging agent 2, 2' -methylene bis- (4-methyl-6-tert-butylphenol); 0.8-1.2 parts of activator ZnO; 0.2-0.6 part of promoter zinc diethyldithiocarbamate; 0.2-0.5 part of stabilizer KOH;
preferably, the complexing agent comprises ZnO, S; the alkaline environment includes the stabilizers KOH of natural latex and ammonia.
It is preferable that: the preparation method of the Zaishen-like graphene comprises the steps of pre-oxidizing graphite, controlling pre-oxidation time, oxidation temperature and oxidant concentration to obtain pre-oxidized graphite only subjected to edge oxidation, and then crushing and stripping the pre-oxidized graphite by using mechanical force to obtain the Zaishen-like graphene. Respectively measuring 5-200ml of concentrated sulfuric acid, weighing 1-5g of graphite and 1-10g of potassium permanganate, sequentially and slowly adding into a dry container, stirring in an ice water bath for 10-600min, heating to 30-40 ℃, continuously stirring for 0-600min, sequentially and slowly adding ice water and hydrogen peroxide, washing to neutrality, adjusting the pH value to 9-14, crushing by using mechanical force, and centrifuging to obtain a supernatant, namely the Janus japonica-like graphene; the mechanical force comprises ultrasound, ball milling, high shear, homogenization and high pressure water jet.
Preferably, the oxidation degree of the Janus-like graphene is asymmetrically distributed, one end of the Janus-like graphene is hydrophilic and has good water dispersibility, and the other end of the Janus-like graphene is hydrophobic, so that the property of the graphene is kept;
it is preferable that: the addition amount of the Janus-like graphene in the composite film is 0.1-10 wt% (dry weight ratio);
it is preferable that: the carbon-oxygen ratio of the Janus-like graphene is 1-12; hydrophilic end in situ Raman test ID/IGGreater than 1, hydrophobic end ID/IGLess than 1; the thickness of the hydrophilic end slice layer is 0.05-0.6nm larger than that of the hydrophobic end slice layer;
it is preferable that: the size of the sheet layer of the Janus-like graphene is 5-6000 nm;
it is preferable that: when the pH value is 7-13, the Zeta potential of the Shuangmian graphene-like aqueous dispersion liquid is-60 to-30.
The third purpose of the invention is to provide the composite membrane prepared by the method, the tensile strength of the composite membrane is 25-40MPa, the 100% stress at definite elongation is 0.8-1.2MPa, and the flexibility of the natural latex membrane is kept under low strain;
it is preferable that: the conductivity of the composite film is 10-8-1S/m; the sensitivity factor is 50-1000 under the strain of 5% -25%;
it is preferable that: at room temperature and 10Hz, the dielectric constant is 300-500 and the dielectric loss is 0.01-2.
A fourth object of the present invention is to provide the use of the above composite film in the fields of artificial skin, sensors, electromagnetic shielding, energy storage, gloves and condom materials.
The natural latex/class two-sided super graphene composite membrane adopted by the invention solves the problem of uniform dispersion of graphene in natural latex products, and in addition, the class two-sided super graphene has low oxidation degree and is easy to reduce in situ under the actions of a compounding agent, an alkaline environment and a post-vulcanization temperature in the natural latex, so that the composite membrane has excellent electrical property while being reinforced. The preparation method has simple process and excellent product performance, and is beneficial to industrial production.
The invention breaks the existing method for preparing natural latex/graphene nano composite aqueous dispersion, and utilizes the asymmetry of the distribution of the oxidation degree of the Janus-like graphene (one end is hydrophilic and has good water dispersibility, the other end is hydrophobic and retains the property of the graphene) to be compounded with the natural latex, so that the Janus-like graphene can be uniformly dispersed in the natural latex; and then, dipping, casting or suction filtering the natural latex/type dihedral graphene composite aqueous dispersion to form a film, and further heating and vulcanizing to obtain the natural latex/type dihedral graphene composite film with high strength and excellent electrical property.
By adopting the technical scheme, the invention has the following advantages:
1. the Shuangmian graphene-like sheet oxidation degree distribution in the invention is asymmetric, one end of the Shuangmian graphene-like sheet oxidation degree distribution is hydrophilic, the Shuangmian graphene-like sheet oxidation degree distribution has good water dispersibility, and when the pH value is 7-13, the Zeta potential value is-60 to-30; the other end is hydrophobic, and the property of graphene is reserved, so that the graphene has excellent mechanical property and conductivity. Therefore, the Janus-like graphene and the natural latex have excellent compatibility, and can be stably and uniformly dispersed in a natural latex matrix without modification or addition of a stabilizer. In addition, in the preparation process of the composite membrane, the natural latex compounding agent, the alkaline environment and the post-vulcanization temperature are utilized to carry out in-situ reduction on the Janus-like graphene, no extra process steps are added, and the method is suitable for natural latex products of various processes. Finally, the natural latex/quasi-dihedral graphene composite film with uniformly dispersed graphene is prepared.
2. The prepared composite film has excellent mechanical property, and under the condition that the elongation at break is improved by 10 percent compared with that of a pure adhesive film, the tensile strength is improved by 50 percent, and the tensile strain is over 900 percent; in addition, the 100% stress at definite elongation of the composite membrane is 0.8-1.2MPa, and the flexibility of the natural latex membrane is kept under low strain. The elasticity of the natural latex film can be well maintained when the rigid graphene with the biosurface is used for reinforcing the natural latex, the hydrophilic end ensures the uniform dispersion of the graphene with the biosurface in a natural latex matrix, the hydrophobic end and natural latex particles form a strong hydrophobic interaction, the graphene does not gather to form a network structure under low strain and deforms along with the natural latex film, the flexibility of the natural latex film is ensured, and the uniformly dispersed graphene sheet serves as a sufficient stress transfer point under high strain, so that the effects of reinforcing the natural latex and improving the elongation at break are achieved.
3. The prepared composite membrane has excellent electrical property: conductivity (conductivity 10)-8-1S/m), strain sensitivity (sensitivity factor 50-1000 at 5% -25% strain) and dielectric properties (room temperature, 10Hz of operating frequency, 300-500 of dielectric constant, 0.01-2 of dielectric loss). The graphene-like graphene still has the conductivity of graphene, and the electrical property of the composite film is excellent due to in-situ reduction in the preparation process of the composite film; in addition, the composite membrane keeps the flexibility of the natural latex membrane under small strain, so that the composite membrane can make more sensitive electrical response under small strain; the oxidation degree of the amphipathy graphene and the in-situ reduction degree in latex are adjusted, the hydrophobic end is conductive, the hydrophilic end is non-conductive, the dielectric constant is improved, and meanwhile, the dielectric loss is reduced, so that the composite film with excellent dielectric property can be obtained.
4. The preparation process of the Janus-like graphene aqueous dispersion is simple, the amount of the used oxidant is greatly reduced due to low oxidation degree, compared with the preparation of graphene oxide, the pollution is greatly reduced, the safety is improved, and the method is suitable for industrial actual production and large-scale preparation.
[ description of the drawings ]
FIG. 1 is a stress-strain curve of a natural latex composite film added with different content of Janus graphene;
FIG. 2 is the resistance sensitivity of a natural latex composite membrane compounded with a content of 0.1 wt% to human breath;
FIG. 3 is the resistance sensitivity of a natural latex composite membrane compounded with a content of 3 wt% to human breath;
FIG. 4 is a graph showing the dielectric constant and dielectric loss of a natural latex composite film compounded at a content of 3 wt%
FIG. 5 is a stress-strain curve of a natural latex composite membrane with different contents of graphene oxide added;
[ detailed description of the invention ]
The technical solution of the present invention is further illustrated below with reference to specific examples, but the scope of the present invention is not limited thereto.
Example 1
Weighing 200mL of concentrated sulfuric acid, adding the concentrated sulfuric acid into a 500mL wide-mouth bottle, performing magnetic stirring at a low rotating speed, then sequentially and slowly adding 10g of potassium permanganate and 10g of graphite, paying attention to the fact that the whole process is performed in an ice-water bath, and continuously stirring for 5 hours. 500mL of ice water is prepared and stirred magnetically, the mixed solution after reaction is slowly added into the ice water for dilution, and then hydrogen peroxide is added dropwise until the mixed solution of the ice water does not generate bubbles any more. The reaction solution was washed to neutrality with 100 mesh filter cloth. Adding the neutral graphite slurry into 100mL of 1mol/L sodium hydroxide solution, and performing ultrasonic treatment for 1 h; centrifuging at 8000rpm for 10min after ultrasonic treatment, repeating for 2-3 times until the supernatant turns black, and collecting the supernatant with a dropper to obtain the Shuangshen graphene-like product. The pH value of the obtained Shuangshen graphene aqueous dispersion is 10.2, the Zeta potential is-42, the carbon-oxygen ratio is 3.0, and the hydrophilic end ID/IGIs 1.2, hydrophobic end ID/IG0.7, an ultraviolet absorption peak position of 265nm, and an atomic force microscope showed an average size of the lamella of 1.1. mu.m. Adding 1 wt% of the Janus-like graphene aqueous dispersion into 60 wt% of pre-vulcanized latex according to the mass part, stirring for 60min, pouring into a glass mold, placing on a horizontal table for drying for 12h, and drying in an oven at 50 ℃ for 5 h. And taking the composite film from the mold, and putting the composite film in an oven at 110 ℃ for vulcanization for 40 min. The obtained composite film has excellent mechanical property and electrical property, the tensile strength of the composite film is 31MPa, the elongation at break is 1080%, the 100% stress at definite elongation is only 0.8MPa, and the flexibility under low strain is kept (figure 1); conductivity 10-5S/m, a sensitivity factor of 300 under 5% -25% strain, a working frequency of 10Hz, a dielectric constant of 270 and a dielectric loss of 0.8, and is suitable for the material fields of artificial skin, sensors, electromagnetic shielding, energy storage, gloves, condoms and the likeThe use of (1).
Example 2:
the types, the amounts and the process flow of the used materials are the same as those of the example 1, except that concentrated sulfuric acid, potassium permanganate and graphite react in an ice-water bath for 2 hours, and then the temperature is raised to 35 ℃ to continue the reaction for 3 hours. The pH value of the obtained Shuangshen graphene aqueous dispersion is 10.1, the Zeta potential is-43, the carbon-oxygen ratio is 2.6, and the hydrophilic end ID/IGIs 1.3, hydrophobic end ID/IGIt was 0.8, the ultraviolet absorption peak position was 260nm, and the atomic force microscope showed that the average size of the lamella was 1.1. mu.m. The obtained composite film has excellent mechanical property and electrical property, the tensile strength of the composite film is 33MPa, the elongation at break is 1100%, the 100% stress at definite elongation is only 0.8MPa, and the flexibility under low strain is kept; conductivity 10-5S/m, a sensitivity factor of 300 under 5% -25% strain, a working frequency of 10Hz, a dielectric constant of 250 and a dielectric loss of 0.5, and is suitable for application in the material fields of artificial skin, sensors, electromagnetic shielding, energy storage, gloves, condoms and the like.
Example 3:
the kind of material, the amount of the material used and the process were the same as in example 1 except that the amount of potassium permanganate was increased to 20 g. The pH value of the obtained Shuangshen graphene aqueous dispersion is 10.2, the Zeta potential is-46, the carbon-oxygen ratio is 2.1, and the hydrophilic end ID/IGIs 1.3, hydrophobic end ID/IG0.85, an ultraviolet absorption peak position of 240nm, and an atomic force microscope showed an average size of the lamella of 1.0. mu.m. The obtained composite film has excellent mechanical property and electrical property, the tensile strength of the composite film is 35MPa, the elongation at break is 1180%, the 100% stress at definite elongation is only 0.8MPa, and the flexibility under low strain is kept; conductivity 10-6S/m, a sensitivity factor of 500 under 5% -25% strain, a working frequency of 10Hz, a dielectric constant of 200 and a dielectric loss of 0.5, and is suitable for application in the material fields of artificial skin, sensors, electromagnetic shielding, energy storage, gloves, condoms and the like.
Example 4:
the kind, amount and process flow of the materials used were the same as those in example 1, except that the ultrasonic treatment time was shortened to 30 min. The obtained Janus-like graphene aqueous dispersionThe pH value of (A) is 10.2, the Zeta potential is-44, the carbon-oxygen ratio is 3.0, ID/IGIt was 1.5, the ultraviolet absorption peak position was 265nm, and the atomic force microscope showed that the average size of the lamella was 1.5. mu.m. The obtained composite film has excellent mechanical property and electrical property, the tensile strength of the composite film is 35MPa, the elongation at break is 997 percent, the 100 percent stress at definite elongation is 1.0MPa, and the flexibility under low strain is kept; conductivity 10-5S/m, a sensitivity factor of 450 under 5% -25% strain, a working frequency of 10Hz, a dielectric constant of 300 and a dielectric loss of 3, and is suitable for application in the field of materials such as artificial skin, sensors, electromagnetic shielding, energy storage, gloves, condoms and the like.
Example 5:
the types, the amounts and the process flow of the used materials are the same as those of example 1, except that the composite amount of the Janus-like graphene is 0.1 wt%. The tensile strength of the obtained composite film is 35MPa, the elongation at break is 1160%, the 100% stress at definite elongation is 0.8MPa, and the flexibility under low strain is kept (figure 1); conductivity 10-8S/m, a sensitivity factor of 500 (figure 2) under 5% -25% strain, a working frequency of 10Hz, a dielectric constant of 200 and a dielectric loss of 0.6, and is suitable for application in the material fields of artificial skin, sensors, electromagnetic shielding, energy storage, gloves, condoms and the like.
Example 6:
the types, the amounts and the process flow of the used materials are the same as those of example 1, except that the composite amount of the Janus-like graphene is 0.5 wt%. The tensile strength of the obtained composite film is 34MPa, the elongation at break is 1150%, the 100% stress at definite elongation is 0.8MPa, and the flexibility under low strain is kept (figure 1); conductivity 10-6S/m, a sensitivity factor under 5% -25% strain of 480, a working frequency of 10Hz, a dielectric constant of 230 and a dielectric loss of 0.8, and is suitable for application in the material fields of artificial skin, sensors, electromagnetic shielding, energy storage, gloves, condoms and the like.
Example 7:
the types, the amounts and the process flow of the used materials are the same as those of example 1, except that the composite amount of the Janus-like graphene is 3 wt%. The tensile strength of the obtained composite film is 31MPa, the elongation at break is 975%, and the 100% stress at definite elongation is 0.9MPa, flexibility at low strain is maintained (fig. 1); conductivity 10-3S/m, a sensitivity factor of 600 (figure 3) under 5% -25% strain, a working frequency of 10Hz, a dielectric constant of 310 and a dielectric loss of 1.58 (figure 4), and is suitable for application in the field of materials such as artificial skin, sensors, electromagnetic shielding, energy storage, gloves, condoms and the like.
Example 8:
the types, the amounts and the process flow of the used materials are the same as those of example 1, except that the composite amount of the Janus-like graphene is 5 wt%. The tensile strength of the obtained composite film is 30.5MPa, the elongation at break is 940%, the 100% stress at definite elongation is 0.95MPa, and the flexibility under low strain is kept (figure 1); conductivity 10-1S/m, the sensitivity factor under 5% -25% strain is 700, the working frequency is 10Hz, the dielectric constant is 350, the dielectric loss is 1.8, and the material is suitable for application in the material fields of artificial skin, sensors, electromagnetic shielding, energy storage, gloves, condoms and the like.
Example 9: the types, the amounts and the process flow of the used materials are the same as those in example 7, except that the natural latex/type Liangshen graphene composite liquid is thickened to 2800mPa s by using a thickening agent (sodium carboxymethyl cellulose), and then the thickened natural latex/type Liangshen graphene composite liquid is dip-coated on glove fabrics. The resulting glove was soft and had a surface conductivity of 10-3And S/m, the touch screen operation can be carried out.
Comparative example 1:
stirring the pre-vulcanized latex with the solid content of 60 wt% for 60min, pouring the mixture into a glass mold, placing the glass mold on a horizontal table for drying for 12h, and then drying the glass mold in an oven at 50 ℃ for 5 h. Taking the natural latex film off the mould, and placing the natural latex film in a 110 ℃ oven for vulcanization for 40 min. The obtained composite film has excellent mechanical property and electrical property, the tensile strength of the composite film is 28MPa, the elongation at break is 1100%, and the 100% stress at definite elongation is 0.8MPa (figure 1); no conductivity, dielectric properties and strain sensitivity.
Comparative example 2:
240ml of concentrated sulfuric acid is poured into a beaker containing 4g of graphite, slowly and stably stirred, and 12g of potassium permanganate is added for a plurality of times in a small amount. The reaction was first carried out in an ice-water bath for 2h, at which point the dispersion appeared dark green. Then slowly heating to 60 ℃, reacting for 4 hours, and changing the green color of the dispersion into viscous liquidAnd (3) stopping heating, cooling to room temperature, finally slowly pouring the dispersion into 1000ml of ultrapure water to stop the reaction, and adding 30ml of hydrogen peroxide to turn the color into golden yellow. And removing acid and metal ions in the dispersion liquid by adopting a multi-centrifugation mode to obtain graphene oxide, and then dialyzing to be neutral. The pH value of the obtained graphene oxide aqueous dispersion is 7, the Zeta potential is-36, the carbon-oxygen ratio is 0.6, ID/IGIt was 1.3, the ultraviolet absorption peak position was 235nm, and the atomic force microscope showed that the average size of the lamella was 1.1. mu.m. Adding 0.1 wt% of graphene oxide aqueous dispersion into 60 wt% of pre-vulcanized latex according to the mass part, stirring for 60min, pouring into a glass mold, drying for 12h on a horizontal table, and drying for 5h in an oven at 50 ℃. And taking the composite film from the mold, and putting the composite film in an oven at 110 ℃ for vulcanization for 40 min. The tensile strength of the obtained composite film is 25MPa, the elongation at break is 1060 percent, and the 100 percent stress at definite elongation is 0.96MPa (figure 5); no conductivity, dielectric properties and strain sensitivity.
Comparative example 3:
the types, the amounts and the process flows of the used materials are the same as those of the comparative example 1, except that the compounding amount of the graphene oxide is 0.5 wt%. The tensile strength of the obtained composite film is 24MPa, the elongation at break is 960 percent, and the 100 percent stress at definite elongation is 1MPa (figure 5); no conductivity, dielectric properties and strain sensitivity.
Comparative example 4:
the types, the amounts and the process flows of the used materials are the same as those of the comparative example 1, except that the compounding amount of the graphene oxide is 1 wt%. The tensile strength of the obtained composite film is 24MPa, the elongation at break is 807%, the 100% stress at definite elongation is 1.2MPa (figure 5), and the hand feeling of the film is hard; no conductivity, dielectric properties and strain sensitivity.
Comparative example 5:
the types, the amounts and the process flows of the used materials are the same as those of the comparative example 1, except that the compounding amount of the graphene oxide is 3 wt%. The tensile strength of the obtained composite film is 19MPa, the elongation at break is 614%, the 100% stress at definite elongation is 2.4MPa (figure 5), and the film has hard hand feeling; no conductivity, dielectric properties and strain sensitivity.
Comparative example 6:
the types, the amounts and the process flows of the used materials are the same as those of the comparative example 1, except that the compounding amount of the graphene oxide is 5 wt%. The tensile strength of the obtained composite film is 13MPa, the elongation at break is 421%, the 100% stress at definite elongation is 3.5MPa (figure 5), and the film has hard hand feeling; no conductivity, dielectric properties and strain sensitivity.
Comparative example 7: the material types, the used amounts and the preparation process flow of the graphene oxide are the same as the comparative example 4, except that the natural latex/graphene oxide composite solution is adjusted to 2800mPa s viscosity by using sodium carboxymethyl cellulose, and then is dipped in the glove fabric, and then is soaked in hydriodic acid solution. The resultant glove fabric was contaminated with hydriodic acid solution and the glove was hard and non-conductive.
Claims (10)
1. A method for stably and uniformly dispersing Janus-like graphene in natural latex is characterized by comprising the following steps:
and (2) mixing the amphiphobic graphene aqueous dispersion with the natural latex according to a proportion and uniformly stirring by utilizing the water dispersibility provided by the amphiphobic graphene hydrophilic part to obtain the stably-dispersed natural latex/amphiphobic graphene dispersion.
2. A preparation method of a natural latex/Niangshen graphene composite film is characterized by comprising the following steps:
uniformly dispersing the Janus-like graphene aqueous dispersion in a natural latex matrix according to a ratio, mixing and stirring uniformly, reducing Janus-like graphene in situ under the action of a compounding agent, an alkaline environment and a post-vulcanization temperature in the natural latex, forming a film, and vulcanizing to obtain the natural latex/Janus-like graphene composite film.
3. The method of claim 2, wherein:
uniformly dispersing the Janus-like graphene aqueous dispersion in a natural latex matrix according to a ratio, mixing and stirring uniformly, pouring into a mold, drying, taking the composite film off the mold, and vulcanizing to obtain the natural latex/Janus-like graphene composite film.
4. The method of claim 2, wherein:
the vulcanization is heating vulcanization, and the used equipment is one or two of vacuum drying and forced air drying;
preferably, the vulcanization temperature is 80-110 ℃ and the time is 0.5-2 h.
5. The method of claim 2, wherein:
forming a film by dipping, casting or suction filtration;
the dipping film forming refers to dipping a dipping die into natural latex-type Shuangshen graphene composite aqueous dispersion, and then pulling to form a film, wherein the pulling speed is 2-10 mm/min;
the casting film forming refers to pouring the natural latex-class Janus graphene composite aqueous dispersion into a mold, and forming a film at the temperature of 25-60 ℃;
the film formation by suction filtration refers to the film formation by vacuum filtration of the natural latex-class Shuangshen graphene composite aqueous dispersion under the condition of a flowing field.
6. The method of claim 1 or 2, wherein:
the uniform mixing and stirring means that the mixture of the Janus-like graphene aqueous dispersion and the natural latex is carried out under the condition of continuous stirring, the stirring speed is 200-2000r/min, the stirring time is 5-120min, the temperature is 10-40 ℃, and the content of the Janus-like graphene in the composite film is controlled to be 0.1-10 wt%.
7. The method of claim 1 or 2, wherein:
the natural latex is pre-vulcanized natural latex, and comprises fresh natural latex derived from hevea trees or concentrated natural latex, and is pre-vulcanized by adopting a vulcanization system consisting of a vulcanizing agent, an accelerator and an activator, an anti-aging agent and a stabilizer;
it is preferable that: the dry rubber solid content of the pre-vulcanized natural rubber latex is 60 wt%;
it is preferable that: the prevulcanized natural latex is prepared from the following raw materials in parts by weight: 100 parts of natural latex; 0.5-1.5 parts of vulcanizing agent sulfur; 0.4-0.6 part of anti-aging agent 2, 6-di-tert-butyl-p-cresol; 0.2-0.6 part of anti-aging agent 2, 2' -methylene bis- (4-methyl-6-tert-butylphenol); 0.8-1.2 parts of activator ZnO; 0.2-0.6 part of promoter zinc diethyldithiocarbamate; 0.2-0.5 part of stabilizer KOH;
preferably, the complexing agent comprises ZnO, S; the alkaline environment includes the stabilizers KOH of natural latex and ammonia.
8. The method of claim 1 or 2, wherein:
the oxidation degree of the Janus-like graphene is asymmetrically distributed, one end of the Janus-like graphene is hydrophilic and has good water dispersibility, and the other end of the Janus-like graphene is hydrophobic, so that the property of the graphene is reserved;
it is preferable that: the addition amount of the Janus-like graphene in the composite film is 0.1-10 wt% (dry weight ratio);
it is preferable that: the carbon-oxygen ratio of the Janus-like graphene is 1-12; hydrophilic end in situ Raman test ID/IGGreater than 1, hydrophobic end ID/IGLess than 1; the thickness of the hydrophilic end sheet layer is thicker than that of the part of the hydrophobic end sheet layer, and the thickness difference is 0.05-0.6 nm;
it is preferable that: the size of the sheet layer of the Janus-like graphene is 5-6000 nm;
it is preferable that: when the pH value is 7-13, the Zeta potential of the Shuangmian graphene-like aqueous dispersion liquid is-60 to-30.
9. A composite membrane prepared by the method of any of claims 2 to 8, wherein:
the tensile strength of the composite membrane is 25-40MPa, the 100% stress at definite elongation is 0.8-1.2MPa, and the flexibility of the natural latex membrane is kept under low strain;
it is preferable that: the conductivity of the composite film is 10-8-1S/m; the sensitivity factor is 50-1000 under the strain of 5% -25%;
it is preferable that: at room temperature and 10Hz, the dielectric constant is 300-500 and the dielectric loss is 0.01-2.
10. Use of the composite film according to claim 9 in the fields of artificial skin, sensors, electromagnetic shielding, energy storage, gloves and condom materials.
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