CN107286403A - A kind of antistatic natural rubber and preparation method thereof - Google Patents
A kind of antistatic natural rubber and preparation method thereof Download PDFInfo
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- CN107286403A CN107286403A CN201710555827.2A CN201710555827A CN107286403A CN 107286403 A CN107286403 A CN 107286403A CN 201710555827 A CN201710555827 A CN 201710555827A CN 107286403 A CN107286403 A CN 107286403A
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- heveatex
- natural rubber
- graphene oxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
- C08L7/02—Latex
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- C—CHEMISTRY; METALLURGY
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/017—Additives being an antistatic agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
Abstract
A kind of antistatic natural rubber and preparation method thereof, is related to conducing composite material field.The preparation method of antistatic natural rubber, including：Graphene oxide is mixed into obtain graphene oxide suspension with water.Cation Heveatex is mixed to obtain after Heveatex is mixed with peregal solution with acid solution.Graphene oxide suspension is mixed into obtain graphene oxide Heveatex suspension with cation Heveatex.Reducing agent and the suspension are mixed and heated to 60~90 DEG C.The agglomeration traits of graphene are this method solve, the rubber with anti-static function can be made in stable system.A kind of antistatic natural rubber, is made by the preparation method of above-mentioned antistatic natural rubber.It has preferable anlistatig function.
Description
Technical field
The present invention relates to conducing composite material field, and more particularly to a kind of antistatic natural rubber and preparation method thereof.
Background technology
With the development of modern electronics industry, information industry and new and high technology, electrically conductive composite, especially filled-type are conductive
Composite new technical field application and development, it is more noticeable.On the definition of conducting polymer composite, to mesh
Before untill there is no unified standard both at home and abroad, broadly, typically by volume conductance ρ be less than 1010Ω cm high polymer material system
Referred to as conducting polymer composite, wherein again by ρ 106~1010It is referred to as antistatic macromolecule material between Ω cm；ρ is existed
100~106It is referred to as semi-conductive high polymer material between Ω cm；ρ is less than 100Ω cm's is referred to as conducting polymer composite.
For composite conductive polymer, the species and performance of filler are to influence its conductance to be most directly also topmost
Factor, current conductive rubber be mainly with conductive filler carbon system (based on graphite, carbon black and carbon fiber), metal system (gold, silver, copper,
Nickel etc.), particle surface plating metal three major types.Carbon system is to prepare the main conductive filler of conductive composite rubber at present, but has a pollution,
Unsuitable preparation has the conductive material of color requirement；Metal system particle surface plating metal ratio it is great, in the polymer disperse compared with
Difficulty, is also less suited to the product of proportion requirement.In recent years, made using graphene as the filler filling of higher-dimension New Type of Carbon system is represented
Standby conductive material causes extensive concern, achieves plentiful and substantial achievement in research.
The content of the invention
It is an object of the invention to provide a kind of preparation method of antistatic natural rubber, graphene this method solve
The rubber with anti-static function can be made in agglomeration traits, stable system.
Another object of the present invention is to provide a kind of antistatic natural rubber, it has preferable anlistatig function.
The present invention is solved its technical problem and realized using following technical scheme.
The present invention proposes a kind of preparation method of antistatic natural rubber, including：It is 1 by weight ratio:5~1000 graphite
Olefinic oxide mixes to obtain graphene oxide suspension with water.
After the Heveatex for being 15%-70% by mass concentration is mixed with the peregal solution that mass concentration is 5%-30%
Cation Heveatex is mixed to obtain for 1%-20% acid solution with mass concentration, the pH value of cation Heveatex is
2.4-2.6；The weight ratio of the dry glue in peregal and Heveatex in peregal solution is 1:20~100.
According to weight ratio it is 1 by graphene oxide suspension and cation Heveatex:1~100 ratio is mixed
Graphene oxide-Heveatex suspension.
Reducing agent is mixed with graphene oxide-Heveatex suspension, 60~90 DEG C are heated to.Reducing agent and graphite
The weight ratio of graphene oxide in olefinic oxide-Heveatex suspension is 1:0.2~10.
The present invention also proposes a kind of antistatic natural rubber, is made by the preparation method of above-mentioned antistatic natural rubber.
The beneficial effect of the embodiment of the present invention is：A kind of preparation method of antistatic natural rubber, be by mass concentration
15%-70% Heveatex with mass concentration is 1%-20% after being mixed with the peregal solution that mass concentration is 5%-30%
Acid solution mix to obtain cation Heveatex.Peregal solution is added in Heveatex, Heveatex can be improved
Stability, prevent after acid adding flocculate.Acid in acid solution can provide hydrogen ion, and acid solution is mixed with Heveatex to be made
The albumen amino band in acid condition so that latex particle surface is wrapped up on the surface of Heveatex particle by hydrogen ion
Positive electricity, latex particle entirety positively charged.According to weight ratio it is 1 by graphene oxide suspension and cation Heveatex:1~
Graphene oxide in 100 ratio mixing, graphene oxide suspension is negatively charged, cation Heveatex positively charged,
In the presence of electrostatic self-assembled, graphene oxide interacts with cation Heveatex, obtains dispersion effect preferable
Graphene oxide-Heveatex suspension.Reducing agent is mixed with graphene oxide-Heveatex suspension, is heated to
60~90 DEG C.Because reducing agent carries out in-situ reducing in graphene oxide-Heveatex suspension to graphene oxide,
It ensure that being reduced obtained graphene is also preferably dispersed in conductive Heveatex, and the reducing condition is gentle, it is ensured that
The stability of whole system, obtained product has high conduction performance, has anti-static function after drying vulcanization.
A kind of antistatic natural rubber, is made by the preparation method of above-mentioned antistatic natural rubber.It has preferable
Anti-static function.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be attached to what is used required in embodiment
Figure is briefly described, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, therefore is not construed as pair
The restriction of scope, for those of ordinary skill in the art, on the premise of not paying creative work, can also be according to this
A little accompanying drawings obtain other related accompanying drawings.
Fig. 1 is the electron microscope picture of test example 2 of the present invention.
Embodiment
, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer
Technical scheme be clearly and completely described.Unreceipted actual conditions person, builds according to normal condition or manufacturer in embodiment
The condition of view is carried out.Agents useful for same or the unreceipted production firm person of instrument, are the conventional production that can be obtained by commercially available purchase
Product.
A kind of antistatic natural rubber of the embodiment of the present invention and preparation method thereof is specifically described below.
A kind of preparation method of antistatic natural rubber, including：It is 1 by weight ratio:5~1000 graphene oxide with
Water mixes to obtain graphene oxide suspension.
In an embodiment of the present invention, after graphene oxide is mixed with water, first is carried out ultrasonically treated.Pass through first
After ultrasonically treated, graphene oxide can preferably be mixed to get uniform suspension with water.In an embodiment of the present invention,
One ultrasonically treated ultrasonic power is 50~500W, and ultrasonic time is 2~60min.Furthermore it is preferred that graphene oxide with
After water mixing, it is ultrasonically treated that control temperature carries out first again in the range of 20~80 DEG C, after 10~50min of magnetic agitation.This
Sample can cause graphene oxide fully to infiltrate, and be conducive to being well mixed with water.
In an embodiment of the present invention, graphene oxide may be selected to peel off or change by chemical oxidation graphite, micromechanics
Learn product made from the method for vapour deposition.Preferably, graphene oxide is made by chemical oxidation graphite.
After the Heveatex for being 15%-70% by mass concentration is mixed with the peregal solution that mass concentration is 5%-30%
Cation Heveatex is mixed to obtain for 1%-20% acid solution with mass concentration, the pH value of cation Heveatex is
2.4-2.6；The weight ratio of the dry glue in peregal and Heveatex in peregal solution is 1:20~100.
Peregal solution is added in Heveatex, the stability of Heveatex can be improved, prevents from flocculating after acid adding.It is excellent
Average in selection of land, peregal solution adds as paregal O -30.Peregal, refers to the addition product of natural fatty alcohol and oxirane,
Belong to nonionic surfactant.
Acid in acid solution can provide hydrogen ion, and acid solution is mixed with Heveatex can cause latex particle surface
Albumen amino positively charged in acid condition, latex particle entirety positively charged.In the present embodiment, Heveatex includes dry glue
And water, dry glue here refers to natural rubber.In an embodiment of the present invention, acid solution includes sulfuric acid solution, formic acid solution
Or acetic acid solution；Preferably, acid solution is acetic acid solution.Furthermore it is preferred that the mass concentration of acid solution is 2%~10%.My god
The mass concentration of right latex is 30%~65%.
According to weight ratio it is 1 by graphene oxide suspension and cation Heveatex:1~100 ratio is mixed
Graphene oxide-Heveatex suspension.
Wherein, the graphene oxide in graphene oxide suspension is negatively charged, cation Heveatex positively charged,
In the presence of electrostatic self-assembled, graphene oxide interacts with cation Heveatex, obtains the preferable stone of dispersion effect
Black olefinic oxide-Heveatex suspension.Preferably, the weight ratio of graphene oxide suspension and cation Heveatex is
1:20~100.In an embodiment of the present invention, first carried out after graphene oxide suspension is mixed with cation Heveatex
Second is ultrasonically treated, and graphene oxide suspension and cation Heveatex dispersion effect are enabled to more by ultrasonically treated
It is good.In an embodiment of the present invention, the second ultrasonically treated ultrasonic power is 50~500W, and ultrasonic time is 5~60min.
In addition, in graphene oxide suspension, due to the good water soluble disperse of graphene oxide, therefore, graphite
Olefinic oxide can be evenly dispersed into cation Heveatex, it is to avoid the reunion of graphene oxide.
Reducing agent is mixed with graphene oxide-Heveatex suspension, 60~90 DEG C is heated to and obtains conductive natural
Rubber latex.The weight ratio of reducing agent and the graphene oxide in graphene oxide-Heveatex suspension is 1:0.2~
10。
, can be by graphene oxide-Heveatex suspension by reducing agent under 60~90 DEG C of temperature conditionss
Graphene oxide be reduced into graphene.Due to reducing agent in graphene oxide-Heveatex suspension to graphene
Oxide carries out in-situ reducing, it is ensured that is reduced obtained graphene and is also preferably dispersed in conductive Heveatex, and
The reducing condition is gentle, it is ensured that the stability of conductive natural rubber latex, obtained product has high conduction performance, through overdrying
There is anti-static function after dry vulcanization.In an embodiment of the present invention, reducing agent includes ascorbic acid, citric acid, sodium borohydride
Or hydrazine hydrate.Preferably, reducing agent includes ascorbic acid or citric acid.
In an embodiment of the present invention, first carried out after reducing agent is mixed with graphene oxide-Heveatex suspension
3rd is ultrasonically treated, is again heated to 60~90 DEG C.
Reducing agent is mixed into progress with graphene oxide-Heveatex suspension the 3rd ultrasonically treated, will can reduced
Agent and graphene oxide-Heveatex suspension are sufficiently mixed, and are conducive in graphene oxide-Heveatex suspension
Graphene oxide is fully contacted with reducing agent, and graphene oxide can fully be reduced into graphene.The present invention's
In embodiment, the 3rd ultrasonically treated ultrasonic power is 50~100W, and ultrasonic time is 5~60min.It should be noted that leading
Electric natural rubber latex both can be practical directly as latex, can also solidify drying it is hot-forming after use.
40-70 DEG C is heated to after conductive natural rubber latex is mixed with vulcanizing system and obtains the conductive natural rubber latex of presulfurization
Breast.The weight ratio of the dry glue in Heveatex in vulcanizing system and graphene oxide-Heveatex suspension is 1:20~
200.The weight ratio of dry glue i.e. in Heveatex of the vulcanizing system with participating in reaction is 1:20~200.
In an embodiment of the present invention, vulcanizing system includes vulcanizing agent and accelerator.Preferably, vulcanizing agent includes sulphur.
Preferably, accelerator includes thiazoles, thiurams, sulfenamide, the Thiocarbamate class of guanidine two, Thiourea or aldehyde amine
Class accelerator.
The conductive natural rubber latex of presulfurization is first subjected to plastic film mulch, dipping film forming or spraying film forming.It is again that presulfurization is conductive
Natural rubber latex is dehydrated under conditions of 20-60 DEG C, is vulcanized under 70-110 DEG C of temperature conditionss.Rubber after vulcanization
Product has anti-static function.
The present invention also provides a kind of antistatic natural rubber, is made by the preparation method of above-mentioned antistatic natural rubber.
It has preferable anti-static function.
The feature and performance to the present invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of antistatic natural rubber, the preparation method of the antistatic natural rubber includes：
It is 1 by weight ratio:100 graphene oxide is mixed with water in beaker, and control temperature is in 20 DEG C, magnetic force
Stir after 30min, ultrasonically treated 15min obtains graphene oxide suspension under 100W power condition.
The peregal solution for being 10% by mass concentration is mixed with the fresh Heveatex that mass concentration is 45%, Ran Houzai
The acetic acid that mass concentration is 3.85% is quickly poured into, until the pH value of system is 2.4, cation natural gum is made in magnetic agitation
Breast.The weight ratio of the dry glue in paregal O -30 and fresh Heveatex wherein in peregal solution is 1:50.
According to weight ratio it is 1 by graphene oxide suspension and cation Heveatex:1 ratio mixing, Ran Hou
Ultrasonically treated 50min obtains graphene oxide-Heveatex suspension under 50W power condition.
Bad hematic acid is added in graphene oxide-Heveatex suspension, it is ultrasonically treated under 50W power condition
60min.Then magnetic agitation is carried out, 80 DEG C are heated to, conductive natural rubber latex is obtained.Wherein, bad hematic acid and graphene oxygen
The weight ratio of graphene oxide in compound-Heveatex suspension is 1:5.
Sulfur cross-linking system will be added in conductive natural rubber, the conductive natural rubber latex of presulfurization is obtained by being heated to 60 DEG C
Breast.The weight ratio of wherein vulcanizing system and the dry glue in the Heveatex in graphene oxide-Heveatex suspension is 1:
100。
By the conductive natural rubber latex of presulfurization by plastic film mulch, dehydrated at a temperature of 30 DEG C, in 110 DEG C of condition
It is lower to be vulcanized.
Embodiment 2
A kind of antistatic natural rubber, the preparation method of the antistatic natural rubber includes：
It is 1 by weight ratio:20 graphene oxide is mixed with water in beaker, and control temperature is in 30 DEG C, magnetic force
Stir after 45min, ultrasonically treated 60min obtains graphene oxide suspension under 80W power condition.
The peregal solution for being 20% by mass concentration is mixed with the fresh Heveatex that mass concentration is 30%, Ran Houzai
The formic acid that mass concentration is 2% is quickly poured into, until the pH value of system is 2.5, cation Heveatex is made in magnetic agitation.Its
The weight ratio of the dry glue in paregal O -30 and fresh Heveatex in middle peregal solution is 3:100.
According to weight ratio it is 1 by graphene oxide suspension and cation Heveatex:1 ratio mixing, Ran Hou
Ultrasonically treated 50min obtains graphene oxide-Heveatex suspension under 50W power condition.
Citric acid is added in graphene oxide-Heveatex suspension, it is ultrasonically treated under 50W power condition
60min.Then magnetic agitation is carried out, 80 DEG C are heated to, conductive natural rubber latex is obtained.Wherein, citric acid and graphene oxygen
The weight ratio of graphene oxide in compound-Heveatex suspension is 1:2.
Sulfur cross-linking system will be added in conductive natural rubber, the conductive natural rubber latex of presulfurization is obtained by being heated to 60 DEG C
Breast.The weight ratio of wherein vulcanizing system and the dry glue in the Heveatex in graphene oxide-Heveatex suspension is 1:
50。
By the conductive natural rubber latex of presulfurization by spraying film forming, dehydrated at a temperature of 20 DEG C, at 95 DEG C
Under the conditions of vulcanized.
Embodiment 3
A kind of antistatic natural rubber, the preparation method of the antistatic natural rubber includes：
It is 1 by weight ratio:10 graphene oxide is mixed with water in beaker, and control temperature is in 40 DEG C, magnetic force
Stir after 50min, ultrasonically treated 60min obtains graphene oxide suspension under 100W power condition.
The peregal solution for being 25% by mass concentration is mixed with the fresh Heveatex that mass concentration is 60%, Ran Houzai
The formic acid that mass concentration is 10% is quickly poured into, until the pH value of system is 2.6, cation Heveatex is made in magnetic agitation.
The weight ratio of the dry glue in paregal O -30 and fresh Heveatex wherein in peregal solution is 1:20.
According to weight ratio it is 1 by graphene oxide suspension and cation Heveatex:100 ratio mixing, then
Ultrasonically treated 45min obtains graphene oxide-Heveatex suspension under 150W power condition.
Citric acid is added in graphene oxide-Heveatex suspension, it is ultrasonically treated under 50W power condition
60min.Then magnetic agitation is carried out, 85 DEG C are heated to, conductive natural rubber latex is obtained.Wherein, citric acid and graphene oxygen
The weight ratio of graphene oxide in compound-Heveatex suspension is 1:7.
Sulfur cross-linking system will be added in conductive natural rubber, the conductive natural rubber latex of presulfurization is obtained by being heated to 65 DEG C
Breast.The weight ratio of wherein vulcanizing system and the dry glue in the Heveatex in graphene oxide-Heveatex suspension is 1:
20。
By the conductive natural rubber latex of presulfurization by impregnating film forming, dehydrated at a temperature of 35 DEG C, at 110 DEG C
Under the conditions of vulcanized.
Embodiment 4
A kind of antistatic natural rubber, the preparation method of the antistatic natural rubber includes：
It is 1 by weight ratio:5 graphene oxide is mixed with water in beaker, and control temperature is at 30 DEG C, and magnetic force is stirred
Mix after 20min, ultrasonically treated 45min obtains graphene oxide suspension under 50W power condition.
The peregal solution for being 5% by mass concentration is mixed with the fresh Heveatex that mass concentration is 60%, Ran Houzai
The formic acid that mass concentration is 10% is quickly poured into, until the pH value of system is 2.6, cation Heveatex is made in magnetic agitation.
The weight ratio of the dry glue in paregal O -30 and fresh Heveatex wherein in peregal solution is 1:100.
According to weight ratio it is 1 by graphene oxide suspension and cation Heveatex:20 ratio mixing, Ran Hou
Ultrasonically treated 30min obtains graphene oxide-Heveatex suspension under 250W power condition.
Sodium borohydride is added in graphene oxide-Heveatex suspension, under 60W power condition at ultrasound
Manage 40min.Then magnetic agitation is carried out, 60 DEG C are heated to, conductive natural rubber latex is obtained.Wherein, sodium borohydride and graphite
The weight ratio of graphene oxide in olefinic oxide-Heveatex suspension is 1:0.2.
Sulfur cross-linking system will be added in conductive natural rubber, the conductive natural rubber latex of presulfurization is obtained by being heated to 40 DEG C
Breast.The weight ratio of wherein vulcanizing system and the dry glue in the Heveatex in graphene oxide-Heveatex suspension is 1:
80。
By the conductive natural rubber latex of presulfurization by spraying film forming, dehydrated at a temperature of 40 DEG C, at 70 DEG C
Under the conditions of vulcanized.
Embodiment 5
A kind of antistatic natural rubber, the preparation method of the antistatic natural rubber includes：
It is 1 by weight ratio:500 graphene oxide is mixed with water in beaker, and control temperature is in 60 DEG C, magnetic force
Stir after 10min, ultrasonically treated 30min obtains graphene oxide suspension under 300W power condition.
The peregal solution for being 20% by mass concentration is mixed with the fresh Heveatex that mass concentration is 65%, Ran Houzai
The acetic acid that mass concentration is 5% is quickly poured into, until the pH value of system is 2.5, cation Heveatex is made in magnetic agitation.Its
The weight ratio of the dry glue in paregal O -30 and fresh Heveatex in middle peregal solution is 1:25.
According to weight ratio it is 1 by graphene oxide suspension and cation Heveatex:500 ratio mixing, then
Ultrasonically treated 20min obtains graphene oxide-Heveatex suspension under 400W power condition.
Hydrazine hydrate is added in graphene oxide-Heveatex suspension, it is ultrasonically treated under 80W power condition
20min.Then magnetic agitation is carried out, 70 DEG C are heated to, conductive natural rubber latex is obtained.Wherein, hydrazine hydrate and graphene oxygen
The weight ratio of graphene oxide in compound-Heveatex suspension is 1:4.
Sulfur cross-linking system will be added in conductive natural rubber, the conductive natural rubber latex of presulfurization is obtained by being heated to 50 DEG C
Breast.The weight ratio of wherein vulcanizing system and the dry glue in the Heveatex in graphene oxide-Heveatex suspension is 1:
200。
By the conductive natural rubber latex of presulfurization by impregnating film forming, dehydrated at a temperature of 50 DEG C, at 90 DEG C
Under the conditions of vulcanized.
Embodiment 6
A kind of antistatic natural rubber, the preparation method of the antistatic natural rubber includes：
It is 1 by weight ratio:1000 graphene oxide is mixed with water in beaker, and control temperature is in 80 DEG C, magnetic
After power stirring 40min, ultrasonically treated 2min obtains graphene oxide suspension under 500W power condition.
The peregal solution for being 30% by mass concentration is mixed with the fresh Heveatex that mass concentration is 55%, Ran Houzai
The sulfuric acid that mass concentration is 20% is quickly poured into, until the pH value of system is 2.5, cation Heveatex is made in magnetic agitation.
The weight ratio of the dry glue in paregal O -30 and fresh Heveatex wherein in peregal solution is 1:10.
According to weight ratio it is 1 by graphene oxide suspension and cation Heveatex:75 ratio mixing, Ran Hou
Ultrasonically treated 5min obtains graphene oxide-Heveatex suspension under 500W power condition.
Bad hematic acid is added in graphene oxide-Heveatex suspension, under 100W power condition at ultrasound
Manage 5min.Then magnetic agitation is carried out, 90 DEG C are heated to, conductive natural rubber latex is obtained.Wherein, bad hematic acid and graphene oxygen
The weight ratio of graphene oxide in compound-Heveatex suspension is 1:10.
Sulfur cross-linking system will be added in conductive natural rubber, the conductive natural rubber latex of presulfurization is obtained by being heated to 70 DEG C
Breast.The weight ratio of wherein vulcanizing system and the dry glue in the Heveatex in graphene oxide-Heveatex suspension is 1:
150。
The conductive natural rubber latex of presulfurization is dehydrated at a temperature of 60 DEG C, sulphur is carried out under conditions of 100 DEG C
Change.
Test example 1
Electrical conductivity is tested：With reference to GB/T2439-2001 (vulcanization rubber or thermoplastic elastomer electric conductivity and dissipative performance electricity
The measure of conductance) test of electrical conductivity is carried out to embodiment 1-6 antistatic natural rubber, its result is recorded in table 1.
Table 1 implements the electrical conductivity of 1-6 antistatic natural rubber
From the results shown in Table 1, the electrical conductivity of embodiment 1-6 antistatic natural rubber is all higher than 10-6S/cm, says
Antistatic effect preferably antistatic day can be made by the preparation method of the antistatic natural rubber of the embodiment of the present invention by understanding
Right rubber.
Test example 2
The antistatic natural rubber of embodiment 2 is carried out after liquid nitrogen brittle failure, electron microscope observation is scanned to section,
Its result is as shown in Figure 1.
Interpretation of result:As can be seen that the graphene oxide being reduced in antistatic natural rubber from Fig. 1 result
(i.e. graphene) establishes partially electronically conductive path.
In summary, a kind of antistatic natural rubber of the embodiment of the present invention and preparation method thereof, in preparation method, in day
Peregal solution is added in right latex, the stability of Heveatex can be improved, prevents from flocculating after acid adding.Acid in acid solution can
To provide hydrogen ion, acid solution is mixed with Heveatex can cause the albumen on latex particle surface amino band in acid condition
Graphene oxide in positive electricity, latex particle entirety positively charged, graphene oxide suspension is negatively charged, cation natural gum
Newborn positively charged, in the presence of electrostatic self-assembled, graphene oxide interacts with cation Heveatex, obtains scattered effect
Fruit preferably graphene oxide-Heveatex suspension.Because reducing agent is in graphene oxide-Heveatex suspension
In-situ reducing is carried out to graphene oxide, it is ensured that be reduced obtained graphene and be also preferably dispersed in conductive Heveatex
In, and the reducing condition is gentle, it is ensured that and the stability of whole system, obtained product has high conduction performance, through overdrying
There is anti-static function after dry vulcanization.
Embodiments described above is a part of embodiment of the invention, rather than whole embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made
Every other embodiment, belongs to the scope of protection of the invention.
Claims (10)
1. a kind of preparation method of antistatic natural rubber, it is characterised in that including：It is 1 by weight ratio:5~1000 graphite
Olefinic oxide mixes to obtain graphene oxide suspension with water；
The Heveatex for being 15%-70% by mass concentration mixed with the peregal solution that mass concentration is 5%-30% after with matter
Amount concentration mixes to obtain cation Heveatex for 1%-20% acid solution, and the pH value of the cation Heveatex is
2.4-2.6；The weight ratio of the dry glue in peregal and the Heveatex in the peregal solution is 1:20~100；
According to weight ratio it is 1 by the graphene oxide suspension and the cation Heveatex:1~100 ratio is mixed
Close to obtain graphene oxide-Heveatex suspension；
Reducing agent is mixed with the graphene oxide-Heveatex suspension, 60~90 DEG C are heated to；The reducing agent with
The weight ratio of the graphene oxide in the graphene oxide-Heveatex suspension is 1:0.2~10.
2. the preparation method of antistatic natural rubber according to claim 1, it is characterised in that the graphene oxide
Weight ratio with water is 1:10~100.
3. the preparation method of antistatic natural rubber according to claim 1, it is characterised in that the acid solution includes sulphur
Acid solution, formic acid solution or acetic acid solution；Preferably, the acid solution is acetic acid solution.
4. the preparation method of antistatic natural rubber according to claim 1, it is characterised in that the quality of the acid solution
Concentration is 2%~10%, and the mass concentration of the Heveatex is 30%~65%.
5. the preparation method of antistatic natural rubber according to claim 1, it is characterised in that the graphene oxide
The weight ratio of suspension and the cation Heveatex is 1:20~100.
6. the preparation method of antistatic natural rubber according to claim 1, it is characterised in that in the peregal solution
Described average add as paregal O -30.
7. the preparation method of antistatic natural rubber according to claim 1, it is characterised in that the reducing agent includes anti-
Bad hematic acid, citric acid, sodium borohydride or hydrazine hydrate；Preferably, the reducing agent includes ascorbic acid or citric acid.
8. the preparation method of antistatic natural rubber according to claim 1, it is characterised in that by the reducing agent and institute
Graphene oxide-Heveatex suspension mixing is stated, is heated to after 60~90 DEG C, then 40- is mixed and heated to vulcanizing system
70 DEG C obtain the conductive natural rubber latex of presulfurization；The conductive natural rubber latex of the presulfurization is taken off under conditions of 20-60 DEG C
Water is dried, and is vulcanized under 70-110 DEG C of temperature conditionss；The vulcanizing system suspends with the graphene oxide-Heveatex
The weight ratio of the dry glue in the Heveatex in liquid is 1:20~200.
9. the preparation method of antistatic natural rubber according to claim 8, it is characterised in that the vulcanizing system includes
Vulcanizing agent and accelerator；Preferably, the vulcanizing agent includes sulphur；The accelerator includes thiazoles, thiurams, secondary sulphonyl
Amine, the Thiocarbamate class of guanidine two, Thiourea or aldehyde amine accelerators.
10. a kind of antistatic natural rubber, it is characterised in that as the antistatic natural rubber described in claim any one of 1-9
Preparation method be made.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110256743A (en) * | 2019-05-27 | 2019-09-20 | 常州暖乐康碳材料科技有限公司 | Antistatic, the wear-resisting graphene-based rubber of tire |
| CN114920999A (en) * | 2022-05-30 | 2022-08-19 | 武汉工程大学 | Multifunctional rubber foam sensing material and preparation method thereof |
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| CN101418089A (en) * | 2008-12-03 | 2009-04-29 | 中国热带农业科学院农产品加工研究所 | Method for preparing natural rubber-carbon nano tube composite material by using static electricity self-assembly |
| CN102161785A (en) * | 2011-03-10 | 2011-08-24 | 四川大学 | Preparation method of graphene/polymer nano composite material |
| CN104817743A (en) * | 2015-04-15 | 2015-08-05 | 奉化市裕隆化工新材料有限公司 | Graphene modified chlorinated rubber composite material and preparation method thereof |
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| CN101418089A (en) * | 2008-12-03 | 2009-04-29 | 中国热带农业科学院农产品加工研究所 | Method for preparing natural rubber-carbon nano tube composite material by using static electricity self-assembly |
| CN102161785A (en) * | 2011-03-10 | 2011-08-24 | 四川大学 | Preparation method of graphene/polymer nano composite material |
| CN104817743A (en) * | 2015-04-15 | 2015-08-05 | 奉化市裕隆化工新材料有限公司 | Graphene modified chlorinated rubber composite material and preparation method thereof |
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| CN110256743A (en) * | 2019-05-27 | 2019-09-20 | 常州暖乐康碳材料科技有限公司 | Antistatic, the wear-resisting graphene-based rubber of tire |
| CN114920999A (en) * | 2022-05-30 | 2022-08-19 | 武汉工程大学 | Multifunctional rubber foam sensing material and preparation method thereof |
| CN114920999B (en) * | 2022-05-30 | 2024-01-23 | 武汉工程大学 | Multifunctional rubber foam sensing material and preparation method thereof |
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