CN107286403B - 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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- CN107286403B CN107286403B CN201710555827.2A CN201710555827A CN107286403B CN 107286403 B CN107286403 B CN 107286403B CN 201710555827 A CN201710555827 A CN 201710555827A CN 107286403 B CN107286403 B CN 107286403B
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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, comprising: graphene oxide is mixed to obtain to graphene oxide suspension with water.Cationic 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 cationic Heveatex.Reducing agent and the suspension are mixed and heated to 60~90 DEG C.This method solve the agglomeration traits of graphene, the rubber product 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 the function of preferable antistatic.
Description
Technical field
The present invention relates to conducing composite material fields, and in particular to a kind of antistatic natural rubber and preparation method thereof.
Background technique
With the development of modern electronics industry, information industry and new and high technology, electrically conductive composite, especially filled-type are conductive
Composite material new technical field application and development, it is more noticeable.About the definition of conductive polymer material, mesh is arrived
Before until there is no unified standard both at home and abroad, broadly, generally by volume conductance ρ less than 1010The high molecular material of Ω cm is united
Referred to as conductive polymer material, wherein again by ρ 106~1010It is known as antistatic macromolecule material between Ω cm；ρ is existed
100~106It is known as semi-conductive high polymer material between Ω cm；By ρ less than 100Ω cm's is known as conductive polymer material.
For composite conductive polymer, the type and performance of filler be influence its conductivity most directly be also it is most important
Factor, at present conductive rubber with conductive filler be mainly carbon system (based on graphite, carbon black and carbon fiber), metal system (gold, silver, copper,
Nickel etc.), particle surface plating metal three categories.Carbon system is to prepare the main conductive filler of conductive composite rubber at present, but have pollution,
Be not suitable for the conductive material for being prepared with color requirement；The ratio of metal system particle surface plating metal is great, disperse in the polymer compared with
Difficulty is also less suited to the product of specific gravity requirement.It in recent years, is to represent higher-dimension New Type of Carbon system's filler filling system with graphene
Standby conductive material attracts wide public concern, and achieves plentiful and substantial research achievement.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of antistatic natural rubber, and this method solve graphenes
The rubber product 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, have the function of preferable antistatic.
The present invention solves its technical problem and adopts the following technical solutions to realize.
The present invention proposes a kind of preparation method of antistatic natural rubber, comprising: is the graphite of 1:5~1000 by weight ratio
Olefinic oxide mixes to obtain graphene oxide suspension with water.
After the Heveatex that mass concentration is 15%-70% is mixed with the peregal solution that mass concentration is 5%-30%
Cationic Heveatex is mixed to obtain for the acid solution of 1%-20% with mass concentration, the pH value of cationic Heveatex is
2.4-2.6；The weight ratio of the dry glue in peregal and Heveatex in peregal solution is 1:20~100.
Graphene oxide suspension is mixed with cationic Heveatex according to the ratio that weight ratio is 1:1~100
Graphene oxide-Heveatex suspension.
Reducing agent is mixed with graphene oxide-Heveatex suspension, is heated to 60~90 DEG C.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: mass concentration is by a kind of preparation method of antistatic natural rubber
The Heveatex of 15%-70% with mass concentration is 1%-20% after mixing with the peregal solution that mass concentration is 5%-30%
Acid solution cationic Heveatex is mixed to obtain.Peregal solution is added in Heveatex, Heveatex can be improved
Stability, flocculate after preventing acid adding.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 are integrally positively charged.By graphene oxide suspension and cationic Heveatex according to weight ratio be 1:1~
100 ratio mixes, and the graphene oxide in graphene oxide suspension is negatively charged, and cationic Heveatex is positively charged,
Under the action of electrostatic self-assembled, graphene oxide and cationic Heveatex interact, and it is preferable to obtain dispersion effect
Graphene oxide-Heveatex suspension.Reducing agent is mixed with graphene oxide-Heveatex suspension, is heated to
60~90 DEG C.Since reducing agent carries out in-situ reducing to graphene oxide in graphene oxide-Heveatex suspension,
It ensure that the graphene being reduced also preferably is dispersed in conductive Heveatex, and the reducing condition is mild, guarantee
The stability of whole system, obtained product have high conduction performance, have anti-static function after dry 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.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the electron microscope picture of test example 2 of the present invention.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is 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, comprising: by weight ratio be 1:5~1000 graphene oxide with
Water mixes to obtain graphene oxide suspension.
In an embodiment of the present invention, after graphene oxide being mixed with water, the first ultrasonic treatment is carried out.Pass through first
After ultrasonic treatment, graphene oxide and water energy are better mixed to obtain uniform suspension.In an embodiment of the present invention,
The ultrasonic power of one ultrasonic treatment is 50~500W, and ultrasonic time is 2~60min.Furthermore it is preferred that graphene oxide with
After water mixing, temperature is controlled in the range of 20~80 DEG C, carries out the first ultrasonic treatment again after 10~50min of magnetic agitation.This
Sample can make graphene oxide sufficiently infiltrate, and be conducive to be uniformly mixed with water.
In an embodiment of the present invention, graphene oxide may be selected through chemical oxidation graphite, micromechanics removing or change
Learn product made from the method for vapor deposition.Preferably, graphene oxide is made by chemical oxidation graphite.
After the Heveatex that mass concentration is 15%-70% is mixed with the peregal solution that mass concentration is 5%-30%
Cationic Heveatex is mixed to obtain for the acid solution of 1%-20% with mass concentration, the pH value of cationic 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, flocculate after preventing acid adding.It is excellent
Selection of land, average in peregal solution add as paregal O -30.Peregal refers to the addition product of natural fatty alcohol and ethylene oxide,
Belong to nonionic surfactant.
Acid in acid solution can provide hydrogen ion, and acid solution is mixed with Heveatex can make latex particle surface
Amino is positively charged in acid condition for albumen, and latex particle is integrally positively charged.It in the present embodiment, include dry glue in Heveatex
And water, dry glue here refer 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%.It
The mass concentration of right latex is 30%~65%.
Graphene oxide suspension is mixed with cationic Heveatex according to the ratio that weight ratio is 1:1~100
Graphene oxide-Heveatex suspension.
Wherein, the graphene oxide in graphene oxide suspension is negatively charged, and cationic Heveatex is positively charged,
Under the action of electrostatic self-assembled, graphene oxide and cationic Heveatex interact, and obtain the preferable stone of dispersion effect
Black olefinic oxide-Heveatex suspension.Preferably, graphene oxide suspension and the weight ratio of cationic Heveatex are
1:20~100.In an embodiment of the present invention, it is first carried out after graphene oxide suspension being mixed with cationic Heveatex
Second ultrasonic treatment enables to graphene oxide suspension and cationic Heveatex dispersion effect more by ultrasonic treatment
It is good.In an embodiment of the present invention, the ultrasonic power of the second ultrasonic treatment 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, graphite
Olefinic oxide can be evenly dispersed into cationic Heveatex, avoid the reunion of graphene oxide.
Reducing agent is mixed with graphene oxide-Heveatex suspension, 60~90 DEG C is heated to and obtains conduction naturally
Rubber latex.The weight ratio of graphene oxide in reducing agent and graphene oxide-Heveatex suspension be 1:0.2~
10。
It, can will be in graphene oxide-Heveatex suspension by reducing agent under the conditions of 60~90 DEG C of temperature
Graphene oxide be reduced into graphene.Due to reducing agent in graphene oxide-Heveatex suspension to graphene
Oxide carries out in-situ reducing, ensure that the graphene being reduced also preferably is dispersed in conductive Heveatex, and
The reducing condition is mild, ensure that the stability of conductive natural rubber latex, and 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, it is first carried out after reducing agent being mixed with graphene oxide-Heveatex suspension
Third ultrasonic treatment, is again heated to 60~90 DEG C.
Reducing agent is mixed with graphene oxide-Heveatex suspension and carries out third ultrasonic treatment, can will be restored
Agent and graphene oxide-Heveatex suspension are sufficiently mixed, and are conducive in graphene oxide-Heveatex suspension
Graphene oxide comes into full contact with reducing agent, and graphene oxide can fully be reduced into graphene.Of the invention
In embodiment, the ultrasonic power of third ultrasonic treatment 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 be solidified dry hot-forming rear use.
It is heated to 40-70 DEG C after conductive natural rubber latex is mixed with vulcanizing system and obtains presulfurization conduction natural rubber latex
Cream.The weight ratio of the dry glue in Heveatex in vulcanizing system and graphene oxide-Heveatex suspension be 1:20~
200.I.e. vulcanizing system is 1:20~200 with the weight ratio for participating in the dry glue in the Heveatex reacted.
In an embodiment of the present invention, vulcanizing system includes vulcanizing agent and promotor.Preferably, vulcanizing agent includes sulphur.
Preferably, promotor includes thiazoles, thiurams, sulfenamide, two Thiocarbamate class of guanidine, Thiourea or aldehyde amine
Class promotor.
Presulfurization conduction natural rubber latex is first subjected to plastic film mulch, dipping forms a film or spraying forms a film.Again by presulfurization conduction
Natural rubber latex dehydrates under conditions of 20-60 DEG C, vulcanizes under the conditions of 70-110 DEG C of temperature.Rubber after vulcanization
Product has anti-static function.
The present invention also provides a kind of antistatic natural rubbers, are made by the preparation method of above-mentioned antistatic natural rubber.
It is with preferable anti-static function.
Feature and performance of the 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 include:
The graphene oxide that weight ratio is 1:100 is mixed in beaker with water, control temperature is at 20 DEG C, magnetic force
After stirring 30min, 15min is ultrasonically treated under the power condition of 100W and obtains graphene oxide suspension.
The peregal solution that mass concentration is 10% is mixed with the fresh Heveatex that mass concentration is 45%, then again
It is quickly poured into the acetic acid that mass concentration is 3.85%, until the pH value of system is 2.4, cationic natural gum is made in magnetic agitation
Cream.Wherein the weight ratio of the paregal O -30 in peregal solution and the dry glue in fresh Heveatex is 1:50.
Graphene oxide suspension is mixed with cationic Heveatex according to the ratio that weight ratio is 1:1, is then existed
It is ultrasonically treated 50min under the power condition of 50W and obtains graphene oxide-Heveatex suspension.
Bad hematic acid is added in graphene oxide-Heveatex suspension, is ultrasonically treated under the power condition of 50W
60min.Then magnetic agitation is carried out, is heated to 80 DEG C, obtains conductive natural rubber latex.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, obtain presulfurization conduction natural rubber latex by being heated to 60 DEG C
Cream.Wherein the weight ratio of the dry glue in the Heveatex in vulcanizing system and graphene oxide-Heveatex suspension is 1:
100。
By presulfurization conduction natural rubber latex by plastic film mulch, 30 DEG C at a temperature of dehydrate, in 110 DEG C of condition
Under vulcanized.
Embodiment 2
A kind of antistatic natural rubber, the preparation method of the antistatic natural rubber include:
The graphene oxide that weight ratio is 1:20 is mixed in beaker with water, control temperature is at 30 DEG C, magnetic force
After stirring 45min, 60min is ultrasonically treated under the power condition of 80W and obtains graphene oxide suspension.
The peregal solution that mass concentration is 20% is mixed with the fresh Heveatex that mass concentration is 30%, then again
It is quickly poured into the formic acid that mass concentration is 2%, until the pH value of system is 2.5, cationic 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.
Graphene oxide suspension is mixed with cationic Heveatex according to the ratio that weight ratio is 1:1, is then existed
It is ultrasonically treated 50min under the power condition of 50W and obtains graphene oxide-Heveatex suspension.
Citric acid is added in graphene oxide-Heveatex suspension, is ultrasonically treated under the power condition of 50W
60min.Then magnetic agitation is carried out, is heated to 80 DEG C, obtains conductive natural rubber latex.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, obtain presulfurization conduction natural rubber latex by being heated to 60 DEG C
Cream.Wherein the weight ratio of the dry glue in the Heveatex in vulcanizing system and graphene oxide-Heveatex suspension is 1:
50。
By presulfurization conduction natural rubber latex by spraying film forming, 20 DEG C at a temperature of dehydrate, 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 include:
The graphene oxide that weight ratio is 1:10 is mixed in beaker with water, control temperature is at 40 DEG C, magnetic force
After stirring 50min, 60min is ultrasonically treated under the power condition of 100W and obtains graphene oxide suspension.
The peregal solution that mass concentration is 25% is mixed with the fresh Heveatex that mass concentration is 60%, then again
It is quickly poured into the formic acid that mass concentration is 10%, until the pH value of system is 2.6, cationic Heveatex is made in magnetic agitation.
Wherein the weight ratio of the paregal O -30 in peregal solution and the dry glue in fresh Heveatex is 1:20.
Graphene oxide suspension is mixed with cationic Heveatex according to the ratio that weight ratio is 1:100, then
It is ultrasonically treated 45min under the power condition of 150W and obtains graphene oxide-Heveatex suspension.
Citric acid is added in graphene oxide-Heveatex suspension, is ultrasonically treated under the power condition of 50W
60min.Then magnetic agitation is carried out, is heated to 85 DEG C, obtains conductive natural rubber latex.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, obtain presulfurization conduction natural rubber latex by being heated to 65 DEG C
Cream.Wherein the weight ratio of the dry glue in the Heveatex in vulcanizing system and graphene oxide-Heveatex suspension is 1:
20。
By presulfurization conduction natural rubber latex by dipping film forming, 35 DEG C at a temperature of dehydrate, 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 include:
The graphene oxide that weight ratio is 1:5 is mixed in beaker with water, controls temperature at 30 DEG C, magnetic force stirs
After mixing 20min, 45min is ultrasonically treated under the power condition of 50W and obtains graphene oxide suspension.
The peregal solution that mass concentration is 5% is mixed with the fresh Heveatex that mass concentration is 60%, then again
It is quickly poured into the formic acid that mass concentration is 10%, until the pH value of system is 2.6, cationic Heveatex is made in magnetic agitation.
Wherein the weight ratio of the paregal O -30 in peregal solution and the dry glue in fresh Heveatex is 1:100.
Graphene oxide suspension is mixed with cationic Heveatex according to the ratio that weight ratio is 1:20, is then existed
It is ultrasonically treated 30min under the power condition of 250W and obtains graphene oxide-Heveatex suspension.
Sodium borohydride is added in graphene oxide-Heveatex suspension, under the power condition of 60W at ultrasound
Manage 40min.Then magnetic agitation is carried out, is heated to 60 DEG C, obtains conductive natural rubber latex.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, obtain presulfurization conduction natural rubber latex by being heated to 40 DEG C
Cream.Wherein the weight ratio of the dry glue in the Heveatex in vulcanizing system and graphene oxide-Heveatex suspension is 1:
80。
By presulfurization conduction natural rubber latex by spraying film forming, 40 DEG C at a temperature of dehydrate, 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 include:
The graphene oxide that weight ratio is 1:500 is mixed in beaker with water, control temperature is at 60 DEG C, magnetic force
After stirring 10min, 30min is ultrasonically treated under the power condition of 300W and obtains graphene oxide suspension.
The peregal solution that mass concentration is 20% is mixed with the fresh Heveatex that mass concentration is 65%, then again
It is quickly poured into the acetic acid that mass concentration is 5%, until the pH value of system is 2.5, cationic 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.
Graphene oxide suspension is mixed with cationic Heveatex according to the ratio that weight ratio is 1:500, then
It is ultrasonically treated 20min under the power condition of 400W and obtains graphene oxide-Heveatex suspension.
Hydrazine hydrate is added in graphene oxide-Heveatex suspension, is ultrasonically treated under the power condition of 80W
20min.Then magnetic agitation is carried out, is heated to 70 DEG C, obtains conductive natural rubber latex.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, obtain presulfurization conduction natural rubber latex by being heated to 50 DEG C
Cream.Wherein the weight ratio of the dry glue in the Heveatex in vulcanizing system and graphene oxide-Heveatex suspension is 1:
200。
By presulfurization conduction natural rubber latex by dipping film forming, 50 DEG C at a temperature of dehydrate, 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 include:
The graphene oxide that weight ratio is 1:1000 is mixed in beaker with water, control temperature is at 80 DEG C, magnetic
After power stirs 40min, 2min is ultrasonically treated under the power condition of 500W and obtains graphene oxide suspension.
The peregal solution that mass concentration is 30% is mixed with the fresh Heveatex that mass concentration is 55%, then again
It is quickly poured into the sulfuric acid that mass concentration is 20%, until the pH value of system is 2.5, cationic Heveatex is made in magnetic agitation.
Wherein the weight ratio of the paregal O -30 in peregal solution and the dry glue in fresh Heveatex is 1:10.
Graphene oxide suspension is mixed with cationic Heveatex according to the ratio that weight ratio is 1:75, is then existed
It is ultrasonically treated 5min under the power condition of 500W and obtains graphene oxide-Heveatex suspension.
Bad hematic acid is added in graphene oxide-Heveatex suspension, under the power condition of 100W at ultrasound
Manage 5min.Then magnetic agitation is carried out, is heated to 90 DEG C, obtains conductive natural rubber latex.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, obtain presulfurization conduction natural rubber latex by being heated to 70 DEG C
Cream.Wherein the weight ratio of the dry glue in the Heveatex in vulcanizing system and graphene oxide-Heveatex suspension is 1:
150。
By presulfurization conduction natural rubber latex 60 DEG C at a temperature of dehydrate, carry out sulphur under conditions of 100 DEG C
Change.
Test example 1
Conductivity test: referring to GB/T2439-2001 (vulcanized rubber or thermoplastic elastomer electric conductivity and dissipative performance electricity
The measurement of conductance) test of conductivity is carried out to the antistatic natural rubber of embodiment 1-6, result is recorded in table 1.
Table 1 implements the conductivity of the antistatic natural rubber of 1-6
From the results shown in Table 1, the conductivity of the antistatic natural rubber of embodiment 1-6 is all larger than 10-6S/cm is said
The preferably antistatic day of antistatic effect can be made in the preparation method that antistatic natural rubber through the embodiment of the present invention is illustrated
Right rubber.
Test example 2
After the antistatic natural rubber of embodiment 2 is carried out liquid nitrogen brittle failure, electron microscope observation is scanned to section,
Its result is as shown in Figure 1.
Interpretation of result: from the result of Fig. 1 as can be seen that the graphene oxide that is reduced in antistatic natural rubber
(i.e. graphene) establishes partially electronically conductive access.
In conclusion a kind of antistatic natural rubber and preparation method thereof of the embodiment of the present invention, in preparation method, in day
Peregal solution is added in right latex, the stability of Heveatex can be improved, flocculate after preventing acid adding.Acid in acid solution can
To provide hydrogen ion, acid solution is mixed with Heveatex can make the albumen on latex particle surface amino band in acid condition
Positive electricity, latex particle is integrally positively charged, and the graphene oxide in graphene oxide suspension is negatively charged, cationic natural gum
Cream is positively charged, and under the action of electrostatic self-assembled, graphene oxide and cationic Heveatex interact, and obtains dispersion effect
The preferable graphene oxide of fruit-Heveatex suspension.Since reducing agent is in graphene oxide-Heveatex suspension
In-situ reducing is carried out to graphene oxide, ensure that the graphene being reduced also preferably is dispersed in conductive Heveatex
In, and the reducing condition is mild, ensure that the stability of whole system, and obtained product has high conduction performance, through overdrying
There is anti-static function after dry vulcanization.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (13)
1. a kind of preparation method of antistatic natural rubber characterized by comprising be the graphite of 1:5~1000 by weight ratio
Olefinic oxide mixes to obtain graphene oxide suspension with water；
After the Heveatex that mass concentration is 15%-70% is mixed with the peregal solution that mass concentration is 5%-30% with matter
Cationic Heveatex is mixed to obtain in the acid solution that amount concentration is 1%-20%, 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；
The graphene oxide suspension and the cationic Heveatex are mixed according to the ratio that weight ratio is 1:1~100
Close to obtain graphene oxide-Heveatex suspension；
Reducing agent is mixed with the graphene oxide-Heveatex suspension, is heated to 60~90 DEG C；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, which is characterized 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, which is characterized in that the acid solution includes sulphur
Acid solution, formic acid solution or acetic acid solution.
4. the preparation method of antistatic natural rubber according to claim 3, which is characterized in that the acid solution is acetic acid
Solution.
5. the preparation method of antistatic natural rubber according to claim 1, which is characterized in that the quality of the acid solution
Concentration is 2%~10%, and the mass concentration of the Heveatex is 30%~65%.
6. the preparation method of antistatic natural rubber according to claim 1, which is characterized in that the graphene oxide
The weight ratio of suspension and the cationic Heveatex is 1:20~100.
7. the preparation method of antistatic natural rubber according to claim 1, which is characterized in that in the peregal solution
Described average add as paregal O -30.
8. the preparation method of antistatic natural rubber according to claim 1, which is characterized in that the reducing agent includes anti-
Bad hematic acid, citric acid, sodium borohydride or hydrazine hydrate.
9. the preparation method of antistatic natural rubber according to claim 1, which is characterized in that the reducing agent includes anti-
Bad hematic acid or citric acid.
10. the preparation method of antistatic natural rubber according to claim 1, which is characterized in that by the reducing agent with
The mixing of the graphene oxide-Heveatex suspension after being heated to 60~90 DEG C, then is mixed and heated to vulcanizing system
40-70 DEG C obtains presulfurization conduction natural rubber latex；By the presulfurization conduction natural rubber latex under conditions of 20-60 DEG C
Dehydration and drying, vulcanizes under the conditions of 70-110 DEG C of temperature；The vulcanizing system and the graphene oxide-Heveatex are outstanding
The weight ratio of the dry glue in the Heveatex in supernatant liquid is 1:20~200.
11. the preparation method of antistatic natural rubber according to claim 8, which is characterized in that the vulcanizing system packet
Include vulcanizing agent and promotor.
12. the preparation method of antistatic natural rubber according to claim 11, which is characterized in that the vulcanizing agent includes
Sulphur；The promotor includes thiazoles, thiurams, sulfenamide, two Thiocarbamate class of guanidine, Thiourea or aldehyde
Amine type accelerator.
13. a kind of antistatic natural rubber, which is characterized in that by the described in any item antistatic natural rubbers of claim 1-12
Preparation method be made.
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| CN201710555827.2A CN107286403B (en) | 2017-07-07 | 2017-07-07 | A kind of antistatic natural rubber and preparation method thereof |
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