CN104877192B - Fe3O4@GO/NR magnetic elastomer composite material and preparation method - Google Patents
Fe3O4@GO/NR magnetic elastomer composite material and preparation method Download PDFInfo
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Abstract
The invention relates to magnetic elastomer composite materials, in particular to a Fe3O4@GO/NR magnetic elastomer composite material and a preparation method, and solves the problem that magnetic particles in existing materials are nonuniform in dispersion, prone to gathering, unstable in structural performance and low in mechanical performance. The preparation method includes: 1), adopting a chemical co-precipitation method to prepare Fe3O4 water-base magnetic liquid; 2), adopting an improved Hummers method to prepare graphite oxide, and preparing GO suspension liquid; 3), preparing stabilizer, vulcanizer and promoter dispersoid; 4), adopting an emulsion blending method to prepare the Fe3O4@GO/NR magnetic elastomer composite material. The Fe3O4@GO/NR magnetic elastomer composite material and the preparation method have the advantages that a, vulcanizing temperature is low, preparation process is simple, dispersity of the magnetic particles and GO is improved, the problem of proneness to gathering is solved, and the composite material is stable in structure; b, graphene oxide serves as reactive enhanceosome, so that mechanical performance is improved, the magnetic particles are stabilized, sedimentation and aggregation are prevented, and mechanical performance and magnetic performance are improved; c, the composite material can display excellent elastic mechanical performance, magnetic performance, heat resistance and solvent resistance under low concentration.
Description
Technical field
The present invention relates to magnetic elastomeric composite material and preparation method, specially Fe3O4@GO/NR magnetic elastomeric bluk recombination
Material and preparation method.
Background technology
Fe3O4/ natural rubber（NR）Magnetic elastomeric composite material is due to having controlled mangneto mould under external magnetic field
Amount, magnetoresistance, magnetostriction, mangneto damping and magnetic performance, thus inhale in damping, the axle bush in noise reduction field, self-tuning formula
Shake device, vibration isolator, suspension, the field such as magnetic sealing device has a wide range of applications.Preparation Fe3O4/ NR magnetic elastomeric bluk recombination
The traditional method of material is mainly by natural rubber rubber, Fe3O4Magnetic powder and other processing aid pass through blend technique system
Standby molding.But, this kind of preparation method leads to dispersion in natural rubber matrix for the magnetic particle uneven, and in curing molding
During magnetic particle easily assemble, lead to structure and the unstable properties of magnetic elastomeric composite material, especially mechanical property
Can decline, greatly limit the range of application of such material.Therefore, design a kind of magnetic particle to be uniformly dispersed, be not easy to assemble,
Performance structure is stable, the good Fe of mechanical property3O4/ NR magnetic elastomeric composite material and preparation method are extremely necessary.
Content of the invention
The present invention solves existing Fe3O4In/NR material, magnetic particle dispersion is uneven, and magnetic particle is easily assembled, structure
Unstable properties, the problem of poor mechanical property, a kind of Fe is provided3O4@GO/NR（Fe3O4@graphene oxide/natural rubber）Magnetic
Elastic composite and preparation method.
The present invention is achieved by the following technical solutions：Fe3O4@GO/NR magnetic elastomer composite material and preparation method thereof,
Comprise the following steps：
1）, preparation stablize Fe3O4Water-base magnetic liquid
By 3.6g FeCl2·4H2O and 6.1g FeCl3·6H2O is dissolved in 90mL deionized water, stirs all at 50 DEG C
After even, under 500r/min stirring, Deca 90mL concentration is the NaOH aqueous solution of 1.34mol/L, reacts after completion of dropping
90min stops, and is cooled to room temperature, and resulting solution Magneto separate is obtained black precipitate, removes the supernatant, then deionized water surpasses
Sound dispersion, Magneto separate, repeated washing, until the pH of supernatant is in neutrality.Then by black magnetic particle ultrasonic disperse in certain
In the deionized water of volume, and with 200r/min mechanical agitation 10min, until forming concentration is stablizing of 0.02 ~ 0.167g/mL
Fe3O4Water-base magnetic liquid；
2）, the GO that is completely exfoliated of preparation（Graphene oxide）Suspension
Under condition of ice bath, 2.0g natural flake graphite and 2.0g sodium nitrate are added in the concentrated sulphuric acid of 46mL, with
600r/min mechanical agitation 30min；6.0g potassium permanganate is added in above-mentioned mixed liquor, with 600r/min mechanical agitation
60min.Above-mentioned mixed liquor is transferred in 45 DEG C of water-baths, after 400r/min mechanical agitation 4h, 80mL deionized water is added
To in mixed liquor, transfer it in 95 DEG C of oil bath；When solution temperature to be mixed reaches 95 DEG C, successively add 200mL
Deionized water and the hydrogen peroxide of 16mL 30% concentration, when solution becomes golden yellow by brown color, stopped reaction；Use successively
2mol/L HCl solution, deionized water and the multiple centrifuge washing of dehydrated alcohol, until after the pH of solution is in neutrality, will be golden yellow heavy
Starch is placed in 60 DEG C of drying in baking oven, obtains final product graphite oxide；A certain amount of graphite oxide is added in 20mL deionized water,
Under 120W power, ultrasonic disperse 3 ~ 7h, form the GO suspension that the concentration being completely exfoliated is 0.5mg/ml ~ 10mg/ml；
3）, prepare stabilizer, vulcanizing agent, accelerator etc. cooperation agent dispersion
a）, weigh a certain amount of KOH and paregal O respectively（Alkyl polyoxyethylene ether）, be dissolved under the conditions of 50 DEG C from
In sub- water, it is configured to the KOH aqueous solution of 20wt% and the paregal O aqueous solution of 20wt% respectively；
b）, at room temperature by 50g sulfur, the casein solution of 20mL 10wt%, 1.25mL concentration be 11.5% ammonia,
28.75mL deionized water and 75mL glass sand are added in container, with 500r/min mechanical agitation 12h, then pass through sieve
Glass sand is separated with the first dispersant suspension, obtains the sulfur dispersion of 50wt%；At room temperature by 50g zinc oxide,
The casein solution of 20mL 10wt% and 3gNF（Methylene sodium dinaphthalenesulfonate）, 5mL concentration be 20% ammonia, 30mL deionized water and
75mL glass sand is added in 500mL enamelled cup, with 500r/min mechanical agitation 10h, then passes through sieve by glass sand
Separate with the second dispersant suspension, obtain the oxidation zinc dispersion of 40wt%；At room temperature by 50g accelerator ZDC（Diethyl
Zinc dithiocarbamate）, 40mL 10wt% casein solution and the deionized water of 1.15gNF, 28.85mL and the glass sand of 75mL
Son mixing is contained in the enamelled cup of 500mL, and with 500r/min mechanical agitation 12h, finally by sieve by glass sand and the
Three dispersant suspensions separate, and obtain the accelerator ZDC dispersion of 50wt%；
4）, emulsion dispersion preparation Fe3O4@GO/NR magnetic elastomeric composite material
a）, first, adjust the pH to 8 ~ 14 of water-soluble natural latex with alkali liquor, and add the KOH of the 20wt% of metering water-soluble
Liquid, the paregal O aqueous solution of 20wt%, wherein KOH and latex butt mass ratio are 1：500 ~ 1000, paregal O and latex butt
Mass ratio is 1：500~1000；
b）, secondly, by step 1）With step 2）Described in certain volume stable Fe3O4Water-base magnetic liquid and described
Certain volume the GO suspension being completely exfoliated, be added to a under 50 DEG C and 150 ~ 250r/min mechanical agitation）Step
Form composite solution in prepared water-soluble natural latex mixed liquor；
c）, the sulfur dispersion, ZnO dispersion and the accelerator ZDC dispersion that add metering in above-mentioned composite solution, former
Position sulfuration 60 ~ 150min, forms presulfurization magnetic coupling emulsion, wherein sulfur and latex butt mass ratio is 1:50 ~ 150, oxygen
Changing zinc with latex butt mass ratio is 1:100 ~ 300, accelerator ZDC and latex butt mass ratio are 1:100~200；Then should
After complex emulsions supersound process 30 ~ 180min under 150 ~ 250r/min mechanical agitation, pour in mould, dry at 20 ~ 80 DEG C
Dry 10 ~ 36h, obtains the homogeneous Fe of structure3O4@GO/NR magnetic elastomeric composite material, Fe3O4Water-base magnetic liquid, shell completely
From GO suspension, 4）a）The consumption of the water-soluble natural latex mixed liquor that step is obtained should ensure that prepared Fe3O4@GO/NR magnetic
84.9wt% containing natural rubber, Fe in property elastic composite3O410wt%, GO3wt%.
Using chemical coprecipitation preparation Fe in this patent3O4Water-base magnetic liquid is so that Fe3O4The dispersion of magnetic particle
Property more preferably, and be difficult to reunite.Graphite oxide is prepared using Hummers method in this patent, then again with prepared graphite oxide system
Standby GO suspension is so that prepared GO suspension dispersibility is more preferable.Prepare sulfur dispersion, ZnO dispersion and accelerator ZDC to divide
A prose style free from parallelism, respectively as vulcanizing agent, stabilizer and accelerator, is added in follow-up mixed solution.Add casein solution or add together
Casein solution and NF（Methylene sodium dinaphthalenesulfonate）As dispersant.Alkali liquor used can be NaOH aqueous solution or KOH aqueous solution or
NH3 .H2One of O aqueous solution.Described KOH and latex butt mass ratio are 1：500 ~ 1000, paregal O and latex butt
Mass ratio is 1：500 ~ 1000 is the solute adding in the quantitative KOH aqueous solution and paregal O aqueous solution of fixed mass fraction
With the mass ratio of latex butt, do not include the KOH comprising in alkali liquor.KOH aqueous solution, paregal O water is added in Heveatex
Solution, to strengthen micelle surface charge, protective layer, degree of hydration it is ensured that latex long-time stable is uniform.Test in laboratory obtains finally
Prepared Fe3O4Contain KOH and paregal O and sulfur in@GO/NR magnetic elastomeric composite material and ZnO and ZDC amount to 1.5 ~
Its material property of 3.5wt%, wherein when containing 2.1wt% is optimum.
When being embodied as, described alkali liquor can be NaOH aqueous solution or KOH aqueous solution or NH3 .H2One of O aqueous solution.
The present invention and existing Fe3O4/ NR magnetic elastomeric composite material and preparation method thereof is compared with advantages below：
1st, curing temperature is low, preparation process is simple, and effectively increases magnetic particle, the GO dispersibility in rubber matrix, overcomes
The problem that magnetic particle, GO easily reunite in elastomer matrix, obtains constitutionally stable Fe3O4@GO/NR magnetic elastomer is multiple
Condensation material；2nd, the graphene oxide introducing can be used as reactive reinforcement, improves the machinery of magnetic elastomeric composite material
Mechanical property, can also stablize magnetic particle, prevent sedimentation and the reunion of magnetic particle, improve magnetic elastomer machinery further
Mechanical property and magnetic property；3rd, Fe obtained by the present invention3O4@GO/NR magnetic elastomeric composite material, can show at low concentrations
Excellent Elasticity performance, magnetic property, heat resistance and solvent resistance are shown.
Brief description
The Fe that Fig. 1 is prepared for the present invention3O4Photo in kind after 1 month for the@GO/NR presulfurization magnetic coupling emulsion standing；
The Fe that Fig. 2 is prepared for the present invention3O4The XRD spectrum of@GO/NR magnetic elastomeric composite material；Can from figure
Go out：There is a larger amorphous peak bulge in the range of 15 ~ 18 °, have individual diffraction maximum to be GO near the angle of diffraction is 10 °, and spreading out
Firing angle is 30.02 °, 35.5 °, 42.12 °, 57.06 °, 62.6 ° etc. show diffraction maximum, they are respectively Fe3O4（fcc）'s
220th, the diffraction of the crystal faces such as 200,311,400,511, shows GO, Fe3O4It is combined well with natural rubber by emulsion composite method
Together；
The Fe that Fig. 3 is prepared for the present invention3O4The SEM figure of@GO/NR magnetic elastomeric composite material, can see from SEM in figure
Observe, Fe3O4, dispersibility in natural rubber matrix for the GO very well, Material cladding more homogeneous；
The Fe that Fig. 4 is prepared for the present invention3O4@GO/NR magnetic elastomer composite sample material object photo；In kind from macroscopic view
Can see in photo, any surface finish of composite, magnetic particle, graphite oxide and rubber have been compounded in one well
Rise；
The Fe that Fig. 5 is prepared for the attraction present invention3O4@GO/NR magnetic elastomeric composite material photo；From photo
The Fe of present invention preparation3O4@GO/NR magnetic elastomeric composite material has good magnetic property；
The Fe that Fig. 6 is prepared for the present invention3O4The hysteresis curve of@GO/NR magnetic elastomeric composite material；System of the present invention is described
Standby Fe3O4@GO/NR magnetic elastomeric composite material has good magnetic property, and magnetic saturation intensity is up to 2.0emu/g；
The Fe that Fig. 7 is prepared for the present invention3O4The load-deformation curve of@GO/NR magnetic elastomeric composite material；Can from figure
To find out, after introducing GO, the mechanical property of magnetic elastomeric composite material increases substantially.
Specific embodiment
Embodiment one：Fe3O4@GO/NR magnetic elastomer composite material and preparation method thereof, comprises the following steps：
1）, preparation stablize Fe3O4Water-base magnetic liquid
By 3.6g FeCl2·4H2O and 6.1g FeCl3·6H2O is dissolved in 90mL deionized water, stirs all at 50 DEG C
After even, under 500r/min stirring, Deca 90mL concentration is the NaOH aqueous solution of 1.34mol/L, reacts 90min after completion of dropping
Stop, being cooled to room temperature, resulting solution Magneto separate is obtained black precipitate, remove the supernatant, more ultrasonic point of deionized water
Scattered, Magneto separate, repeated washing, until the pH of supernatant is in neutrality.Then by black magnetic particle ultrasonic disperse in certain volume
Deionized water in, and with 200r/min mechanical agitation 10min, until forming the stable Fe that concentration is 0.02g/mL3O4Water base magnetic
Property liquid；
2）, the GO suspension that is completely exfoliated of preparation
Under condition of ice bath, 2.0g natural flake graphite and 2.0g sodium nitrate are added in the concentrated sulphuric acid of 46mL, with
600r/min mechanical agitation 30min；6.0g potassium permanganate is added in above-mentioned mixed liquor, with 600r/min mechanical agitation
60min.Above-mentioned mixed liquor is transferred in 45 DEG C of water-baths, after 400r/min mechanical agitation 4h, 80mL deionized water is added
To in mixed liquor, transfer it in 95 DEG C of oil bath；When solution temperature to be mixed reaches 95 DEG C, successively add 200mL
Deionized water and the hydrogen peroxide of 16mL 30% concentration, when solution becomes golden yellow by brown color, stopped reaction；Use successively
2mol/L HCl solution, deionized water and the multiple centrifuge washing of dehydrated alcohol, until after the pH of solution is in neutrality, will be golden yellow heavy
Starch is placed in 60 DEG C of drying in baking oven, obtains final product graphite oxide；A certain amount of graphite oxide is added in 20mL deionized water,
Under 120W power, ultrasonic disperse 5h, form the GO suspension that the concentration being completely exfoliated is 0.5mg/ml；
3）, prepare stabilizer, vulcanizing agent, accelerator etc. cooperation agent dispersion
a）, weigh a certain amount of KOH and paregal O respectively, be dissolved under the conditions of 50 DEG C in deionized water, be configured to respectively
The KOH aqueous solution of 20wt% and the paregal O aqueous solution of 20wt%；
b）, at room temperature by 50g sulfur, the casein solution of 20mL 10wt%, 1.25mL concentration be 11.5% ammonia,
28.75mL deionized water and 75mL glass sand are added in container, with 500r/min mechanical agitation 12h, then pass through sieve
Glass sand is separated with the first dispersant suspension, obtains the sulfur dispersion of 50wt%；At room temperature by 50g zinc oxide,
The casein solution of 20mL 10wt% and ammonia, 30mL deionized water and 75mL glass sand that 3gNF, 5mL concentration is 20% add
To in 500mL enamelled cup, with 500r/min mechanical agitation 10h, then pass through sieve and glass sand and the second dispersant suspend
Liquid separates, and obtains the oxidation zinc dispersion of 40wt%；At room temperature by 50g accelerator ZDC, 40mL 10wt% casein solution and
The glass sand mixing of the deionized water of 1.15gNF, 28.85mL and 75mL is contained in the enamelled cup of 500mL, and with 500r/min
Glass sand is separated with the 3rd dispersant suspension by mechanical agitation 12h finally by sieve, obtains the accelerator ZDC of 50wt%
Dispersion；
4）, emulsion dispersion preparation Fe3O4@GO/NR magnetic elastomeric composite material
a）, first, adjust the pH to 11 of water-soluble natural latex with NaOH aqueous solution, and add the KOH of the 20wt% of metering
Aqueous solution, the paregal O aqueous solution of 20wt%, wherein KOH and latex butt mass ratio are 1：900, paregal O and latex butt
Mass ratio is 1：650；
b）, secondly, by step 1）With step 2）Described in certain volume stable Fe3O4Water-base magnetic liquid and described
Certain volume the GO suspension being completely exfoliated, be added to a under 50 DEG C and 200r/min mechanical agitation）Step is obtained
Water-soluble natural latex mixed liquor in formed composite solution；
c）, the sulfur dispersion, ZnO dispersion and the accelerator ZDC dispersion that add metering in above-mentioned composite solution, former
Position sulfuration 80min, forms presulfurization magnetic coupling emulsion, wherein sulfur and latex butt mass ratio is 1：150, zinc oxide and glue
Newborn butt mass ratio:1：100, accelerator ZDC and latex butt mass ratio are 1:120；Then by this complex emulsions in 225r/
After supersound process 30min under min mechanical agitation, pour in mould, 22h is dried at 35 DEG C, obtain the homogeneous Fe of structure3O4@
GO/NR magnetic elastomeric composite material, Fe3O4Water-base magnetic liquid, the GO suspension being completely exfoliated, 4）a）The water that step is obtained
The consumption of soluble natural latex mixed liquor should ensure that prepared Fe3O4Natural rubber is contained in@GO/NR magnetic elastomeric composite material
84.9wt%, Fe3O410wt%, GO3wt%.
Embodiment two：Fe3O4@GO/NR magnetic elastomer composite material and preparation method thereof, comprises the following steps：
1）, preparation stablize Fe3O4Water-base magnetic liquid
By 3.6g FeCl2·4H2O and 6.1g FeCl3·6H2O is dissolved in 90mL deionized water, stirs all at 50 DEG C
After even, under 500r/min stirring, Deca 90mL concentration is the NaOH aqueous solution of 1.34mol/L, reacts 90min after completion of dropping
Stop, being cooled to room temperature, resulting solution Magneto separate is obtained black precipitate, remove the supernatant, more ultrasonic point of deionized water
Scattered, Magneto separate, repeated washing, until the pH of supernatant is in neutrality.Then by black magnetic particle ultrasonic disperse in certain volume
Deionized water in, and with 200r/min mechanical agitation 10min, until forming the stable Fe that concentration is 0.126g/mL3O4Water base
Magnetic liquid；
2）, the GO suspension that is completely exfoliated of preparation
Under condition of ice bath, 2.0g natural flake graphite and 2.0g sodium nitrate are added in the concentrated sulphuric acid of 46mL, with
600r/min mechanical agitation 30min；6.0g potassium permanganate is added in above-mentioned mixed liquor, with 600r/min mechanical agitation
60min.Above-mentioned mixed liquor is transferred in 45 DEG C of water-baths, after 400r/min mechanical agitation 4h, 80mL deionized water is added
To in mixed liquor, transfer it in 95 DEG C of oil bath；When solution temperature to be mixed reaches 95 DEG C, successively add 200mL
Deionized water and the hydrogen peroxide of 16mL 30% concentration, when solution becomes golden yellow by brown color, stopped reaction；Use successively
2mol/L HCl solution, deionized water and the multiple centrifuge washing of dehydrated alcohol, until after the pH of solution is in neutrality, will be golden yellow heavy
Starch is placed in 60 DEG C of drying in baking oven, obtains final product graphite oxide；A certain amount of graphite oxide is added in 20mL deionized water,
Under 120W power, ultrasonic disperse 4h, form the GO suspension that the concentration being completely exfoliated is 7.5mg/ml；
3）, prepare stabilizer, vulcanizing agent, accelerator etc. cooperation agent dispersion
a）, weigh a certain amount of KOH and paregal O respectively, be dissolved under the conditions of 50 DEG C in deionized water, be configured to respectively
The KOH aqueous solution of 20wt% and the paregal O aqueous solution of 20wt%；
b）, at room temperature by 50g sulfur, the casein solution of 20mL 10wt%, 1.25mL concentration be 11.5% ammonia,
28.75mL deionized water and 75mL glass sand are added in container, with 500r/min mechanical agitation 12h, then pass through sieve
Glass sand is separated with the first dispersant suspension, obtains the sulfur dispersion of 50wt%；At room temperature by 50g zinc oxide,
The casein solution of 20mL 10wt% and ammonia, 30mL deionized water and 75mL glass sand that 3gNF, 5mL concentration is 20% add
To in 500mL enamelled cup, with 500r/min mechanical agitation 10h, then pass through sieve and glass sand and the second dispersant suspend
Liquid separates, and obtains the oxidation zinc dispersion of 40wt%；At room temperature by 50g accelerator ZDC, 40mL 10wt% casein solution and
The glass sand mixing of the deionized water of 1.15gNF, 28.85mL and 75mL is contained in the enamelled cup of 500mL, and with 500r/min
Glass sand is separated with the 3rd dispersant suspension by mechanical agitation 12h finally by sieve, obtains the accelerator ZDC of 50wt%
Dispersion；
4）, emulsion dispersion preparation Fe3O4@GO/NR magnetic elastomeric composite material
a）, first, adjust the pH to 8 of water-soluble natural latex with KOH aqueous solution, and add the KOH water of the 20wt% of metering
Solution, the paregal O aqueous solution of 20wt%, wherein KOH and latex butt mass ratio are 1：650, paregal O and latex butt matter
Amount ratio is 1：1000；
b）, secondly, by step 1）With step 2）Described in certain volume stable Fe3O4Water-base magnetic liquid and described
Certain volume the GO suspension being completely exfoliated, be added to a under 50 DEG C and 170r/min mechanical agitation）Step is obtained
Water-soluble natural latex mixed liquor in formed composite solution；
c）, the sulfur dispersion, ZnO dispersion and the accelerator ZDC dispersion that add metering in above-mentioned composite solution, former
Position sulfuration 150min, forms presulfurization magnetic coupling emulsion, wherein sulfur and latex butt mass ratio is 1:90, zinc oxide and glue
Newborn butt mass ratio is 1:260, accelerator ZDC and latex butt mass ratio are 1:200；Then by this complex emulsions in 250r/
After supersound process 150min under min mechanical agitation, pour in mould, 16h is dried at 20 DEG C, obtain the homogeneous Fe of structure3O4@
GO/NR magnetic elastomeric composite material, Fe3O4Water-base magnetic liquid, the GO suspension being completely exfoliated, 4）a）The water that step is obtained
The consumption of soluble natural latex mixed liquor should ensure that prepared Fe3O4Natural rubber is contained in@GO/NR magnetic elastomeric composite material
96.4wt%, Fe3O41wt%, GO 1wt%.
Embodiment three：Fe3O4@GO/NR magnetic elastomer composite material and preparation method thereof, comprises the following steps：
1）, preparation stablize Fe3O4Water-base magnetic liquid
By 3.6g FeCl2·4H2O and 6.1g FeCl3·6H2O is dissolved in 90mL deionized water, stirs all at 50 DEG C
After even, under 500r/min stirring, Deca 90mL concentration is the NaOH aqueous solution of 1.34mol/L, reacts 90min after completion of dropping
Stop, being cooled to room temperature, resulting solution Magneto separate is obtained black precipitate, remove the supernatant, more ultrasonic point of deionized water
Scattered, Magneto separate, repeated washing, until the pH of supernatant is in neutrality.Then by black magnetic particle ultrasonic disperse in certain volume
Deionized water in, and with 200r/min mechanical agitation 10min, until forming the stable Fe that concentration is 0.167g/mL3O4Water base
Magnetic liquid；
2）, the GO suspension that is completely exfoliated of preparation
Under condition of ice bath, 2.0g natural flake graphite and 2.0g sodium nitrate are added in the concentrated sulphuric acid of 46mL, with
600r/min mechanical agitation 30min；6.0g potassium permanganate is added in above-mentioned mixed liquor, with 600r/min mechanical agitation
60min.Above-mentioned mixed liquor is transferred in 45 DEG C of water-baths, after 400r/min mechanical agitation 4h, 80mL deionized water is added
To in mixed liquor, transfer it in 95 DEG C of oil bath；When solution temperature to be mixed reaches 95 DEG C, successively add 200mL
Deionized water and the hydrogen peroxide of 16mL 30% concentration, when solution becomes golden yellow by brown color, stopped reaction；Use successively
2mol/L HCl solution, deionized water and the multiple centrifuge washing of dehydrated alcohol, until after the pH of solution is in neutrality, will be golden yellow heavy
Starch is placed in 60 DEG C of drying in baking oven, obtains final product graphite oxide；A certain amount of graphite oxide is added in 20mL deionized water,
Under 120W power, ultrasonic disperse 7h, form the GO suspension that the concentration being completely exfoliated is 5mg/ml；
3）, prepare stabilizer, vulcanizing agent, accelerator etc. cooperation agent dispersion
a）, weigh a certain amount of KOH and paregal O respectively, be dissolved under the conditions of 50 DEG C in deionized water, be configured to respectively
The KOH aqueous solution of 20wt% and the paregal O aqueous solution of 20wt%；
b）, at room temperature by 50g sulfur, the casein solution of 20mL 10wt%, 1.25mL concentration be 11.5% ammonia,
28.75mL deionized water and 75mL glass sand are added in container, with 500r/min mechanical agitation 12h, then pass through sieve
Glass sand is separated with the first dispersant suspension, obtains the sulfur dispersion of 50wt%；At room temperature by 50g zinc oxide,
The casein solution of 20mL 10wt% and ammonia, 30mL deionized water and 75mL glass sand that 3gNF, 5mL concentration is 20% add
To in 500mL enamelled cup, with 500r/min mechanical agitation 10h, then pass through sieve and glass sand and the second dispersant suspend
Liquid separates, and obtains the oxidation zinc dispersion of 40wt%；At room temperature by 50g accelerator ZDC, 40mL 10wt% casein solution and
The glass sand mixing of the deionized water of 1.15gNF, 28.85mL and 75mL is contained in the enamelled cup of 500mL, and with 500r/min
Glass sand is separated with the 3rd dispersant suspension by mechanical agitation 12h finally by sieve, obtains the accelerator ZDC of 50wt%
Dispersion；
4）, emulsion dispersion preparation Fe3O4@GO/NR magnetic elastomeric composite material
a）, first, use NH3 .H2The pH to 9.5 of O aqueous solution regulation water-soluble natural latex, and add the 20wt% of metering
KOH aqueous solution, the paregal O aqueous solution of 20wt%, wherein KOH and latex butt mass ratio are 1：500, paregal O is done with latex
Base mass ratio is 1：800；
b）, secondly, by step 1）With step 2）Described in certain volume stable Fe3O4Water-base magnetic liquid and described
Certain volume the GO suspension being completely exfoliated, be added to a under 50 DEG C and 220r/min mechanical agitation）Step is obtained
Water-soluble natural latex mixed liquor in formed composite solution；
c）, the sulfur dispersion, ZnO dispersion and the accelerator ZDC dispersion that add metering in above-mentioned composite solution, former
Position sulfuration 60min, forms presulfurization magnetic coupling emulsion, wherein sulfur and latex butt mass ratio is 1:120, zinc oxide and glue
Newborn butt mass ratio is 1:300, accelerator ZDC and latex butt mass ratio are 1:140；Then by this complex emulsions in 150r/
After supersound process 180min under min mechanical agitation, pour in mould, 36h is dried at 65 DEG C, obtain the homogeneous Fe of structure3O4@
GO/NR magnetic elastomeric composite material, Fe3O4Water-base magnetic liquid, the GO suspension being completely exfoliated, 4）a）The water that step is obtained
The consumption of soluble natural latex mixed liquor should ensure that prepared Fe3O4Natural rubber is contained in@GO/NR magnetic elastomeric composite material
93.9wt%, Fe3O43wt%, GO 1wt%.
Example IV：Fe3O4@GO/NR magnetic elastomer composite material and preparation method thereof, comprises the following steps：
1）, preparation stablize Fe3O4Water-base magnetic liquid
By 3.6g FeCl2·4H2O and 6.1g FeCl3·6H2O is dissolved in 90mL deionized water, stirs all at 50 DEG C
After even, under 500r/min stirring, Deca 90mL concentration is the NaOH aqueous solution of 1.34mol/L, reacts 90min after completion of dropping
Stop, being cooled to room temperature, resulting solution Magneto separate is obtained black precipitate, remove the supernatant, more ultrasonic point of deionized water
Scattered, Magneto separate, repeated washing, until the pH of supernatant is in neutrality.Then by black magnetic particle ultrasonic disperse in certain volume
Deionized water in, and with 200r/min mechanical agitation 10min, until forming the stable Fe that concentration is 0.056g/mL3O4Water base
Magnetic liquid；
2）, the GO suspension that is completely exfoliated of preparation
Under condition of ice bath, 2.0g natural flake graphite and 2.0g sodium nitrate are added in the concentrated sulphuric acid of 46mL, with
600r/min mechanical agitation 30min；6.0g potassium permanganate is added in above-mentioned mixed liquor, with 600r/min mechanical agitation
60min.Above-mentioned mixed liquor is transferred in 45 DEG C of water-baths, after 400r/min mechanical agitation 4h, 80mL deionized water is added
To in mixed liquor, transfer it in 95 DEG C of oil bath；When solution temperature to be mixed reaches 95 DEG C, successively add 200mL
Deionized water and the hydrogen peroxide of 16mL 30% concentration, when solution becomes golden yellow by brown color, stopped reaction；Use successively
2mol/L HCl solution, deionized water and the multiple centrifuge washing of dehydrated alcohol, until after the pH of solution is in neutrality, will be golden yellow heavy
Starch is placed in 60 DEG C of drying in baking oven, obtains final product graphite oxide；A certain amount of graphite oxide is added in 20mL deionized water,
Under 120W power, ultrasonic disperse 3h, form the GO suspension that the concentration being completely exfoliated is 10mg/ml；
3）, prepare stabilizer, vulcanizing agent, accelerator etc. cooperation agent dispersion
a）, weigh a certain amount of KOH and paregal O respectively, be dissolved under the conditions of 50 DEG C in deionized water, be configured to respectively
The KOH aqueous solution of 20wt% and the paregal O aqueous solution of 20wt%；
b）, at room temperature by 50g sulfur, the casein solution of 20mL 10wt%, 1.25mL concentration be 11.5% ammonia,
28.75mL deionized water and 75mL glass sand are added in container, with 500r/min mechanical agitation 12h, then pass through sieve
Glass sand is separated with the first dispersant suspension, obtains the sulfur dispersion of 50wt%；At room temperature by 50g zinc oxide,
The casein solution of 20mL 10wt% and ammonia, 30mL deionized water and 75mL glass sand that 3gNF, 5mL concentration is 20% add
To in 500mL enamelled cup, with 500r/min mechanical agitation 10h, then pass through sieve and glass sand and the second dispersant suspend
Liquid separates, and obtains the oxidation zinc dispersion of 40wt%；At room temperature by 50g accelerator ZDC, 40mL 10wt% casein solution and
The glass sand mixing of the deionized water of 1.15gNF, 28.85mL and 75mL is contained in the enamelled cup of 500mL, and with 500r/min
Glass sand is separated with the 3rd dispersant suspension by mechanical agitation 12h finally by sieve, obtains the accelerator ZDC of 50wt%
Dispersion；
4）, emulsion dispersion preparation Fe3O4@GO/NR magnetic elastomeric composite material
a）, first, adjust the pH to 14 of water-soluble natural latex with NaOH aqueous solution, and add the KOH of the 20wt% of metering
Aqueous solution, the paregal O aqueous solution of 20wt%, wherein KOH and latex butt mass ratio are 1：1000, paregal O and latex butt
Mass ratio is 1：900；
b）, secondly, by step 1）With step 2）Described in certain volume stable Fe3O4Water-base magnetic liquid and described
Certain volume the GO suspension being completely exfoliated, be added to a under 50 DEG C and 150r/min mechanical agitation）Step is obtained
Water-soluble natural latex mixed liquor in formed composite solution；
c）, the sulfur dispersion, ZnO dispersion and the accelerator ZDC dispersion that add metering in above-mentioned composite solution, former
Position sulfuration 100min, forms presulfurization magnetic coupling emulsion, wherein sulfur and latex butt mass ratio is 1:70, zinc oxide and glue
Newborn butt mass ratio is 1:180, accelerator ZDC and latex butt mass ratio are 1:100；Then by this complex emulsions in 175r/
After supersound process 110min under min mechanical agitation, pour in mould, 10h is dried at 80 DEG C, obtain the homogeneous Fe of structure3O4@
GO/NR magnetic elastomeric composite material, Fe3O4Water-base magnetic liquid, the GO suspension being completely exfoliated, 4）a）The water that step is obtained
The consumption of soluble natural latex mixed liquor should ensure that prepared Fe3O4Natural rubber is contained in@GO/NR magnetic elastomeric composite material
87.9wt%, Fe3O47.6wt%, GO2.3wt%.
Embodiment five：Fe3O4@GO/NR magnetic elastomer composite material and preparation method thereof, comprises the following steps：
1）, preparation stablize Fe3O4Water-base magnetic liquid
By 3.6g FeCl2·4H2O and 6.1g FeCl3·6H2O is dissolved in 90mL deionized water, stirs all at 50 DEG C
After even, under 500r/min stirring, Deca 90mL concentration is the NaOH aqueous solution of 1.34mol/L, reacts 90min after completion of dropping
Stop, being cooled to room temperature, resulting solution Magneto separate is obtained black precipitate, remove the supernatant, more ultrasonic point of deionized water
Scattered, Magneto separate, repeated washing, until the pH of supernatant is in neutrality.Then by black magnetic particle ultrasonic disperse in certain volume
Deionized water in, and with 200r/min mechanical agitation 10min, until forming the stable Fe that concentration is 0.09g/mL3O4Water base magnetic
Property liquid；
2）, the GO suspension that is completely exfoliated of preparation
Under condition of ice bath, 2.0g natural flake graphite and 2.0g sodium nitrate are added in the concentrated sulphuric acid of 46mL, with
600r/min mechanical agitation 30min；6.0g potassium permanganate is added in above-mentioned mixed liquor, with 600r/min mechanical agitation
60min.Above-mentioned mixed liquor is transferred in 45 DEG C of water-baths, after 400r/min mechanical agitation 4h, 80mL deionized water is added
To in mixed liquor, transfer it in 95 DEG C of oil bath；When solution temperature to be mixed reaches 95 DEG C, successively add 200mL
Deionized water and the hydrogen peroxide of 16mL 30% concentration, when solution becomes golden yellow by brown color, stopped reaction；Use successively
2mol/L HCl solution, deionized water and the multiple centrifuge washing of dehydrated alcohol, until after the pH of solution is in neutrality, will be golden yellow heavy
Starch is placed in 60 DEG C of drying in baking oven, obtains final product graphite oxide；A certain amount of graphite oxide is added in 20mL deionized water,
Under 120W power, ultrasonic disperse 6h, form the GO suspension that the concentration being completely exfoliated is 2.5mg/ml；
3）, prepare stabilizer, vulcanizing agent, accelerator etc. cooperation agent dispersion
a）, weigh a certain amount of KOH and paregal O respectively, be dissolved under the conditions of 50 DEG C in deionized water, be configured to respectively
The KOH aqueous solution of 20wt% and the paregal O aqueous solution of 20wt%；
b）, at room temperature by 50g sulfur, the casein solution of 20mL 10wt%, 1.25mL concentration be 11.5% ammonia,
28.75mL deionized water and 75mL glass sand are added in container, with 500r/min mechanical agitation 12h, then pass through sieve
Glass sand is separated with the first dispersant suspension, obtains the sulfur dispersion of 50wt%；At room temperature by 50g zinc oxide,
The casein solution of 20mL 10wt% and ammonia, 30mL deionized water and 75mL glass sand that 3gNF, 5mL concentration is 20% add
To in 500mL enamelled cup, with 500r/min mechanical agitation 10h, then pass through sieve and glass sand and the second dispersant suspend
Liquid separates, and obtains the oxidation zinc dispersion of 40wt%；At room temperature by 50g accelerator ZDC, 40mL 10wt% casein solution and
The glass sand mixing of the deionized water of 1.15gNF, 28.85mL and 75mL is contained in the enamelled cup of 500mL, and with 500r/min
Glass sand is separated with the 3rd dispersant suspension by mechanical agitation 12h finally by sieve, obtains the accelerator ZDC of 50wt%
Dispersion；
4）, emulsion dispersion preparation Fe3O4@GO/NR magnetic elastomeric composite material
a）, first, adjust the pH to 12.5 of water-soluble natural latex with KOH aqueous solution, and add the 20wt% of metering
KOH solution, the paregal O solution of 20wt%, wherein KOH and latex butt mass ratio are 1：800, paregal O and latex butt matter
Amount ratio is 1：500；
b）, secondly, by step 1）With step 2）Described in certain volume stable Fe3O4Water-base magnetic liquid and described
Certain volume the GO suspension being completely exfoliated, be added to a under 50 DEG C and 250r/min mechanical agitation）Step is obtained
Water-soluble natural latex mixed liquor in formed composite solution；
c）, the sulfur dispersion, ZnO dispersion and the accelerator ZDC dispersion that add metering in above-mentioned composite solution, former
Position sulfuration 120min, forms presulfurization magnetic coupling emulsion, wherein sulfur and latex butt mass ratio is 1:50, zinc oxide and glue
Newborn butt mass ratio is 1:220, accelerator ZDC and latex butt mass ratio are 1:160；Then by this complex emulsions in 200r/
After supersound process 70min under min mechanical agitation, pour in mould, 28h is dried at 50 DEG C, obtain the homogeneous Fe of structure3O4@
GO/NR magnetic elastomeric composite material, Fe3O4Water-base magnetic liquid, the GO suspension being completely exfoliated, 4）a）The water that step is obtained
The consumption of soluble natural latex mixed liquor should ensure that prepared Fe3O4Natural rubber is contained in@GO/NR magnetic elastomeric composite material
93.9wt%, Fe3O45.5wt%, GO1.5wt%.
Claims (2)
1. a kind of Fe3O4@GO/NR magnetic elastomer composite material and preparation method thereof, it is characterized by：Comprise the following steps：
1）, preparation stablize Fe3O4Water-base magnetic liquid
By 3.6g FeCl2·4H2O and 6.1g FeCl3·6H2O is dissolved in 90mL deionized water, after stirring at 50 DEG C,
Under 500r/min stirring, Deca 90mL concentration is the NaOH aqueous solution of 1.34mol/L, and after completion of dropping, reaction 90min stops
Only, it is cooled to room temperature, resulting solution Magneto separate is obtained black precipitate, remove the supernatant, then deionized water ultrasonic disperse,
Magneto separate, repeated washing, until the pH of supernatant is in neutrality；
Then by black magnetic particle ultrasonic disperse in the deionized water of certain volume, and with 200r/min mechanical agitation
10min, until form the stable Fe that concentration is 0.02 ~ 0.167g/mL3O4Water-base magnetic liquid；
2）, the GO suspension that is completely exfoliated of preparation
Under condition of ice bath, 2.0g natural flake graphite and 2.0g sodium nitrate are added in the concentrated sulphuric acid of 46mL, with 600r/
Min mechanical agitation 30min；6.0g potassium permanganate is added in above-mentioned mixed liquor, with 600r/min mechanical agitation 60min；
Above-mentioned mixed liquor is transferred in 45 DEG C of water-baths, after 400r/min mechanical agitation 4h, 80mL deionized water is added to
In mixed liquor, transfer it in 95 DEG C of oil bath；When solution temperature to be mixed reaches 95 DEG C, 200mL is successively added to go
Ionized water and the hydrogen peroxide of 16mL 30% concentration, when solution becomes golden yellow by brown color, stopped reaction；Use 2mol/L successively
HCl solution, deionized water and the multiple centrifuge washing of dehydrated alcohol, until after the pH of solution is in neutrality, golden yellow precipitate thing is put
In baking oven, 60 DEG C of drying, obtain final product graphite oxide；A certain amount of graphite oxide is added in 20mL deionized water, in 120W work(
Under rate, ultrasonic disperse 3 ~ 7h, form the GO suspension that the concentration being completely exfoliated is 0.5mg/ml ~ 10mg/ml；
3）, prepare stabilizer, vulcanizing agent, accelerator etc. cooperation agent dispersion
a）, weigh a certain amount of KOH and paregal O respectively, be dissolved under the conditions of 50 DEG C in deionized water, be configured to respectively
The KOH aqueous solution of 20wt% and the paregal O aqueous solution of 20wt%；
b）, at room temperature by 50g sulfur, the casein solution of 20mL 10wt%, 1.25mL concentration be 11.5% ammonia,
28.75mL deionized water and 75mL glass sand are added in container, with 500r/min mechanical agitation 12h, then pass through sieve
Glass sand is separated with the first dispersant suspension, obtains the sulfur dispersion of 50wt%；At room temperature by 50g zinc oxide,
The casein solution of 20mL 10wt% and ammonia, 30mL deionized water and 75mL glass sand that 3gNF, 5mL concentration is 20% add
To in 500mL enamelled cup, with 500r/min mechanical agitation 10h, then pass through sieve and glass sand and the second dispersant suspend
Liquid separates, and obtains the oxidation zinc dispersion of 40wt%；At room temperature by 50g accelerator ZDC, 40mL 10wt% casein solution and
The glass sand mixing of the deionized water of 1.15gNF, 28.85mL and 75mL is contained in the enamelled cup of 500mL, and with 500r/min
Glass sand is separated with the 3rd dispersant suspension by mechanical agitation 12h finally by sieve, obtains the accelerator ZDC of 50wt%
Dispersion；
4）, emulsion dispersion preparation Fe3O4@GO/NR magnetic elastomeric composite material
a）, first, with alkali liquor adjust water-soluble natural latex pH to 8 ~ 14, and add the 20wt% of metering KOH aqueous solution,
The paregal O aqueous solution of 20wt%, wherein KOH and latex butt mass ratio are 1：500 ~ 1000, paregal O and latex butt matter
Amount ratio is 1：500~1000；
b）, secondly, by step 1）With step 2）Described in certain volume stable Fe3O4Water-base magnetic liquid and described one
Determine the GO suspension being completely exfoliated of volume, under 50 DEG C and 150 ~ 250r/min mechanical agitation, be added to a）Step is obtained
Water-soluble natural latex mixed liquor in formed composite solution；
c）, the sulfur dispersion, ZnO dispersion and the accelerator ZDC dispersion that add metering in above-mentioned composite solution, original position sulfur
Change 60 ~ 150min, form presulfurization magnetic coupling emulsion, wherein sulfur and latex butt mass ratio is 1:50 ~ 150, zinc oxide
It is 1 with latex butt mass ratio:100 ~ 300, accelerator ZDC and latex butt mass ratio are 1:100~200；Then this is combined
After emulsion supersound process 30 ~ 180min under 150 ~ 250r/min mechanical agitation, pour in mould, dry 10 at 20 ~ 80 DEG C ~
36h, obtains the homogeneous Fe of structure3O4@GO/NR magnetic elastomeric composite material, Fe3O4Water-base magnetic liquid, the GO being completely exfoliated
Suspension, 4）a）The consumption of the water-soluble natural latex mixed liquor that step is obtained should ensure that prepared Fe3O4@GO/NR magnetic elastomeric
84.9 ~ 96.4wt% containing natural rubber in composite material, Fe3O41 ~ 10wt%, GO 0.5 ~ 3wt%.
2. Fe according to claim 13O4@GO/NR magnetic elastomer composite material and preparation method thereof, it is characterized by：Described step
Rapid 4）a）Alkali liquor used can be NaOH aqueous solution or KOH aqueous solution or NH3 .H2One of O aqueous solution.
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| CN113248744B (en) * | 2021-06-22 | 2021-10-22 | 中国热带农业科学院南亚热带作物研究所 | Preparation method of graphite microchip/natural latex composite material and product |
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