CN104877192A - Fe3O4@GO/NR magnetic elastomer composite material and preparation method - Google Patents

Fe3O4@GO/NR magnetic elastomer composite material and preparation method Download PDF

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CN104877192A
CN104877192A CN201510298287.5A CN201510298287A CN104877192A CN 104877192 A CN104877192 A CN 104877192A CN 201510298287 A CN201510298287 A CN 201510298287A CN 104877192 A CN104877192 A CN 104877192A
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deionized water
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CN104877192B (en
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赵贵哲
孙友谊
侯春林
高莉
刘亚青
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North University of China
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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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
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/01—Magnetic additives
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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

Fe 3o 4gO/NR magnetic elastomeric composite material and preparation method
Technical field
The present invention relates to magnetic elastomeric composite material and preparation method, be specially Fe 3o 4gO/NR magnetic elastomeric composite material and preparation method.
Background technology
Fe 3o 4/ natural rubber (NR) magnetic elastomeric composite material is owing to having controlled magneto-induced modulus, magnetoresistance, magnetostriction, mangneto damping and magnetic performance under outside magnetic field effect, thus the axle bush in damping, noise reduction field, self-tuning formula bump leveller, vibration isolator, suspension, the fields such as magnetic sealing device have a wide range of applications.Preparation Fe 3o 4the traditional method of/NR magnetic elastomeric composite material is mainly by natural rubber rubber, Fe 3o 4magnetic and other processing aid are prepared shaping by blend technique.But, this kind of preparation method causes the dispersion of magnetic particle in natural rubber matrix uneven, and magnetic particle is easily assembled in curing molding process, cause the stuctures and properties of magnetic elastomeric composite material unstable, especially mechanical properties decrease, greatly limit the range of application of such material.Therefore, design a kind of magnetic particle and be uniformly dispersed, be not easy to assemble, performance structure is stablized, the Fe that mechanical property is good 3o 4/ NR magnetic elastomeric composite material and preparation method are extremely necessary.
Summary of the invention
The present invention solves existing Fe 3o 4in/NR material, magnetic particle dispersion is uneven, and magnetic particle is easily assembled, and structure properties is unstable, and the problem of poor mechanical property, provides a kind of Fe 3o 4gO/NR(Fe 3o 4graphene oxide/natural rubber) magnetic elastomeric composite material and preparation method.
The present invention is achieved by the following technical solutions: Fe 3o 4gO/NR magnetic elastomer composite material and preparation method thereof, comprises the following steps:
1), Fe is stablized in preparation 3o 4water-base magnetic liquid
By 3.6g FeCl 24H 2o and 6.1g FeCl 36H 2o is dissolved in 90mL deionized water, after stirring at 50 DEG C, under 500r/min stirs, drip the NaOH aqueous solution that 90mL concentration is 1.34mol/L, dropwise rear reaction 90min and stop, be cooled to room temperature, gained solution Magneto separate is obtained black precipitate, removing supernatant liquid, then use deionized water ultrasonic disperse, Magneto separate, repeated washing, until the pH of supernatant liquor is in neutral.Then by black magnetic particle ultrasonic disperse in the deionized water of certain volume, and with 200r/min mechanical stirring 10min, until form the stable Fe that concentration is 0.02 ~ 0.167g/mL 3o 4water-base magnetic liquid;
2) the GO(graphene oxide peeled off completely, is prepared) suspension
Under condition of ice bath, 2.0g natural flake graphite and 2.0g SODIUMNITRATE are joined in the vitriol oil of 46mL, with 600r/min mechanical stirring 30min; 6.0g potassium permanganate is joined in above-mentioned mixed solution, with 600r/min mechanical stirring 60min.Above-mentioned mixed solution is transferred in 45 DEG C of water-baths, after 400r/min mechanical stirring 4h, 80mL deionized water is joined in mixed solution, then transferred in the oil bath of 95 DEG C; When solution temperature to be mixed reaches 95 DEG C, successively add the hydrogen peroxide of 200mL deionized water and 16mL 30% concentration, when solution becomes golden yellow by brown color, stopped reaction; Use 2mol/L HCl solution, deionized water and dehydrated alcohol repeatedly centrifuge washing successively, until the pH of solution is after neutrality, golden yellow precipitate thing is placed in 60 DEG C of oven dry in baking oven, obtains graphite oxide; Joined by a certain amount of graphite oxide in 20mL deionized water, under 120W power, ultrasonic disperse 3 ~ 7h, forms the GO suspension that the concentration peeled off completely is 0.5mg/ml ~ 10mg/ml;
3) the Synergist S-421 95 dispersions such as stablizer, vulcanizing agent, promotor, are prepared
A) a certain amount of KOH and peregal O(alkyl polyoxyethylene ether is taken, respectively), be dissolved under 50 DEG C of conditions in deionized water, be mixed with the KOH aqueous solution of 20wt% and the paregal O aqueous solution of 20wt% respectively;
B), by the casein solution of 50g sulphur, 20mL 10wt%, 1.25mL concentration be at room temperature 11.5% ammoniacal liquor, 28.75mL deionized water and 75mL glass sand join in container, with 500r/min mechanical stirring 12h, then by sieve, glass sand is separated with the first dispersion agent suspension, obtains the sulphur dispersion of 50wt%; At room temperature by the casein solution of 50g zinc oxide, 20mL 10wt% and 3gNF(methylene sodium dinaphthalenesulfonate), 5mL concentration be 20% ammoniacal liquor, 30mL deionized water and 75mL glass sand join in 500mL enamelled cup, with 500r/min mechanical stirring 10h, then by sieve, glass sand is separated with the second dispersion agent suspension, obtains the zinc oxide dispersion of 40wt%; At room temperature by 50g promotor ZDC(zinc diethyldithiocarbamate), the deionized water of 40mL 10wt% casein solution and 1.15gNF, 28.85mL and the glass sand mixing of 75mL contain in the enamelled cup of 500mL, and with 500r/min mechanical stirring 12h, finally by sieve, glass sand is separated with the 3rd dispersion agent suspension, obtains the promotor ZDC dispersion of 50wt%;
4), emulsion dispersion prepares Fe 3o 4gO/NR magnetic elastomeric composite material
A), first, pH to 8 ~ 14 of water-soluble natural latex are regulated with alkali lye, and add the KOH aqueous solution of the 20wt% of metering, the paregal O aqueous solution of 20wt%, wherein KOH and latex butt mass ratio are 1:500 ~ 1000, and paregal O and latex butt mass ratio are 1:500 ~ 1000;
B), secondly, by step 1) and step 2) described in the stable Fe of certain volume 3o 4the GO suspension peeled off completely of water-base magnetic liquid and described certain volume, joins in the obtained water-soluble natural latex mixed solution of a) step and forms composite solution under 50 DEG C and 150 ~ 250r/min mechanical agitation;
C) in above-mentioned composite solution, add the sulphur dispersion of metering, ZnO dispersion and promotor ZDC dispersion, In-situ sulphiding 60 ~ 150min, form prevulcanized magnetic coupling emulsion, wherein sulphur and latex butt mass ratio are 1:50 ~ 150, zinc oxide and latex butt mass ratio are 1:100 ~ 300, and promotor ZDC and latex butt mass ratio are 1:100 ~ 200; Then after supersound process 30 ~ 180min, pour in mould by this composite emulsion under 150 ~ 250r/min mechanical stirring, at 20 ~ 80 DEG C, dry 10 ~ 36h, obtains the Fe that structure is homogeneous 3o 4gO/NR magnetic elastomeric composite material, Fe 3o 4water-base magnetic liquid, the GO suspension, 4 peeled off completely) consumption of water-soluble natural latex mixed solution that a) step obtains should ensure the Fe that obtains 3o 4containing natural rubber 84.9wt%, Fe in GO/NR magnetic elastomeric composite material 3o 410wt%, GO3wt%.
Chemical coprecipitation in this patent is adopted to prepare Fe 3o 4water-base magnetic liquid, makes Fe 3o 4the dispersiveness of magnetic particle is better, and not easily reunites.To adopt in this patent Hummers legal system for graphite oxide, and then prepare GO suspension with obtained graphite oxide, make the GO suspension that obtains better dispersed.Prepare sulphur dispersion, ZnO dispersion and promotor ZDC dispersion respectively as vulcanizing agent, stablizer and promotor, join in follow-up mixing solutions.Add casein solution or add casein solution and NF(methylene sodium dinaphthalenesulfonate together) as dispersion agent.Alkali lye used can be the NaOH aqueous solution or the KOH aqueous solution or NH 3 .h 2one in the O aqueous solution.Described KOH and latex butt mass ratio are 1:500 ~ 1000, to be 1:500 ~ 1000 be adds the mass ratio of solute in the KOH aqueous solution of quantitative fixed mass mark and the paregal O aqueous solution and latex butt for paregal O and latex butt mass ratio, do not comprise the KOH comprised in alkali lye.In natural rubber latex, add the KOH aqueous solution, the paregal O aqueous solution, to strengthen micelle surface charge, protective layer, hydrauture, guarantee that latex long-time stable is even.Test in laboratory obtains finally obtained Fe 3o 41.5 ~ 3.5wt% is amounted to containing KOH and paregal O and sulphur and ZnO and ZDC in GO/NR magnetic elastomeric composite material, wherein optimum containing its material property during 2.1wt%.
During concrete enforcement, described alkali lye can be the NaOH aqueous solution or the KOH aqueous solution or NH 3 .h 2one in the O aqueous solution.
The present invention and existing Fe 3o 4/ NR magnetic elastomeric composite material and preparation method thereof is compared and is had the following advantages: 1, curing temperature is low, preparation technology is simple, and effectively improve magnetic particle, the GO dispersiveness in rubber matrix, overcome the problem that magnetic particle, GO easily reunite in elastomer matrix, obtain constitutionally stable Fe 3o 4gO/NR magnetic elastomeric composite material; 2, the graphene oxide introduced not only can be used as reactive reinforcement, improve the mechanical mechanics property of magnetic elastomeric composite material, all right stabilized magnetic particle, prevents sedimentation and the reunion of magnetic particle, improves magnetic elastomer mechanical mechanics property and magnetic property further; 3, Fe obtained by the present invention 3o 4gO/NR magnetic elastomeric composite material, can demonstrate excellent theory of elasticity performance, magnetic property, resistance toheat and solvent resistance at low concentrations.
Embodiment
Embodiment one: Fe 3o 4gO/NR magnetic elastomer composite material and preparation method thereof, comprises the following steps:
1), Fe is stablized in preparation 3o 4water-base magnetic liquid
By 3.6g FeCl 24H 2o and 6.1g FeCl 36H 2o is dissolved in 90mL deionized water, after stirring at 50 DEG C, under 500r/min stirs, drip the NaOH aqueous solution that 90mL concentration is 1.34mol/L, dropwise rear reaction 90min and stop, be cooled to room temperature, gained solution Magneto separate is obtained black precipitate, removing supernatant liquid, then use deionized water ultrasonic disperse, Magneto separate, repeated washing, until the pH of supernatant liquor is in neutral.Then by black magnetic particle ultrasonic disperse in the deionized water of certain volume, and with 200r/min mechanical stirring 10min, until form the stable Fe that concentration is 0.02g/mL 3o 4water-base magnetic liquid;
2) the GO suspension peeled off completely, is prepared
Under condition of ice bath, 2.0g natural flake graphite and 2.0g SODIUMNITRATE are joined in the vitriol oil of 46mL, with 600r/min mechanical stirring 30min; 6.0g potassium permanganate is joined in above-mentioned mixed solution, with 600r/min mechanical stirring 60min.Above-mentioned mixed solution is transferred in 45 DEG C of water-baths, after 400r/min mechanical stirring 4h, 80mL deionized water is joined in mixed solution, then transferred in the oil bath of 95 DEG C; When solution temperature to be mixed reaches 95 DEG C, successively add the hydrogen peroxide of 200mL deionized water and 16mL 30% concentration, when solution becomes golden yellow by brown color, stopped reaction; Use 2mol/L HCl solution, deionized water and dehydrated alcohol repeatedly centrifuge washing successively, until the pH of solution is after neutrality, golden yellow precipitate thing is placed in 60 DEG C of oven dry in baking oven, obtains graphite oxide; Joined by a certain amount of graphite oxide in 20mL deionized water, under 120W power, ultrasonic disperse 5h, forms the GO suspension that the concentration peeled off completely is 0.5mg/ml;
3) the Synergist S-421 95 dispersions such as stablizer, vulcanizing agent, promotor, are prepared
A) take a certain amount of KOH and paregal O, respectively, be dissolved under 50 DEG C of conditions in deionized water, be mixed with the KOH aqueous solution of 20wt% and the paregal O aqueous solution of 20wt% respectively;
B), by the casein solution of 50g sulphur, 20mL 10wt%, 1.25mL concentration be at room temperature 11.5% ammoniacal liquor, 28.75mL deionized water and 75mL glass sand join in container, with 500r/min mechanical stirring 12h, then by sieve, glass sand is separated with the first dispersion agent suspension, obtains the sulphur dispersion of 50wt%; Be at room temperature that the ammoniacal liquor of 20%, 30mL deionized water and 75mL glass sand join in 500mL enamelled cup by the casein solution of 50g zinc oxide, 20mL 10wt% and 3gNF, 5mL concentration, with 500r/min mechanical stirring 10h, then by sieve, glass sand is separated with the second dispersion agent suspension, obtains the zinc oxide dispersion of 40wt%; At room temperature the glass sand mixing of the deionized water of 50g promotor ZDC, 40mL 10wt% casein solution and 1.15gNF, 28.85mL and 75mL is contained in the enamelled cup of 500mL, and with 500r/min mechanical stirring 12h, finally by sieve, glass sand is separated with the 3rd dispersion agent suspension, obtains the promotor ZDC dispersion of 50wt%;
4), emulsion dispersion prepares Fe 3o 4gO/NR magnetic elastomeric composite material
A), first, the pH to 11 of water-soluble natural latex is regulated with the NaOH aqueous solution, and add the KOH aqueous solution of the 20wt% of metering, the paregal O aqueous solution of 20wt%, wherein KOH and latex butt mass ratio are 1:900, and paregal O and latex butt mass ratio are 1:650;
B), secondly, by step 1) and step 2) described in the stable Fe of certain volume 3o 4the GO suspension peeled off completely of water-base magnetic liquid and described certain volume, joins and a) forms composite solution in water-soluble natural latex mixed solution that step is obtained under 50 DEG C and 200r/min mechanical agitation;
C) in above-mentioned composite solution, add the sulphur dispersion of metering, ZnO dispersion and promotor ZDC dispersion, In-situ sulphiding 80min, form prevulcanized magnetic coupling emulsion, wherein sulphur and latex butt mass ratio are 1:150, zinc oxide and latex butt mass ratio: 1:100, promotor ZDC and latex butt mass ratio are 1:120; Then this composite emulsion after supersound process 30min, is poured in mould under 225r/min mechanical stirring, dry 22h at 35 DEG C, obtain the Fe that structure is homogeneous 3o 4gO/NR magnetic elastomeric composite material, Fe 3o 4water-base magnetic liquid, the GO suspension, 4 peeled off completely) consumption of water-soluble natural latex mixed solution that a) step obtains should ensure the Fe that obtains 3o 4containing natural rubber 84.9wt%, Fe in GO/NR magnetic elastomeric composite material 3o 410wt%, GO3wt%.
Embodiment two: Fe 3o 4gO/NR magnetic elastomer composite material and preparation method thereof, comprises the following steps:
1), Fe is stablized in preparation 3o 4water-base magnetic liquid
By 3.6g FeCl 24H 2o and 6.1g FeCl 36H 2o is dissolved in 90mL deionized water, after stirring at 50 DEG C, under 500r/min stirs, drip the NaOH aqueous solution that 90mL concentration is 1.34mol/L, dropwise rear reaction 90min and stop, be cooled to room temperature, gained solution Magneto separate is obtained black precipitate, removing supernatant liquid, then use deionized water ultrasonic disperse, Magneto separate, repeated washing, until the pH of supernatant liquor is in neutral.Then by black magnetic particle ultrasonic disperse in the deionized water of certain volume, and with 200r/min mechanical stirring 10min, until form the stable Fe that concentration is 0.126g/mL 3o 4water-base magnetic liquid;
2) the GO suspension peeled off completely, is prepared
Under condition of ice bath, 2.0g natural flake graphite and 2.0g SODIUMNITRATE are joined in the vitriol oil of 46mL, with 600r/min mechanical stirring 30min; 6.0g potassium permanganate is joined in above-mentioned mixed solution, with 600r/min mechanical stirring 60min.Above-mentioned mixed solution is transferred in 45 DEG C of water-baths, after 400r/min mechanical stirring 4h, 80mL deionized water is joined in mixed solution, then transferred in the oil bath of 95 DEG C; When solution temperature to be mixed reaches 95 DEG C, successively add the hydrogen peroxide of 200mL deionized water and 16mL 30% concentration, when solution becomes golden yellow by brown color, stopped reaction; Use 2mol/L HCl solution, deionized water and dehydrated alcohol repeatedly centrifuge washing successively, until the pH of solution is after neutrality, golden yellow precipitate thing is placed in 60 DEG C of oven dry in baking oven, obtains graphite oxide; Joined by a certain amount of graphite oxide in 20mL deionized water, under 120W power, ultrasonic disperse 4h, forms the GO suspension that the concentration peeled off completely is 7.5mg/ml;
3) the Synergist S-421 95 dispersions such as stablizer, vulcanizing agent, promotor, are prepared
A) take a certain amount of KOH and paregal O, respectively, be dissolved under 50 DEG C of conditions in deionized water, be mixed with the KOH aqueous solution of 20wt% and the paregal O aqueous solution of 20wt% respectively;
B), by the casein solution of 50g sulphur, 20mL 10wt%, 1.25mL concentration be at room temperature 11.5% ammoniacal liquor, 28.75mL deionized water and 75mL glass sand join in container, with 500r/min mechanical stirring 12h, then by sieve, glass sand is separated with the first dispersion agent suspension, obtains the sulphur dispersion of 50wt%; Be at room temperature that the ammoniacal liquor of 20%, 30mL deionized water and 75mL glass sand join in 500mL enamelled cup by the casein solution of 50g zinc oxide, 20mL 10wt% and 3gNF, 5mL concentration, with 500r/min mechanical stirring 10h, then by sieve, glass sand is separated with the second dispersion agent suspension, obtains the zinc oxide dispersion of 40wt%; At room temperature the glass sand mixing of the deionized water of 50g promotor ZDC, 40mL 10wt% casein solution and 1.15gNF, 28.85mL and 75mL is contained in the enamelled cup of 500mL, and with 500r/min mechanical stirring 12h, finally by sieve, glass sand is separated with the 3rd dispersion agent suspension, obtains the promotor ZDC dispersion of 50wt%;
4), emulsion dispersion prepares Fe 3o 4gO/NR magnetic elastomeric composite material
A), first, the pH to 8 of water-soluble natural latex is regulated with the KOH aqueous solution, and add the KOH aqueous solution of the 20wt% of metering, the paregal O aqueous solution of 20wt%, wherein KOH and latex butt mass ratio are 1:650, and paregal O and latex butt mass ratio are 1:1000;
B), secondly, by step 1) and step 2) described in the stable Fe of certain volume 3o 4the GO suspension peeled off completely of water-base magnetic liquid and described certain volume, joins and a) forms composite solution in water-soluble natural latex mixed solution that step is obtained under 50 DEG C and 170r/min mechanical agitation;
C) in above-mentioned composite solution, add the sulphur dispersion of metering, ZnO dispersion and promotor ZDC dispersion, In-situ sulphiding 150min, form prevulcanized magnetic coupling emulsion, wherein sulphur and latex butt mass ratio are 1:90, zinc oxide and latex butt mass ratio are 1:260, and promotor ZDC and latex butt mass ratio are 1:200; Then this composite emulsion after supersound process 150min, is poured in mould under 250r/min mechanical stirring, dry 16h at 20 DEG C, obtain the Fe that structure is homogeneous 3o 4gO/NR magnetic elastomeric composite material, Fe 3o 4water-base magnetic liquid, the GO suspension, 4 peeled off completely) consumption of water-soluble natural latex mixed solution that a) step obtains should ensure the Fe that obtains 3o 4containing natural rubber 96.4wt%, Fe in GO/NR magnetic elastomeric composite material 3o 41wt%, GO 1wt%.
Embodiment three: Fe 3o 4gO/NR magnetic elastomer composite material and preparation method thereof, comprises the following steps:
1), Fe is stablized in preparation 3o 4water-base magnetic liquid
By 3.6g FeCl 24H 2o and 6.1g FeCl 36H 2o is dissolved in 90mL deionized water, after stirring at 50 DEG C, under 500r/min stirs, drip the NaOH aqueous solution that 90mL concentration is 1.34mol/L, dropwise rear reaction 90min and stop, be cooled to room temperature, gained solution Magneto separate is obtained black precipitate, removing supernatant liquid, then use deionized water ultrasonic disperse, Magneto separate, repeated washing, until the pH of supernatant liquor is in neutral.Then by black magnetic particle ultrasonic disperse in the deionized water of certain volume, and with 200r/min mechanical stirring 10min, until form the stable Fe that concentration is 0.167g/mL 3o 4water-base magnetic liquid;
2) the GO suspension peeled off completely, is prepared
Under condition of ice bath, 2.0g natural flake graphite and 2.0g SODIUMNITRATE are joined in the vitriol oil of 46mL, with 600r/min mechanical stirring 30min; 6.0g potassium permanganate is joined in above-mentioned mixed solution, with 600r/min mechanical stirring 60min.Above-mentioned mixed solution is transferred in 45 DEG C of water-baths, after 400r/min mechanical stirring 4h, 80mL deionized water is joined in mixed solution, then transferred in the oil bath of 95 DEG C; When solution temperature to be mixed reaches 95 DEG C, successively add the hydrogen peroxide of 200mL deionized water and 16mL 30% concentration, when solution becomes golden yellow by brown color, stopped reaction; Use 2mol/L HCl solution, deionized water and dehydrated alcohol repeatedly centrifuge washing successively, until the pH of solution is after neutrality, golden yellow precipitate thing is placed in 60 DEG C of oven dry in baking oven, obtains graphite oxide; Joined by a certain amount of graphite oxide in 20mL deionized water, under 120W power, ultrasonic disperse 7h, forms the GO suspension that the concentration peeled off completely is 5mg/ml;
3) the Synergist S-421 95 dispersions such as stablizer, vulcanizing agent, promotor, are prepared
A) take a certain amount of KOH and paregal O, respectively, be dissolved under 50 DEG C of conditions in deionized water, be mixed with the KOH aqueous solution of 20wt% and the paregal O aqueous solution of 20wt% respectively;
B), by the casein solution of 50g sulphur, 20mL 10wt%, 1.25mL concentration be at room temperature 11.5% ammoniacal liquor, 28.75mL deionized water and 75mL glass sand join in container, with 500r/min mechanical stirring 12h, then by sieve, glass sand is separated with the first dispersion agent suspension, obtains the sulphur dispersion of 50wt%; Be at room temperature that the ammoniacal liquor of 20%, 30mL deionized water and 75mL glass sand join in 500mL enamelled cup by the casein solution of 50g zinc oxide, 20mL 10wt% and 3gNF, 5mL concentration, with 500r/min mechanical stirring 10h, then by sieve, glass sand is separated with the second dispersion agent suspension, obtains the zinc oxide dispersion of 40wt%; At room temperature the glass sand mixing of the deionized water of 50g promotor ZDC, 40mL 10wt% casein solution and 1.15gNF, 28.85mL and 75mL is contained in the enamelled cup of 500mL, and with 500r/min mechanical stirring 12h, finally by sieve, glass sand is separated with the 3rd dispersion agent suspension, obtains the promotor ZDC dispersion of 50wt%;
4), emulsion dispersion prepares Fe 3o 4gO/NR magnetic elastomeric composite material
A), first, NH is used 3 .h 2the O aqueous solution regulates the pH to 9.5 of water-soluble natural latex, and adds the KOH aqueous solution of the 20wt% of metering, the paregal O aqueous solution of 20wt%, and wherein KOH and latex butt mass ratio are 1:500, and paregal O and latex butt mass ratio are 1:800;
B), secondly, by step 1) and step 2) described in the stable Fe of certain volume 3o 4the GO suspension peeled off completely of water-base magnetic liquid and described certain volume, joins and a) forms composite solution in water-soluble natural latex mixed solution that step is obtained under 50 DEG C and 220r/min mechanical agitation;
C) in above-mentioned composite solution, add the sulphur dispersion of metering, ZnO dispersion and promotor ZDC dispersion, In-situ sulphiding 60min, form prevulcanized magnetic coupling emulsion, wherein sulphur and latex butt mass ratio are 1:120, zinc oxide and latex butt mass ratio are 1:300, and promotor ZDC and latex butt mass ratio are 1:140; Then this composite emulsion after supersound process 180min, is poured in mould under 150r/min mechanical stirring, dry 36h at 65 DEG C, obtain the Fe that structure is homogeneous 3o 4gO/NR magnetic elastomeric composite material, Fe 3o 4water-base magnetic liquid, the GO suspension, 4 peeled off completely) consumption of water-soluble natural latex mixed solution that a) step obtains should ensure the Fe that obtains 3o 4containing natural rubber 93.9wt%, Fe in GO/NR magnetic elastomeric composite material 3o 43wt%, GO 1wt%.
Embodiment four: Fe 3o 4gO/NR magnetic elastomer composite material and preparation method thereof, comprises the following steps:
1), Fe is stablized in preparation 3o 4water-base magnetic liquid
By 3.6g FeCl 24H 2o and 6.1g FeCl 36H 2o is dissolved in 90mL deionized water, after stirring at 50 DEG C, under 500r/min stirs, drip the NaOH aqueous solution that 90mL concentration is 1.34mol/L, dropwise rear reaction 90min and stop, be cooled to room temperature, gained solution Magneto separate is obtained black precipitate, removing supernatant liquid, then use deionized water ultrasonic disperse, Magneto separate, repeated washing, until the pH of supernatant liquor is in neutral.Then by black magnetic particle ultrasonic disperse in the deionized water of certain volume, and with 200r/min mechanical stirring 10min, until form the stable Fe that concentration is 0.056g/mL 3o 4water-base magnetic liquid;
2) the GO suspension peeled off completely, is prepared
Under condition of ice bath, 2.0g natural flake graphite and 2.0g SODIUMNITRATE are joined in the vitriol oil of 46mL, with 600r/min mechanical stirring 30min; 6.0g potassium permanganate is joined in above-mentioned mixed solution, with 600r/min mechanical stirring 60min.Above-mentioned mixed solution is transferred in 45 DEG C of water-baths, after 400r/min mechanical stirring 4h, 80mL deionized water is joined in mixed solution, then transferred in the oil bath of 95 DEG C; When solution temperature to be mixed reaches 95 DEG C, successively add the hydrogen peroxide of 200mL deionized water and 16mL 30% concentration, when solution becomes golden yellow by brown color, stopped reaction; Use 2mol/L HCl solution, deionized water and dehydrated alcohol repeatedly centrifuge washing successively, until the pH of solution is after neutrality, golden yellow precipitate thing is placed in 60 DEG C of oven dry in baking oven, obtains graphite oxide; Joined by a certain amount of graphite oxide in 20mL deionized water, under 120W power, ultrasonic disperse 3h, forms the GO suspension that the concentration peeled off completely is 10mg/ml;
3) the Synergist S-421 95 dispersions such as stablizer, vulcanizing agent, promotor, are prepared
A) take a certain amount of KOH and paregal O, respectively, be dissolved under 50 DEG C of conditions in deionized water, be mixed with the KOH aqueous solution of 20wt% and the paregal O aqueous solution of 20wt% respectively;
B), by the casein solution of 50g sulphur, 20mL 10wt%, 1.25mL concentration be at room temperature 11.5% ammoniacal liquor, 28.75mL deionized water and 75mL glass sand join in container, with 500r/min mechanical stirring 12h, then by sieve, glass sand is separated with the first dispersion agent suspension, obtains the sulphur dispersion of 50wt%; Be at room temperature that the ammoniacal liquor of 20%, 30mL deionized water and 75mL glass sand join in 500mL enamelled cup by the casein solution of 50g zinc oxide, 20mL 10wt% and 3gNF, 5mL concentration, with 500r/min mechanical stirring 10h, then by sieve, glass sand is separated with the second dispersion agent suspension, obtains the zinc oxide dispersion of 40wt%; At room temperature the glass sand mixing of the deionized water of 50g promotor ZDC, 40mL 10wt% casein solution and 1.15gNF, 28.85mL and 75mL is contained in the enamelled cup of 500mL, and with 500r/min mechanical stirring 12h, finally by sieve, glass sand is separated with the 3rd dispersion agent suspension, obtains the promotor ZDC dispersion of 50wt%;
4), emulsion dispersion prepares Fe 3o 4gO/NR magnetic elastomeric composite material
A), first, the pH to 14 of water-soluble natural latex is regulated with the NaOH aqueous solution, and add the KOH aqueous solution of the 20wt% of metering, the paregal O aqueous solution of 20wt%, wherein KOH and latex butt mass ratio are 1:1000, and paregal O and latex butt mass ratio are 1:900;
B), secondly, by step 1) and step 2) described in the stable Fe of certain volume 3o 4the GO suspension peeled off completely of water-base magnetic liquid and described certain volume, joins and a) forms composite solution in water-soluble natural latex mixed solution that step is obtained under 50 DEG C and 150r/min mechanical agitation;
C) in above-mentioned composite solution, add the sulphur dispersion of metering, ZnO dispersion and promotor ZDC dispersion, In-situ sulphiding 100min, form prevulcanized magnetic coupling emulsion, wherein sulphur and latex butt mass ratio are 1:70, zinc oxide and latex butt mass ratio are 1:180, and promotor ZDC and latex butt mass ratio are 1:100; Then this composite emulsion after supersound process 110min, is poured in mould under 175r/min mechanical stirring, dry 10h at 80 DEG C, obtain the Fe that structure is homogeneous 3o 4gO/NR magnetic elastomeric composite material, Fe 3o 4water-base magnetic liquid, the GO suspension, 4 peeled off completely) consumption of water-soluble natural latex mixed solution that a) step obtains should ensure the Fe that obtains 3o 4containing natural rubber 87.9wt%, Fe in GO/NR magnetic elastomeric composite material 3o 47.6wt%, GO2.3wt%.
Embodiment five: Fe 3o 4gO/NR magnetic elastomer composite material and preparation method thereof, comprises the following steps:
1), Fe is stablized in preparation 3o 4water-base magnetic liquid
By 3.6g FeCl 24H 2o and 6.1g FeCl 36H 2o is dissolved in 90mL deionized water, after stirring at 50 DEG C, under 500r/min stirs, drip the NaOH aqueous solution that 90mL concentration is 1.34mol/L, dropwise rear reaction 90min and stop, be cooled to room temperature, gained solution Magneto separate is obtained black precipitate, removing supernatant liquid, then use deionized water ultrasonic disperse, Magneto separate, repeated washing, until the pH of supernatant liquor is in neutral.Then by black magnetic particle ultrasonic disperse in the deionized water of certain volume, and with 200r/min mechanical stirring 10min, until form the stable Fe that concentration is 0.09g/mL 3o 4water-base magnetic liquid;
2) the GO suspension peeled off completely, is prepared
Under condition of ice bath, 2.0g natural flake graphite and 2.0g SODIUMNITRATE are joined in the vitriol oil of 46mL, with 600r/min mechanical stirring 30min; 6.0g potassium permanganate is joined in above-mentioned mixed solution, with 600r/min mechanical stirring 60min.Above-mentioned mixed solution is transferred in 45 DEG C of water-baths, after 400r/min mechanical stirring 4h, 80mL deionized water is joined in mixed solution, then transferred in the oil bath of 95 DEG C; When solution temperature to be mixed reaches 95 DEG C, successively add the hydrogen peroxide of 200mL deionized water and 16mL 30% concentration, when solution becomes golden yellow by brown color, stopped reaction; Use 2mol/L HCl solution, deionized water and dehydrated alcohol repeatedly centrifuge washing successively, until the pH of solution is after neutrality, golden yellow precipitate thing is placed in 60 DEG C of oven dry in baking oven, obtains graphite oxide; Joined by a certain amount of graphite oxide in 20mL deionized water, under 120W power, ultrasonic disperse 6h, forms the GO suspension that the concentration peeled off completely is 2.5mg/ml;
3) the Synergist S-421 95 dispersions such as stablizer, vulcanizing agent, promotor, are prepared
A) take a certain amount of KOH and paregal O, respectively, be dissolved under 50 DEG C of conditions in deionized water, be mixed with the KOH aqueous solution of 20wt% and the paregal O aqueous solution of 20wt% respectively;
B), by the casein solution of 50g sulphur, 20mL 10wt%, 1.25mL concentration be at room temperature 11.5% ammoniacal liquor, 28.75mL deionized water and 75mL glass sand join in container, with 500r/min mechanical stirring 12h, then by sieve, glass sand is separated with the first dispersion agent suspension, obtains the sulphur dispersion of 50wt%; Be at room temperature that the ammoniacal liquor of 20%, 30mL deionized water and 75mL glass sand join in 500mL enamelled cup by the casein solution of 50g zinc oxide, 20mL 10wt% and 3gNF, 5mL concentration, with 500r/min mechanical stirring 10h, then by sieve, glass sand is separated with the second dispersion agent suspension, obtains the zinc oxide dispersion of 40wt%; At room temperature the glass sand mixing of the deionized water of 50g promotor ZDC, 40mL 10wt% casein solution and 1.15gNF, 28.85mL and 75mL is contained in the enamelled cup of 500mL, and with 500r/min mechanical stirring 12h, finally by sieve, glass sand is separated with the 3rd dispersion agent suspension, obtains the promotor ZDC dispersion of 50wt%;
4), emulsion dispersion prepares Fe 3o 4gO/NR magnetic elastomeric composite material
A), first, the pH to 12.5 of water-soluble natural latex is regulated with the KOH aqueous solution, and add the KOH solution of the 20wt% of metering, the paregal O solution of 20wt%, wherein KOH and latex butt mass ratio are 1:800, and paregal O and latex butt mass ratio are 1:500;
B), secondly, by step 1) and step 2) described in the stable Fe of certain volume 3o 4the GO suspension peeled off completely of water-base magnetic liquid and described certain volume, joins and a) forms composite solution in water-soluble natural latex mixed solution that step is obtained under 50 DEG C and 250r/min mechanical agitation;
C) in above-mentioned composite solution, add the sulphur dispersion of metering, ZnO dispersion and promotor ZDC dispersion, In-situ sulphiding 120min, form prevulcanized magnetic coupling emulsion, wherein sulphur and latex butt mass ratio are 1:50, zinc oxide and latex butt mass ratio are 1:220, and promotor ZDC and latex butt mass ratio are 1:160; Then this composite emulsion after supersound process 70min, is poured in mould under 200r/min mechanical stirring, dry 28h at 50 DEG C, obtain the Fe that structure is homogeneous 3o 4gO/NR magnetic elastomeric composite material, Fe 3o 4water-base magnetic liquid, the GO suspension, 4 peeled off completely) consumption of water-soluble natural latex mixed solution that a) step obtains should ensure the Fe that obtains 3o 4containing natural rubber 93.9wt%, Fe in GO/NR magnetic elastomeric composite material 3o 45.5wt%, GO1.5wt%.
Accompanying drawing explanation
Fig. 1 is Fe prepared by the present invention 3o 4gO/NR prevulcanized magnetic coupling emulsion leaves standstill the photo in kind after 1 month;
Fig. 2 is Fe prepared by the present invention 3o 4the XRD figure spectrum of GO/NR magnetic elastomeric composite material; As can be seen from the figure: within the scope of 15 ~ 18 °, have the amorphous peak bulge that larger, be near 10 °, have individual diffraction peak to be GO in diffraction angle, and be that the places such as 30.02 °, 35.5 °, 42.12 °, 57.06 °, 62.6 ° demonstrate diffraction peak in diffraction angle, they are respectively Fe 3o 4(fcc) diffraction of the crystal faces such as 220,200,311,400,511, shows GO, Fe 3o 4well be combined with each other by emulsion composite algorithm and natural rubber;
Fig. 3 is Fe prepared by the present invention 3o 4the SEM figure of GO/NR magnetic elastomeric composite material, can observe, Fe from SEM figure 3o 4, the dispersiveness of GO in natural rubber matrix be fine, Material cladding comparatively homogeneous;
Fig. 4 is Fe prepared by the present invention 3o 4gO/NR magnetic elastomer composite sample photo in kind; Can see from macroscopic view photo in kind, any surface finish of matrix material, magnetic particle, graphite oxide and rubber are well combined with each other;
Fig. 5 is Fe prepared by attraction the present invention 3o 4gO/NR magnetic elastomeric composite material photo; The Fe prepared by the known the present invention of photo 3o 4gO/NR magnetic elastomeric composite material has good magnetic property;
Fig. 6 is Fe prepared by the present invention 3o 4the magnetic hysteresis loop of GO/NR magnetic elastomeric composite material; Fe prepared by the present invention is described 3o 4gO/NR magnetic elastomeric composite material has good magnetic property, and magnetic saturation intensity can reach 2.0emu/g;
Fig. 7 is Fe prepared by the present invention 3o 4the stress-strain curve of GO/NR magnetic elastomeric composite material; As can be seen from the figure, after introducing GO, the mechanical property of magnetic elastomeric composite material increases substantially.

Claims (2)

1. a Fe 3o 4gO/NR magnetic elastomer composite material and preparation method thereof, is characterized by: comprise the following steps:
1), Fe is stablized in preparation 3o 4water-base magnetic liquid
By 3.6g FeCl 24H 2o and 6.1g FeCl 36H 2o is dissolved in 90mL deionized water, after stirring at 50 DEG C, under 500r/min stirs, drip the NaOH aqueous solution that 90mL concentration is 1.34mol/L, dropwise rear reaction 90min and stop, be cooled to room temperature, gained solution Magneto separate is obtained black precipitate, removing supernatant liquid, then use deionized water ultrasonic disperse, Magneto separate, repeated washing, until the pH of supernatant liquor is in neutral;
Then by black magnetic particle ultrasonic disperse in the deionized water of certain volume, and with 200r/min mechanical stirring 10min, until form the stable Fe that concentration is 0.02 ~ 0.167g/mL 3o 4water-base magnetic liquid;
2) the GO suspension peeled off completely, is prepared
Under condition of ice bath, 2.0g natural flake graphite and 2.0g SODIUMNITRATE are joined in the vitriol oil of 46mL, with 600r/min mechanical stirring 30min; 6.0g potassium permanganate is joined in above-mentioned mixed solution, with 600r/min mechanical stirring 60min;
Above-mentioned mixed solution is transferred in 45 DEG C of water-baths, after 400r/min mechanical stirring 4h, 80mL deionized water is joined in mixed solution, then transferred in the oil bath of 95 DEG C; When solution temperature to be mixed reaches 95 DEG C, successively add the hydrogen peroxide of 200mL deionized water and 16mL 30% concentration, when solution becomes golden yellow by brown color, stopped reaction; Use 2mol/L HCl solution, deionized water and dehydrated alcohol repeatedly centrifuge washing successively, until the pH of solution is after neutrality, golden yellow precipitate thing is placed in 60 DEG C of oven dry in baking oven, obtains graphite oxide; Joined by a certain amount of graphite oxide in 20mL deionized water, under 120W power, ultrasonic disperse 3 ~ 7h, forms the GO suspension that the concentration peeled off completely is 0.5mg/ml ~ 10mg/ml;
3) the Synergist S-421 95 dispersions such as stablizer, vulcanizing agent, promotor, are prepared
A) take a certain amount of KOH and paregal O, respectively, be dissolved under 50 DEG C of conditions in deionized water, be mixed with the KOH aqueous solution of 20wt% and the paregal O aqueous solution of 20wt% respectively;
B), by the casein solution of 50g sulphur, 20mL 10wt%, 1.25mL concentration be at room temperature 11.5% ammoniacal liquor, 28.75mL deionized water and 75mL glass sand join in container, with 500r/min mechanical stirring 12h, then by sieve, glass sand is separated with the first dispersion agent suspension, obtains the sulphur dispersion of 50wt%; Be at room temperature that the ammoniacal liquor of 20%, 30mL deionized water and 75mL glass sand join in 500mL enamelled cup by the casein solution of 50g zinc oxide, 20mL 10wt% and 3gNF, 5mL concentration, with 500r/min mechanical stirring 10h, then by sieve, glass sand is separated with the second dispersion agent suspension, obtains the zinc oxide dispersion of 40wt%; At room temperature the glass sand mixing of the deionized water of 50g promotor ZDC, 40mL 10wt% casein solution and 1.15gNF, 28.85mL and 75mL is contained in the enamelled cup of 500mL, and with 500r/min mechanical stirring 12h, finally by sieve, glass sand is separated with the 3rd dispersion agent suspension, obtains the promotor ZDC dispersion of 50wt%;
4), emulsion dispersion prepares Fe 3o 4gO/NR magnetic elastomeric composite material
A), first, pH to 8 ~ 14 of water-soluble natural latex are regulated with alkali lye, and add the KOH aqueous solution of the 20wt% of metering, the paregal O aqueous solution of 20wt%, wherein KOH and latex butt mass ratio are 1:500 ~ 1000, and paregal O and latex butt mass ratio are 1:500 ~ 1000;
B), secondly, by step 1) and step 2) described in the stable Fe of certain volume 3o 4the GO suspension peeled off completely of water-base magnetic liquid and described certain volume, joins in the obtained water-soluble natural latex mixed solution of a) step and forms composite solution under 50 DEG C and 150 ~ 250r/min mechanical agitation;
C) in above-mentioned composite solution, add the sulphur dispersion of metering, ZnO dispersion and promotor ZDC dispersion, In-situ sulphiding 60 ~ 150min, form prevulcanized magnetic coupling emulsion, wherein sulphur and latex butt mass ratio are 1:50 ~ 150, zinc oxide and latex butt mass ratio are 1:100 ~ 300, and promotor ZDC and latex butt mass ratio are 1:100 ~ 200; Then after supersound process 30 ~ 180min, pour in mould by this composite emulsion under 150 ~ 250r/min mechanical stirring, at 20 ~ 80 DEG C, dry 10 ~ 36h, obtains the Fe that structure is homogeneous 3o 4gO/NR magnetic elastomeric composite material, Fe 3o 4water-base magnetic liquid, the GO suspension, 4 peeled off completely) consumption of water-soluble natural latex mixed solution that a) step obtains should ensure the Fe that obtains 3o 4containing natural rubber 84.9 ~ 96.4wt%, Fe in GO/NR magnetic elastomeric composite material 3o 41 ~ 10wt%, GO 0.5 ~ 3wt%.
2. Fe according to claim 1 3o 4gO/NR magnetic elastomer composite material and preparation method thereof, is characterized by: described step 4) a) alkali lye used can be the NaOH aqueous solution or the KOH aqueous solution or NH 3 .h 2one in the O aqueous solution.
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