CN104592477A - Preparation method of high-performance magnetic polyurethane elastomer composites - Google Patents
Preparation method of high-performance magnetic polyurethane elastomer composites Download PDFInfo
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Abstract
The invention relates to magnetic polyurethane elastomer composites, in particular to a preparation method of high-performance magnetic polyurethane elastomer composites, and aims to solve the problem that the mechanical and magnetic properties of magnetic elastomer composites are difficult to be optimized simultaneously, wherein the solution is that the preparation method comprises the following steps: preparing Fe3O4 water-based magnetic fluid by a chemical coprecipitation method, and preparing graphene @ Fe3O4 composite magnetic particles by adsorption; purifying and dispersing the graphene @ Fe3O4 composite magnetic particles in an organic solvent to obtain graphene @ Fe3O4 composite organic magnetic fluid; taking graphene @ Fe3O4 composite organic magnetic fluid as one of the main raw materials to prepare graphene @ Fe3O4 polyurethane elastomer composites by a magnetic controlled in-situ polymerization method. The preparation method of high-performance magnetic polyurethane elastomer composites has the advantages that the problem of easy aggregation of functional fillers in the preparation and forming process of composites is solved, the dispersion and distribution of functional particles in polymer matrix are improved and controlled, graphene is introduced to improve the mechanical and magnetic properties of magnetic elastomer composites simultaneously, and the magnetic elastomer composites have excellent mechanical and magnetic properties.
Description
Technical field
The present invention relates to magnetic polyurethane elastic composite, be specially high performance magnetic polyurethane elastic composite preparation method.
Background technology
Fe
3o
4magnetic polyurethane elastic composite is because have excellent properties, as magnetism characteristic, lightweight, low magnetic loss, good stability, easily process, thus can be widely used in the fields such as intelligent damping, electromagnetic shielding, wide-band microwave absorption, magnetoresistive sensor, magnetic seal device.But this magnetic functional material exists the contradictory problems that mechanical mechanics property and magnetic property are difficult to improve all the time simultaneously, greatly limit its application.Cause the reason mainly magnetic particle bad dispersibility in the elastomer of this phenomenon, Fe
3o
4magnetic particle there occurs that serious reunion causes.At present in order to solve the problem of functional stuffing bad dispersibility in the base, domestic and international investigator reduces the reunion of magnetic particle by carrying out the methods such as the concentration of surperficial organic decoration or reduction magnetic particle to magnetic particle.But although this surperficial organic decoration improves the dispersiveness of magnetic particle, decrease reunion, mechanical property still can reduce along with the increase of magnetic particle doping content, and reduce magnetic particle doping content and will reduce the magnetic property of matrix material.The contradictory problems that the mechanical mechanics property of traditional magnetic elastomeric composite material and magnetic property are difficult to optimize simultaneously is still one of challenging problem of this research field most, is also that magnetic elastomeric composite material applies one of problem of urgent needs solution.
Summary of the invention
The present invention solves existing magnetic elastomer matrix material machinery mechanical property and magnetic property is difficult to the problem simultaneously optimized, provides a kind of high performance magnetic polyurethane elastic composite preparation method.
The present invention is achieved by the following technical solutions: high performance magnetic polyurethane elastic composite preparation method, comprises the steps:
1), stable Graphene@Fe is prepared
3o
4organic magnetic liquid;
A, under condition of ice bath, 2g natural flake graphite and 2g SODIUMNITRATE are joined in the vitriol oil of 46ml, with the speed violent stirring 30min of 600r/min; Further 6g potassium permanganate is joined with the speed of 0.5g/min in the mixing solutions of above-mentioned three kinds of materials, then with the speed violent stirring 60min of 600r/min; The mixed solution of above-mentioned four kinds of materials is transferred in 45 DEG C of water-baths, after stirring 4h with the speed of 400r/min, 80ml deionized water is joined in above-mentioned four kinds of material mixed solutions, then transferred in the oil bath of 95 DEG C; When the temperature of question response solution reaches 95 DEG C, point connects and adds 200ml deionized water lineally, more dropwise adds the hydrogen peroxide that 16ml concentration is 30%, and solution generates golden yellow precipitate thing gradually by brown color; Be the HCl solution of 2mol/L, deionized water and dehydrated alcohol repeatedly centrifuge washing by concentration successively, until the pH value of solution is after neutrality, filters, golden yellow precipitate thing is placed in 60 DEG C of oven dry in baking oven, namely derives from oxygenerating graphite;
B, by 3.58g FeCl
24H
2o and 6.08g FeCl
36H
2o is dissolved in 90mL deionized water, be placed in 50 DEG C of waters bath with thermostatic control, after stirring, low whipping speed is under the vigorous mechanical agitation of 500r/min, slowly drip with the speed of 1 drop/sec the NaOH solution that 90mL concentration is 1.34mol/L, stop after continuing reaction 90min after dropwising, be cooled to room temperature, gained solution is carried out Magneto separate and obtains black precipitate, be i.e. Fe
3o
4magnetic particle, removing supernatant liquid, then use deionized water ultrasonic disperse, Magneto separate, repeated washing 6 ~ 8 times, until the pH of supernatant liquor is in neutral; Then by Fe
3o
4magnetic particle stirs 10min with the speed mechanical of 200r/min, and in 120mL deionized water for ultrasonic dispersion 20min, forms the Fe that stable concentration is 0.025g/mL
3o
4water-base magnetic liquid;
C, the described self-control graphite oxide taking certain mass join in 120ml deionized water, and ultrasonic disperse 1 ~ 3h is placed in 80 DEG C of water-baths after forming graphene oxide uniform dispersion, add wherein certain volume described concentration be the Fe of 0.025g/ml
3o
4water-base magnetic liquid, wherein makes graphite oxide and Fe by oneself
3o
4mass ratio be 0.05 ~ 1.5:1, at N
2under protection, stir after 30min with the speed mechanical of 300r/min, drips the xitix of 1.5 ~ 3 times of described self-control graphite oxide quality or hydrazine hydrate or hydroiodic acid HI as reductive agent, after continuing to react 1h, obtain Graphene@Fe
3o
4composite aqueous magnetic liquid; Magneto separate removing supernatant liquid, then by surplus solution ultrasonic disperse, Magneto separate, repetitive scrubbing 5 times, obtains Graphene@Fe
3o
4composite magnetic particle;
D, by Graphene@Fe described in 0.4g
3o
4composite magnetic particle joins 40ml volatile (boiling point is lower than 90 DEG C), dissolves each other with water and PTMG, and do not occur in the organic solvent of chemical reaction with water and PTMG, stir with the speed of 100r/min, and simultaneously ultrasonic disperse 20min, Magneto separate removes upper liquid subsequently, again with described organic solvent ultrasonic disperse, Magneto separate, repetitive scrubbing 7 times; The Graphene@Fe obtained after finally Magneto separate being purified
3o
4composite magnetic particle ultrasonic disperse is in the described organic solvent of certain volume, and forming concentration is the Graphene@Fe that 0.005 ~ 0.08g/mL is stable
3o
4organic magnetic liquid;
2), magnetic control situ aggregation method prepares Graphene@Fe
3o
4polyurethane elastic composite;
A, by the described Graphene@Fe of certain volume
3o
4organic magnetic liquid mixes with a certain amount of liquid PTMG, the while of stirring also with the speed of 400r/min after ultrasonic 1.5h, be warming up to 60 ~ 90 DEG C, being warming up to 100 ~ 120 DEG C after stirring 30min with the speed of 400r/min, is keep 3 ~ 5h under the condition of 0.08kPa in vacuum tightness;
B, then, be cooled to 25 ~ 40 DEG C, a certain amount of tolylene diisocyanate is joined in reaction system, stir with the speed of 400r/min, after reacting 50min under remaining on 40 ~ 60 DEG C of temperature, temperature is increased to 80 ~ 95 DEG C of reaction 1.5 ~ 3h, obtains Graphene@Fe
3o
4base polyurethane prepolymer for use as;
C, finally a certain amount of chainextender methylene-bis-o-chloroaniline is joined described Graphene@Fe
3o
4in base polyurethane prepolymer for use as, the mass ratio of described PTMG, tolylene diisocyanate and methylene-bis-o-chloroaniline is 40 ~ 220:12 ~ 68:7 ~ 39; With the speed rapid stirring 1min of 600r/min, vacuumizing and defoaming 3 ~ 6min under room temperature and vacuum tightness are the condition of 0.08kPa, pour into and be preheating in the swage tool of 100 ~ 120 DEG C, sulfuration 25 ~ 35min under temperature 100 ~ 120 DEG C, pressure 10MPa and additional 0.1 ~ 2.0T magnetic field condition, be placed in 100 DEG C of baking oven postcure 24h again, obtain Graphene@Fe
3o
4polyurethane elastic composite, described Graphene@Fe
3o
4graphene@Fe in polyurethane elastic composite
3o
4the doping of composite magnetic particle is greater than 0 and is less than or equal to 20wt%.
Prepare Graphene@Fe
3o
4during organic magnetic liquid, adopt the inventive method first to prepare graphite oxide, then prepare Fe
3o
4magnetic particle, and by Fe
3o
4magnetic particle ultrasonic disperse, in deionized water, is adjusted neutral, is formed the Fe that stable concentration is 0.025g/mL
3o
4water-base magnetic liquid, then by described homemade graphite oxide ultrasonic disperse in deionized water, with Fe
3o
4water-base magnetic liquid is at N
2drip reductive agent under protection, obtain Graphene@Fe
3o
4composite aqueous magnetic liquid; Magneto separate is removed after supernatant liquor, by aqueous solution ultrasonic disperse, Magneto separate, repetitive scrubbing repeatedly after, purify and obtain Graphene@Fe
3o
4composite magnetic particle; Finally by Graphene@Fe
3o
4ultrasonic disperse after composite magnetic particle mixes with organic solvent, Magneto separate removes supernatant liquor, then uses organic solvent ultrasonic disperse, Magneto separate, repetitive scrubbing, to remove moisture residual between magnetic particle; Finally by the Graphene@Fe after purification
3o
4composite magnetic particle ultrasonic disperse, in organic solvent, forms the stable Graphene@Fe that concentration is 0.005 ~ 0.08g/mL
3o
4organic magnetic liquid.Magnetic control situ aggregation method prepares Graphene@Fe
3o
4during polyurethane elastic composite, first by Graphene@Fe
3o
4organic magnetic liquid mixes with PTMG, to remove wherein residual moisture and organic solvent, prevents and subsequent reactions thing generation chemical reaction; Then add tolylene diisocyanate, obtain Graphene@Fe
3o
4base polyurethane prepolymer for use as; Finally add chainextender methylene-bis-o-chloroaniline, imported by obtained material in the swage tool of preheating, sulfuration under externally-applied magnetic field condition, oven dry, obtain Graphene@Fe
3o
4polyurethane elastic composite.The present invention 2) Graphene@Fe involved in step
3o
4the consumption of organic magnetic liquid, PTMG, tolylene diisocyanate and methylene-bis-o-chloroaniline is all expressed as " a certain amount of ", and its consumption is determined to realize through following steps: the described concentration of first taking arbitrary volume is the Graphene@Fe that 0.005 ~ 0.08g/mL is stable
3o
4organic magnetic liquid, wherein Graphene@Fe
3o
4the quality of composite magnetic particle can be multiplied by volume computing according to density and draw, then according to Graphene@Fe
3o
4graphene@Fe in polyurethane elastic composite
3o
4the doping of composite magnetic particle is greater than 0 and is less than or equal to 20wt%, can calculate a certain particular graphite alkene@Fe to be prepared
3o
4the Graphene@Fe of composite magnetic particle content
3o
4the total mass of polyurethane elastic composite, then any value in the scope that the mass ratio of PTMG, tolylene diisocyanate and methylene-bis-o-chloroaniline is 40 ~ 220:12 ~ 68:7 ~ 39, the mutual proportionlity of three is determined, and three shared Graphene@Fe altogether
3o
4the massfraction of polyurethane elastic composite is 100% deduct Graphene@Fe
3o
4the content of composite magnetic particle, so just well-determinedly can calculate the consumption of PTMG, tolylene diisocyanate and methylene-bis-o-chloroaniline three.Display is summed up as Graphene@Fe according to lot of experimental data
3o
4when the content of composite magnetic particle is greater than 20wt%, Graphene@Fe
3o
4the mechanical mechanics property of polyurethane elastic composite significantly declines, and can not realize the problem of " mechanical mechanics property and magnetic property are optimized simultaneously " to be solved by this invention, and theoretically, as long as Graphene@is Fe
3o
4containing Graphene@Fe in polyurethane elastic composite
3o
4composite magnetic particle, it has mechanical mechanics property and magnetic property, therefore determines Graphene@Fe
3o
4the content range of composite magnetic particle is for being greater than 0 and being less than or equal to 20wt%.
Described volatile (boiling point is lower than 90 DEG C), dissolve each other with water and PTMG, and be tetrahydrofuran (THF) or dehydrated alcohol or acetone with the organic solvent that chemical reaction do not occur for water and PTMG.During described ultrasonic disperse, ultrasonic power is 80W.Learn through lot of experimental data statistics, ultrasonic disperse under this power, obtained dispersion liquid is dispersed and stability is better.
The present invention compared with prior art has the following advantages: 1), by flake graphite alkene and Fe
3o
4magnetic particle carries out compound and can to deperm the reunion of particle in machine-shaping process, effectively improves the dispersing uniformity of magnetic particle in polymeric matrix; 2), Graphene is as one of best strongthener known up to now, be introduced in magnetic elastomer, can effectively improve elastomeric mechanical mechanics property, and magnetic particle load can prevent Graphene stacking at graphenic surface, effectively improve the reinforced effects of Graphene; 3), adopt situ aggregation method to prepare magnetic nano-particle doping elastic composite, effectively can improve magnetic nano-particle dispersed in elastomer matrix; 4), magnetic control is shaping prepares magnetic elastomeric composite material, and controllable magnetic particle distributes in elastomer matrix, improves mechanical mechanics property and the magnetic property of matrix material further.
Accompanying drawing explanation
The Graphene@Fe of Fig. 1 prepared by the specific embodiment of the invention one-embodiment five
3o
4the machinery of polyurethane elastic composite, mechanics and magnetic property and resistance toheat experimental data; Graphene@Fe prepared by the inventive method can be found out
3o
4polyurethane elastic composite has good mechanics of machinery and magnetic property, and compared with the material prepared with existing method, mechanical mechanics property and magnetic property are improved simultaneously, also have good resistance toheat simultaneously;
Fig. 2 is Graphene@Fe prepared by embodiment one, two, four and five
3o
4the XRD figure of composite magnetic particle; Can find out that from XRD figure 30.5 °, 36.0 °, 43.6 °, 54.0 °, 57.8 ° and 63.0 ° is Fe
3o
4characteristic peak, 24.5 ° is the characteristic peak of Graphene.It can thus be appreciated that containing Fe in this magnetic particle
3o
4and Graphene;
Fig. 3 is stable Graphene@Fe prepared by embodiment three
3o
4the optical photograph of tetrahydrofuran (THF) magnetic liquid; Graphene@Fe is demonstrated by figure
3o
4can be good at being scattered in tetrahydrofuran (THF);
Fig. 4, for one block of magnet being placed on the side of magnetic liquid shown in Fig. 3, presenting good magnetic, and show further satisfactory stability;
Fig. 5 is Graphene@Fe prepared by embodiment one
3o
4the optical photograph of polyurethane elastic composite film;
Fig. 6 is by the Fe of equivalent
3o
4dried powder replaces Graphene@Fe in the present invention
3o
4the optical photograph of the polyurethane elastic composite film that magnetic particle obtains; Can be found out by Fig. 5 Fig. 6 two photo comparison, the matrix material color obtained by method in the present invention is comparatively dark, illustrates that magnetic particle dispersiveness is in the base better;
Fig. 7 is Graphene@Fe prepared by embodiment four
3o
4the stress-strain curve of polyurethane elastic composite under stretching condition; As can be seen from Figure, the material that prepared by the inventive method has good mechanical tensile strength and elasticity;
Fig. 8 is Graphene@Fe prepared by embodiment four
3o
4the magnetic hysteresis loop of polyurethane elastic composite; As can be seen from Figure, the matrix material that prepared by the inventive method has good magnetic property.
Embodiment
embodiment one:
High performance magnetic polyurethane elastic composite preparation method, comprises the steps:
1), stable Graphene@Fe is prepared
3o
4organic magnetic liquid;
A, under condition of ice bath, 2g natural flake graphite and 2g SODIUMNITRATE are joined in the vitriol oil of 46ml, with the speed violent stirring 30min of 600r/min; Further 6g potassium permanganate is joined with the speed of 0.5g/min in the mixing solutions of above-mentioned three kinds of materials, then with the speed violent stirring 60min of 600r/min; The mixed solution of above-mentioned four kinds of materials is transferred in 45 DEG C of water-baths, after stirring 4h with the speed of 400r/min, 80ml deionized water is joined in above-mentioned four kinds of material mixed solutions, then transferred in the oil bath of 95 DEG C; The temperature of question response solution reaches 95 DEG C and is, point connects and adds 200ml deionized water lineally, more dropwise adds the hydrogen peroxide that 16ml concentration is 30%, and solution generates golden yellow precipitate thing gradually by brown color; Be the HCl solution of 2mol/L, deionized water and dehydrated alcohol repeatedly centrifuge washing by concentration successively, until the pH value of solution is after neutrality, filters, golden yellow precipitate thing is placed in 60 DEG C of oven dry in baking oven, namely derives from oxygenerating graphite;
B, by 3.58g FeCl
24H
2o and 6.08g FeCl
36H
2o is dissolved in 90mL deionized water, be placed in 50 DEG C of waters bath with thermostatic control, after stirring, low whipping speed is under the vigorous mechanical agitation of 500r/min, slowly drip with the speed of 1 drop/sec the NaOH solution that 90mL concentration is 1.34mol/L, stop after continuing reaction 90min after dropwising, be cooled to room temperature, gained solution is carried out Magneto separate and obtains black precipitate, be i.e. Fe
3o
4magnetic particle, removing supernatant liquid, then use deionized water ultrasonic disperse, Magneto separate, repeated washing 6 ~ 8 times, until the pH of supernatant liquor is in neutral; Then by Fe
3o
4magnetic particle stirs 10min with the speed mechanical of 200r/min, and in 120mL deionized water for ultrasonic dispersion 20min, forms the Fe that stable concentration is 0.025g/mL
3o
4water-base magnetic liquid;
C, the described self-control graphite oxide taking certain mass join in 120ml deionized water, and ultrasonic disperse 1h is placed in 80 DEG C of water-baths after forming graphene oxide uniform dispersion, add wherein certain volume described concentration be the Fe of 0.025g/ml
3o
4water-base magnetic liquid, wherein makes graphite oxide and Fe by oneself
3o
4mass ratio be 1:1, at N
2under protection, after stirring 30min with the speed mechanical of 300r/min, drip the hydroiodic acid HI of 3 times of described self-control graphite oxide quality as reductive agent, after continuing reaction 1h, obtain Graphene@Fe
3o
4composite aqueous magnetic liquid; Magneto separate removing supernatant liquid, then by surplus solution ultrasonic disperse, Magneto separate, repetitive scrubbing 5 times, obtains Graphene@Fe
3o
4composite magnetic particle;
D, by Graphene@Fe described in 0.4g
3o
4composite magnetic particle joins in 40ml dehydrated alcohol, stirs with the speed of 100r/min, and simultaneously ultrasonic disperse 20min, and Magneto separate removes upper liquid subsequently, then with described organic solvent ultrasonic disperse, Magneto separate, repetitive scrubbing 7 times; The Graphene@Fe obtained after finally Magneto separate being purified
3o
4composite magnetic particle ultrasonic disperse is in the dehydrated alcohol of certain volume, and forming concentration is the Graphene@Fe that 0.005 ~ 0.08g/mL is stable
3o
4composite anhydrous ethanol magnetic liquid;
2), magnetic control situ aggregation method prepares Graphene@Fe
3o
4polyurethane elastic composite;
A, by the described Graphene@Fe of certain volume
3o
4composite anhydrous ethanol magnetic liquid mixes with a certain amount of liquid PTMG, the while of stirring also with the speed of 400r/min after ultrasonic 1.5h, be warming up to 60 DEG C, being warming up to 110 DEG C after stirring 30min with the speed of 400r/min, is keep 5h under the condition of 0.08kPa in vacuum tightness;
B, then, be cooled to 30 DEG C, a certain amount of tolylene diisocyanate joined in reaction system, stirs with the speed of 400r/min, after reacting 50min under remaining on 60 DEG C of temperature, temperature is increased to 95 DEG C of reaction 2.5h, obtains Graphene@Fe
3o
4base polyurethane prepolymer for use as;
C, finally a certain amount of chainextender methylene-bis-o-chloroaniline is joined described Graphene@Fe
3o
4in base polyurethane prepolymer for use as, the mass ratio of described PTMG, tolylene diisocyanate and methylene-bis-o-chloroaniline is 85:30:39; With the speed rapid stirring 1min of 600r/min, vacuumizing and defoaming 3min under room temperature and vacuum tightness are the condition of 0.08kPa, pour into and be preheating in the swage tool of 100 DEG C, sulfuration 30min under temperature 110 DEG C, pressure 10MPa and additional 0.5T magnetic field condition, be placed in 100 DEG C of baking oven postcure 24h again, obtain Graphene@Fe
3o
4polyurethane elastic composite, described Graphene@Fe
3o
4graphene@Fe in polyurethane elastic composite
3o
4the doping of composite magnetic particle is 15wt%.
embodiment two:
high performance magnetic polyurethane elastic composite preparation method, comprises the steps:
1), stable Graphene@Fe is prepared
3o
4organic magnetic liquid;
A, under condition of ice bath, 2g natural flake graphite and 2g SODIUMNITRATE are joined in the vitriol oil of 46ml, with the speed violent stirring 30min of 600r/min; Further 6g potassium permanganate is joined with the speed of 0.5g/min in the mixing solutions of above-mentioned three kinds of materials, then with the speed violent stirring 60min of 600r/min; The mixed solution of above-mentioned four kinds of materials is transferred in 45 DEG C of water-baths, after stirring 4h with the speed of 400r/min, 80ml deionized water is joined in above-mentioned four kinds of material mixed solutions, then transferred in the oil bath of 95 DEG C; The temperature of question response solution reaches 95 DEG C and is, point connects and adds 200ml deionized water lineally, more dropwise adds the hydrogen peroxide that 16ml concentration is 30%, and solution generates golden yellow precipitate thing gradually by brown color; Be the HCl solution of 2mol/L, deionized water and dehydrated alcohol repeatedly centrifuge washing by concentration successively, until the pH value of solution is after neutrality, filters, golden yellow precipitate thing is placed in 60 DEG C of oven dry in baking oven, namely derives from oxygenerating graphite;
B, by 3.58g FeCl
24H
2o and 6.08g FeCl
36H
2o is dissolved in 90mL deionized water, be placed in 50 DEG C of waters bath with thermostatic control, after stirring, low whipping speed is under the vigorous mechanical agitation of 500r/min, slowly drip with the speed of 1 drop/sec the NaOH solution that 90mL concentration is 1.34mol/L, stop after continuing reaction 90min after dropwising, be cooled to room temperature, gained solution is carried out Magneto separate and obtains black precipitate, be i.e. Fe
3o
4magnetic particle, removing supernatant liquid, then use deionized water ultrasonic disperse, Magneto separate, repeated washing 6 ~ 8 times, until the pH of supernatant liquor is in neutral; Then by Fe
3o
4magnetic particle stirs 10min with the speed mechanical of 200r/min, and in 120mL deionized water for ultrasonic dispersion 20min, forms the Fe that stable concentration is 0.025g/mL
3o
4water-base magnetic liquid;
C, the described self-control graphite oxide taking certain mass join in 120ml deionized water, and ultrasonic disperse 3h is placed in 80 DEG C of water-baths after forming graphene oxide uniform dispersion, add wherein certain volume described concentration be the Fe of 0.025g/ml
3o
4water-base magnetic liquid, wherein makes graphite oxide and Fe by oneself
3o
4mass ratio be 0.05:1, at N
2under protection, after stirring 30min with the speed mechanical of 300r/min, drip the xitix of 1.5 times of described self-control graphite oxide quality as reductive agent, after continuing reaction 1h, obtain Graphene@Fe
3o
4composite aqueous magnetic liquid; Magneto separate removing supernatant liquid, then by surplus solution ultrasonic disperse, Magneto separate, repetitive scrubbing 5 times, obtains Graphene@Fe
3o
4composite magnetic particle;
D, by Graphene@Fe described in 0.4g
3o
4composite magnetic particle joins in 40ml acetone, stirs with the speed of 100r/min, and simultaneously ultrasonic disperse 20min, and Magneto separate removes upper liquid subsequently, then with described organic solvent ultrasonic disperse, Magneto separate, repetitive scrubbing 7 times; The Graphene@Fe obtained after finally Magneto separate being purified
3o
4composite magnetic particle ultrasonic disperse is in the acetone of certain volume, and forming concentration is the Graphene@Fe that 0.005 ~ 0.08g/mL is stable
3o
4compound acetone magnetic liquid;
2), magnetic control situ aggregation method prepares Graphene@Fe
3o
4polyurethane elastic composite;
A, by the described Graphene@Fe of certain volume
3o
4compound acetone magnetic liquid mixes with a certain amount of liquid PTMG, the while of stirring also with the speed of 400r/min after ultrasonic 1.5h, be warming up to 90 DEG C, being warming up to 120 DEG C after stirring 30min with the speed of 400r/min, is keep 3h under the condition of 0.08kPa in vacuum tightness;
B, then, be cooled to 25 DEG C, a certain amount of tolylene diisocyanate joined in reaction system, stirs with the speed of 400r/min, after reacting 50min under remaining on 40 DEG C of temperature, temperature is increased to 90 DEG C of reaction 1.5h, obtains Graphene@Fe
3o
4base polyurethane prepolymer for use as;
C, finally a certain amount of chainextender methylene-bis-o-chloroaniline is joined described Graphene@Fe
3o
4in base polyurethane prepolymer for use as, the mass ratio of described PTMG, tolylene diisocyanate and methylene-bis-o-chloroaniline is 175:68:22; With the speed rapid stirring 1min of 600r/min, vacuumizing and defoaming 4min under room temperature and vacuum tightness are the condition of 0.08kPa, pour into and be preheating in the swage tool of 100 DEG C, sulfuration 25min under temperature 120 DEG C, pressure 10MPa and additional 0.1T magnetic field condition, be placed in 100 DEG C of baking oven postcure 24h again, obtain Graphene@Fe
3o
4polyurethane elastic composite, described Graphene@Fe
3o
4graphene@Fe in polyurethane elastic composite
3o
4the doping of composite magnetic particle is 10wt%.
embodiment three:
high performance magnetic polyurethane elastic composite preparation method, comprises the steps:
1), stable Graphene@Fe is prepared
3o
4organic magnetic liquid;
A, under condition of ice bath, 2g natural flake graphite and 2g SODIUMNITRATE are joined in the vitriol oil of 46ml, with the speed violent stirring 30min of 600r/min; Further 6g potassium permanganate is joined with the speed of 0.5g/min in the mixing solutions of above-mentioned three kinds of materials, then with the speed violent stirring 60min of 600r/min; The mixed solution of above-mentioned four kinds of materials is transferred in 45 DEG C of water-baths, after stirring 4h with the speed of 400r/min, 80ml deionized water is joined in above-mentioned four kinds of material mixed solutions, then transferred in the oil bath of 95 DEG C; The temperature of question response solution reaches 95 DEG C and is, point connects and adds 200ml deionized water lineally, more dropwise adds the hydrogen peroxide that 16ml concentration is 30%, and solution generates golden yellow precipitate thing gradually by brown color; Be the HCl solution of 2mol/L, deionized water and dehydrated alcohol repeatedly centrifuge washing by concentration successively, until the pH value of solution is after neutrality, filters, golden yellow precipitate thing is placed in 60 DEG C of oven dry in baking oven, namely derives from oxygenerating graphite;
B, by 3.58g FeCl
24H
2o and 6.08g FeCl
36H
2o is dissolved in 90mL deionized water, be placed in 50 DEG C of waters bath with thermostatic control, after stirring, low whipping speed is under the vigorous mechanical agitation of 500r/min, slowly drip with the speed of 1 drop/sec the NaOH solution that 90mL concentration is 1.34mol/L, stop after continuing reaction 90min after dropwising, be cooled to room temperature, gained solution is carried out Magneto separate and obtains black precipitate, be i.e. Fe
3o
4magnetic particle, removing supernatant liquid, then use deionized water ultrasonic disperse, Magneto separate, repeated washing 6 ~ 8 times, until the pH of supernatant liquor is in neutral; Then by Fe
3o
4magnetic particle stirs 10min with the speed mechanical of 200r/min, and in 120mL deionized water for ultrasonic dispersion 20min, forms the Fe that stable concentration is 0.025g/mL
3o
4water-base magnetic liquid;
C, the described self-control graphite oxide taking certain mass join in 120ml deionized water, and ultrasonic disperse 2h is placed in 80 DEG C of water-baths after forming graphene oxide uniform dispersion, add wherein certain volume described concentration be the Fe of 0.025g/ml
3o
4water-base magnetic liquid, wherein makes graphite oxide and Fe by oneself
3o
4mass ratio be 1.5:1, at N
2under protection, after stirring 30min with the speed mechanical of 300r/min, drip the hydrazine hydrate of 2 times of described self-control graphite oxide quality as reductive agent, after continuing reaction 1h, obtain Graphene@Fe
3o
4composite aqueous magnetic liquid; Magneto separate removing supernatant liquid, then by surplus solution ultrasonic disperse, Magneto separate, repetitive scrubbing 5 times, obtains Graphene@Fe
3o
4composite magnetic particle;
D, by Graphene@Fe described in 0.4g
3o
4composite magnetic particle joins in 40ml tetrahydrofuran (THF), stirs with the speed of 100r/min, and simultaneously ultrasonic disperse 20min, and Magneto separate removes upper liquid subsequently, then with described organic solvent ultrasonic disperse, Magneto separate, repetitive scrubbing 7 times; The Graphene@Fe obtained after finally Magneto separate being purified
3o
4composite magnetic particle ultrasonic disperse is in the tetrahydrofuran (THF) of certain volume, and forming concentration is the Graphene@Fe that 0.005 ~ 0.08g/mL is stable
3o
4compound tetrahydrofuran (THF) magnetic liquid;
2), magnetic control situ aggregation method prepares Graphene@Fe
3o
4polyurethane elastic composite;
A, by the described Graphene@Fe of certain volume
3o
4compound tetrahydrofuran (THF) magnetic liquid mixes with a certain amount of liquid PTMG, the while of stirring also with the speed of 400r/min after ultrasonic 1.5h, be warming up to 75 DEG C, being warming up to 100 DEG C after stirring 30min with the speed of 400r/min, is keep 4h under the condition of 0.08kPa in vacuum tightness;
B, then, be cooled to 40 DEG C, a certain amount of tolylene diisocyanate joined in reaction system, stirs with the speed of 400r/min, after reacting 50min under remaining on 50 DEG C of temperature, temperature is increased to 80 DEG C of reaction 3h, obtains Graphene@Fe
3o
4base polyurethane prepolymer for use as;
C, finally a certain amount of chainextender methylene-bis-o-chloroaniline is joined described Graphene@Fe
3o
4in base polyurethane prepolymer for use as, the mass ratio of described PTMG, tolylene diisocyanate and methylene-bis-o-chloroaniline is 40:12:7; With the speed rapid stirring 1min of 600r/min, vacuumizing and defoaming 6min under room temperature and vacuum tightness are the condition of 0.08kPa, pour into and be preheating in the swage tool of 120 DEG C, sulfuration 35min under temperature 120 DEG C, pressure 10MPa and additional 2.0T magnetic field condition, be placed in 100 DEG C of baking oven postcure 24h again, obtain Graphene@Fe
3o
4polyurethane elastic composite, described Graphene@Fe
3o
4graphene@Fe in polyurethane elastic composite
3o
4the doping of composite magnetic particle is 20wt%.
embodiment four:
high performance magnetic polyurethane elastic composite preparation method, comprises the steps:
1), stable Graphene@Fe is prepared
3o
4organic magnetic liquid;
A, under condition of ice bath, 2g natural flake graphite and 2g SODIUMNITRATE are joined in the vitriol oil of 46ml, with the speed violent stirring 30min of 600r/min; Further 6g potassium permanganate is joined with the speed of 0.5g/min in the mixing solutions of above-mentioned three kinds of materials, then with the speed violent stirring 60min of 600r/min; The mixed solution of above-mentioned four kinds of materials is transferred in 45 DEG C of water-baths, after stirring 4h with the speed of 400r/min, 80ml deionized water is joined in above-mentioned four kinds of material mixed solutions, then transferred in the oil bath of 95 DEG C; The temperature of question response solution reaches 95 DEG C and is, point connects and adds 200ml deionized water lineally, more dropwise adds the hydrogen peroxide that 16ml concentration is 30%, and solution generates golden yellow precipitate thing gradually by brown color; Be the HCl solution of 2mol/L, deionized water and dehydrated alcohol repeatedly centrifuge washing by concentration successively, until the pH value of solution is after neutrality, filters, golden yellow precipitate thing is placed in 60 DEG C of oven dry in baking oven, namely derives from oxygenerating graphite;
B, by 3.58g FeCl
24H
2o and 6.08g FeCl
36H
2o is dissolved in 90mL deionized water, be placed in 50 DEG C of waters bath with thermostatic control, after stirring, low whipping speed is under the vigorous mechanical agitation of 500r/min, slowly drip with the speed of 1 drop/sec the NaOH solution that 90mL concentration is 1.34mol/L, stop after continuing reaction 90min after dropwising, be cooled to room temperature, gained solution is carried out Magneto separate and obtains black precipitate, be i.e. Fe
3o
4magnetic particle, removing supernatant liquid, then use deionized water ultrasonic disperse, Magneto separate, repeated washing 6 ~ 8 times, until the pH of supernatant liquor is in neutral; Then by Fe
3o
4magnetic particle stirs 10min with the speed mechanical of 200r/min, and in 120mL deionized water for ultrasonic dispersion 20min, forms the Fe that stable concentration is 0.025g/mL
3o
4water-base magnetic liquid;
C, the described self-control graphite oxide taking certain mass join in 120ml deionized water, and ultrasonic disperse 1h is placed in 80 DEG C of water-baths after forming graphene oxide uniform dispersion, add wherein certain volume described concentration be the Fe of 0.025g/ml
3o
4water-base magnetic liquid, wherein makes graphite oxide and Fe by oneself
3o
4mass ratio be 0.5:1, at N
2under protection, after stirring 30min with the speed mechanical of 300r/min, drip the xitix of 2.5 times of described self-control graphite oxide quality as reductive agent, after continuing reaction 1h, obtain Graphene@Fe
3o
4composite aqueous magnetic liquid; Magneto separate removing supernatant liquid, then by surplus solution ultrasonic disperse, Magneto separate, repetitive scrubbing 5 times, obtains Graphene@Fe
3o
4composite magnetic particle;
D, by Graphene@Fe described in 0.4g
3o
4composite magnetic particle joins in 40ml tetrahydrofuran (THF), stirs with the speed of 100r/min, and simultaneously ultrasonic disperse 20min, and Magneto separate removes upper liquid subsequently, then with described organic solvent ultrasonic disperse, Magneto separate, repetitive scrubbing 7 times; The Graphene@Fe obtained after finally Magneto separate being purified
3o
4composite magnetic particle ultrasonic disperse is in the tetrahydrofuran (THF) of certain volume, and forming concentration is the Graphene@Fe that 0.005 ~ 0.08g/mL is stable
3o
4compound tetrahydrofuran (THF) magnetic liquid;
2), magnetic control situ aggregation method prepares Graphene@Fe
3o
4polyurethane elastic composite;
A, by the described Graphene@Fe of certain volume
3o
4compound tetrahydrofuran (THF) magnetic liquid mixes with a certain amount of liquid PTMG, the while of stirring also with the speed of 400r/min after ultrasonic 1.5h, be warming up to 68 DEG C, being warming up to 105 DEG C after stirring 30min with the speed of 400r/min, is keep 3h under the condition of 0.08kPa in vacuum tightness;
B, then, be cooled to 35 DEG C, a certain amount of tolylene diisocyanate joined in reaction system, stirs with the speed of 400r/min, after reacting 50min under remaining on 60 DEG C of temperature, temperature is increased to 85 DEG C of reaction 2.5h, obtains Graphene@Fe
3o
4base polyurethane prepolymer for use as;
C, finally a certain amount of chainextender methylene-bis-o-chloroaniline is joined described Graphene@Fe
3o
4in base polyurethane prepolymer for use as, the mass ratio of described PTMG, tolylene diisocyanate and methylene-bis-o-chloroaniline is 220:40:15; With the speed rapid stirring 1min of 600r/min, vacuumizing and defoaming 5min under room temperature and vacuum tightness are the condition of 0.08kPa, pour into and be preheating in the swage tool of 100 DEG C, sulfuration 25min under temperature 100 DEG C, pressure 10MPa and additional 1T magnetic field condition, be placed in 100 DEG C of baking oven postcure 24h again, obtain Graphene@Fe
3o
4polyurethane elastic composite, described Graphene@Fe
3o
4graphene@Fe in polyurethane elastic composite
3o
4the doping of composite magnetic particle is 0.2wt%.
embodiment five:
high performance magnetic polyurethane elastic composite preparation method, comprises the steps:
1), stable Graphene@Fe is prepared
3o
4organic magnetic liquid;
A, under condition of ice bath, 2g natural flake graphite and 2g SODIUMNITRATE are joined in the vitriol oil of 46ml, with the speed violent stirring 30min of 600r/min; Further 6g potassium permanganate is joined with the speed of 0.5g/min in the mixing solutions of above-mentioned three kinds of materials, then with the speed violent stirring 60min of 600r/min; The mixed solution of above-mentioned four kinds of materials is transferred in 45 DEG C of water-baths, after stirring 4h with the speed of 400r/min, 80ml deionized water is joined in above-mentioned four kinds of material mixed solutions, then transferred in the oil bath of 95 DEG C; The temperature of question response solution reaches 95 DEG C and is, point connects and adds 200ml deionized water lineally, more dropwise adds the hydrogen peroxide that 16ml concentration is 30%, and solution generates golden yellow precipitate thing gradually by brown color; Be the HCl solution of 2mol/L, deionized water and dehydrated alcohol repeatedly centrifuge washing by concentration successively, until the pH value of solution is after neutrality, filters, golden yellow precipitate thing is placed in 60 DEG C of oven dry in baking oven, namely derives from oxygenerating graphite;
B, by 3.58g FeCl
24H
2o and 6.08g FeCl
36H
2o is dissolved in 90mL deionized water, be placed in 50 DEG C of waters bath with thermostatic control, after stirring, low whipping speed is under the vigorous mechanical agitation of 500r/min, slowly drip with the speed of 1 drop/sec the NaOH solution that 90mL concentration is 1.34mol/L, stop after continuing reaction 90min after dropwising, be cooled to room temperature, gained solution is carried out Magneto separate and obtains black precipitate, be i.e. Fe
3o
4magnetic particle, removing supernatant liquid, then use deionized water ultrasonic disperse, Magneto separate, repeated washing 6 ~ 8 times, until the pH of supernatant liquor is in neutral; Then by Fe
3o
4magnetic particle stirs 10min with the speed mechanical of 200r/min, and in 120mL deionized water for ultrasonic dispersion 20min, forms the Fe that stable concentration is 0.025g/mL
3o
4water-base magnetic liquid;
C, the described self-control graphite oxide taking certain mass join in 120ml deionized water, and ultrasonic disperse 3h is placed in 80 DEG C of water-baths after forming graphene oxide uniform dispersion, add wherein certain volume described concentration be the Fe of 0.025g/ml
3o
4water-base magnetic liquid, wherein makes graphite oxide and Fe by oneself
3o
4mass ratio be 1.2:1, at N
2under protection, after stirring 30min with the speed mechanical of 300r/min, drip the hydrazine hydrate of 1.75 times of described self-control graphite oxide quality as reductive agent, after continuing reaction 1h, obtain Graphene@Fe
3o
4composite aqueous magnetic liquid; Magneto separate removing supernatant liquid, then by surplus solution ultrasonic disperse, Magneto separate, repetitive scrubbing 5 times, obtains Graphene@Fe
3o
4composite magnetic particle;
D, by Graphene@Fe described in 0.4g
3o
4composite magnetic particle joins in 40ml dehydrated alcohol, stirs with the speed of 100r/min, and simultaneously ultrasonic disperse 20min, and Magneto separate removes upper liquid subsequently, then with described organic solvent ultrasonic disperse, Magneto separate, repetitive scrubbing 7 times; The Graphene@Fe obtained after finally Magneto separate being purified
3o
4composite magnetic particle ultrasonic disperse is in the dehydrated alcohol of certain volume, and forming concentration is the Graphene@Fe that 0.005 ~ 0.08g/mL is stable
3o
4composite anhydrous ethanol magnetic liquid;
2), magnetic control situ aggregation method prepares Graphene@Fe
3o
4polyurethane elastic composite;
A, by the described Graphene@Fe of certain volume
3o
4composite anhydrous ethanol magnetic liquid mixes with a certain amount of liquid PTMG, the while of stirring also with the speed of 400r/min after ultrasonic 1.5h, be warming up to 82 DEG C, being warming up to 115 DEG C after stirring 30min with the speed of 400r/min, is keep 4.5h under the condition of 0.08kPa in vacuum tightness;
B, then, be cooled to 32 DEG C, a certain amount of tolylene diisocyanate joined in reaction system, stirs with the speed of 400r/min, after reacting 50min under remaining on 55 DEG C of temperature, temperature is increased to 92 DEG C of reaction 2h, obtains Graphene@Fe
3o
4base polyurethane prepolymer for use as;
C, finally a certain amount of chainextender methylene-bis-o-chloroaniline is joined described Graphene@Fe
3o
4in base polyurethane prepolymer for use as, the mass ratio of described PTMG, tolylene diisocyanate and methylene-bis-o-chloroaniline is 130:52:30; With the speed rapid stirring 1min of 600r/min, vacuumizing and defoaming 4.5min under room temperature and vacuum tightness are the condition of 0.08kPa, pour into and be preheating in the swage tool of 110 DEG C, sulfuration 28min under temperature 120 DEG C, pressure 10MPa and additional 1.5T magnetic field condition, be placed in 100 DEG C of baking oven postcure 24h again, obtain Graphene@Fe
3o
4polyurethane elastic composite, described Graphene@Fe
3o
4graphene@Fe in polyurethane elastic composite
3o
4the doping of composite magnetic particle is 5wt%.
Claims (3)
1. a high performance magnetic polyurethane elastic composite preparation method, is characterized in that comprising the following steps:
1), stable Graphene@Fe is prepared
3o
4organic magnetic liquid;
A, under condition of ice bath, 2g natural flake graphite and 2g SODIUMNITRATE are joined in the vitriol oil of 46ml, with the speed violent stirring 30min of 600r/min; Further 6g potassium permanganate is joined with the speed of 0.5g/min in the mixing solutions of above-mentioned three kinds of materials, then with the speed violent stirring 60min of 600r/min; The mixed solution of above-mentioned four kinds of materials is transferred in 45 DEG C of water-baths, after stirring 4h with the speed of 400r/min, 80ml deionized water is joined in above-mentioned four kinds of material mixed solutions, then transferred in the oil bath of 95 DEG C; The temperature of question response solution reaches 95 DEG C and is, point connects and adds 200ml deionized water lineally, more dropwise adds the hydrogen peroxide that 16ml concentration is 30%, and solution generates golden yellow precipitate thing gradually by brown color; Be the HCl solution of 2mol/L, deionized water and dehydrated alcohol repeatedly centrifuge washing by concentration successively, until the pH value of solution is after neutrality, filters, golden yellow precipitate thing is placed in 60 DEG C of oven dry in baking oven, namely derives from oxygenerating graphite;
B, by 3.58g FeCl
24H
2o and 6.08g FeCl
36H
2o is dissolved in 90mL deionized water, be placed in 50 DEG C of waters bath with thermostatic control, after stirring, low whipping speed is under the vigorous mechanical agitation of 500r/min, slowly drip with the speed of 1 drop/sec the NaOH solution that 90mL concentration is 1.34mol/L, stop after continuing reaction 90min after dropwising, be cooled to room temperature, gained solution is carried out Magneto separate and obtains black precipitate, be i.e. Fe
3o
4magnetic particle, removing supernatant liquid, then use deionized water ultrasonic disperse, Magneto separate, repeated washing 6 ~ 8 times, until the pH of supernatant liquor is in neutral; Then by Fe
3o
4magnetic particle stirs 10min with the speed mechanical of 200r/min, and in 120mL deionized water for ultrasonic dispersion 20min, forms the Fe that stable concentration is 0.025g/mL
3o
4water-base magnetic liquid;
C, the described self-control graphite oxide taking certain mass join in 120ml deionized water, and ultrasonic disperse 1 ~ 3h is placed in 80 DEG C of water-baths after forming graphene oxide uniform dispersion, add wherein certain volume described concentration be the Fe of 0.025g/ml
3o
4water-base magnetic liquid, wherein makes graphite oxide and Fe by oneself
3o
4mass ratio be 0.05 ~ 1.5:1, at N
2under protection, stir after 30min with the speed mechanical of 300r/min, drips the xitix of 1.5 ~ 3 times of described self-control graphite oxide quality or hydrazine hydrate or hydroiodic acid HI as reductive agent, after continuing to react 1h, obtain Graphene@Fe
3o
4composite aqueous magnetic liquid; Magneto separate removing supernatant liquid, then by surplus solution ultrasonic disperse, Magneto separate, repetitive scrubbing 5 times, obtains Graphene@Fe
3o
4composite magnetic particle;
D, by Graphene@Fe described in 0.4g
3o
4composite magnetic particle join 40ml volatile, dissolve each other with water and PTMG, and do not occur in the organic solvent of chemical reaction with water and PTMG, stir with the speed of 100r/min, and simultaneously ultrasonic disperse 20min, Magneto separate removes upper liquid subsequently, again with described organic solvent ultrasonic disperse, Magneto separate, repetitive scrubbing 7 times; The Graphene@Fe obtained after finally Magneto separate being purified
3o
4composite magnetic particle ultrasonic disperse is in the described organic solvent of certain volume, and forming concentration is the Graphene@Fe that 0.005 ~ 0.08g/mL is stable
3o
4organic magnetic liquid;
2), magnetic control situ aggregation method prepares Graphene@Fe
3o
4polyurethane elastic composite;
A, by the described Graphene@Fe of certain volume
3o
4organic magnetic liquid mixes with a certain amount of liquid PTMG, the while of stirring also with the speed of 400r/min after ultrasonic 1.5h, be warming up to 60 ~ 90 DEG C, being warming up to 100 ~ 120 DEG C after stirring 30min with the speed of 400r/min, is keep 3 ~ 5h under the condition of 0.08kPa in vacuum tightness;
B, then, be cooled to 25 ~ 40 DEG C, a certain amount of tolylene diisocyanate is joined in reaction system, stir with the speed of 400r/min, after reacting 50min under remaining on 40 ~ 60 DEG C of temperature, temperature is increased to 80 ~ 95 DEG C of reaction 1.5 ~ 3h, obtains Graphene@Fe
3o
4base polyurethane prepolymer for use as;
C, finally a certain amount of chainextender methylene-bis-o-chloroaniline is joined described Graphene@Fe
3o
4in base polyurethane prepolymer for use as, the mass ratio of described PTMG, tolylene diisocyanate and methylene-bis-o-chloroaniline is 40 ~ 220:12 ~ 68:7 ~ 39; With the speed rapid stirring 1min of 600r/min, vacuumizing and defoaming 3 ~ 6min under room temperature and vacuum tightness are the condition of 0.08kPa, pour into and be preheating in the swage tool of 100 ~ 120 DEG C, sulfuration 25 ~ 35min under temperature 100 ~ 120 DEG C, pressure 10MPa and additional 0.1 ~ 2.0T magnetic field condition, be placed in 100 DEG C of baking oven postcure 24h again, obtain Graphene@Fe
3o
4polyurethane elastic composite, described Graphene@Fe
3o
4graphene@Fe in polyurethane elastic composite
3o
4the doping of composite magnetic particle is greater than 0 and is less than or equal to 20wt%.
2. high performance magnetic polyurethane elastic composite preparation method according to claim 1, it is characterized in that: described volatile, dissolve each other with water and PTMG, and be tetrahydrofuran (THF) or dehydrated alcohol or acetone with the organic solvent that chemical reaction do not occur for water and PTMG.
3. high performance magnetic polyurethane elastic composite preparation method according to claim 2, is characterized in that: during described ultrasonic disperse, and ultrasonic power is 80W.
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| CN104861146A (en) * | 2015-05-08 | 2015-08-26 | 中北大学 | Preparation method for high-performance magnetic Fe3O4/polyurethane elastomer composite material |
| CN104962185A (en) * | 2015-06-03 | 2015-10-07 | 陕西科技大学 | Graphene-loaded nanometer Fe3O4/aqueous polyurethane composite magnetic conductive wave absorbing coating material and preparation method thereof |
| CN105131563A (en) * | 2015-09-30 | 2015-12-09 | 中北大学 | Preparation method for Fe3O4/graphene oxide/waterborne polyurethane composite |
| CN105860007A (en) * | 2016-04-26 | 2016-08-17 | 浙江和也健康科技有限公司 | Modified TPU (thermoplastic polyurethane) material and manufacturing method thereof |
| CN106566226A (en) * | 2016-10-21 | 2017-04-19 | 中国科学院宁波材料技术与工程研究所 | Thermoplastic polyurethane/graphene foam material and preparation method and application thereof |
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| CN108285517A (en) * | 2018-02-12 | 2018-07-17 | 化州市联合民生轮业有限公司 | A kind of graphene/ester ether copoly type heat-curable urethane composite material and preparation method |
| CN109776749A (en) * | 2019-01-14 | 2019-05-21 | 长春工业大学 | A kind of lignin-base flexible electromagnetic shielding material |
| CN109943907A (en) * | 2019-01-30 | 2019-06-28 | 华峰重庆氨纶有限公司 | A kind of preparation method of magnetic polyurethane elastomer |
| CN110028777A (en) * | 2019-04-24 | 2019-07-19 | 重庆邮电大学 | A kind of intelligent magneto-rheological elastic composite and preparation method thereof with from perceptional function |
| CN111484724A (en) * | 2020-02-11 | 2020-08-04 | 常德艾利特新材料科技有限公司 | Polyurethane composite material and preparation method thereof |
| CN113198052A (en) * | 2021-04-14 | 2021-08-03 | 成都理工大学 | Ferroferric oxide/polytetrahydrofuran composite bone repair material and application thereof |
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