CN103772722B - There is the Graphene-Fe of electro-magnetic screen function 3o 4the preparation method of/aqueous polyurethane nano matrix material - Google Patents
There is the Graphene-Fe of electro-magnetic screen function 3o 4the preparation method of/aqueous polyurethane nano matrix material Download PDFInfo
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- CN103772722B CN103772722B CN201410006051.5A CN201410006051A CN103772722B CN 103772722 B CN103772722 B CN 103772722B CN 201410006051 A CN201410006051 A CN 201410006051A CN 103772722 B CN103772722 B CN 103772722B
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Abstract
The present invention relates to a kind of Graphene-Fe with electro-magnetic screen function
3o
4the preparation method of/aqueous polyurethane nano matrix material, belongs to field of composite material preparation, refers in particular to and first utilizes hydrothermal method to prepare Graphene-Fe
3o
4, then by Graphene-Fe
3o
4disperse in aqueous, utilize situ aggregation method, add Graphene-Fe in the emulsion reaction process that adds water preparing aqueous polyurethane
3o
4solution, deionized water and quadrol emulsification, prepare Graphene-Fe
3o
4/ aqueous polyurethane nano matrix material.The nanoparticle of gained of the present invention be uniformly dispersed in emulsion and there is satisfactory stability, nano composite material has good electromagnetic shielding effect, can be applicable to the electromagnetic shielding field of phone housing, clothes, industrial engineering.
Description
Technical field
The present invention relates to field of composite material preparation, particularly relate to a kind of Graphene-Fe with electro-magnetic screen function
3o
4the preparation method of/aqueous polyurethane nano matrix material.
Background technology
The development of contemporary electronic information technology and the universal of electronic product, while meeting people's living needs, make hertzian wave extensively exist in people's daily life.The thorny problems such as electromagenetic wave radiation causes electromagnetic pollution, electromagnetic interference, divulge a secret, hamper the development of electronic information industry high speed.The scheme effectively addressed this problem, be develop to absorb the electromagnetic material of special frequency channel, therefore, electromagnetic shielding material is with a wide range of applications in civil field.
Graphene is the thinnest in the world is at present the hardest nano material also, it is almost completely transparent, under normal temperature, its electronic mobility is more than 15000cm2/vs, again than CNT (carbon nano-tube) or silicon wafer height, and resistivity only about 10-6 Ω cm, than copper or silver lower, be the material that at present in the world resistivity is minimum.Compared with traditional material, Graphene can break through original limitation, becomes novel effective wave absorbing agent, meets the requirement of absorbing material to " thin, light, wide, strong ".Aqueous polyurethane has the performance of solvent borne polyurethane, overcomes again the pollution of solvent evaporates to environment, in sizing agent, car paint, building coating, damping material, protective system etc., has great application prospect.
Therefore, hydrothermal method is first utilized to prepare Graphene-Fe
3o
4, then by Graphene-Fe
3o
4disperse in aqueous, utilize situ aggregation method, add Graphene-Fe in the emulsion reaction process that adds water preparing aqueous polyurethane
3o
4solution, deionized water and quadrol emulsification, prepare Graphene-Fe
3o
4/ aqueous polyurethane nano matrix material.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of Graphene-Fe with electro-magnetic screen function is provided
3o
4the preparation method of/aqueous polyurethane nano matrix material.
There is the Graphene-Fe of electro-magnetic screen function
3o
4the preparation method of/aqueous polyurethane nano matrix material, comprises the steps:
1) graphite of 1-10 mass parts is joined dispersed with stirring in the vitriol oil of 5-100 mass parts even, be cooled to less than 0 DEG C; Slowly add the potassium permanganate of 5-100 mass parts, then be warming up to 25-40 DEG C and keep 2-6h; Slowly add deionized water, then to add 5-100 mass parts mass percentage concentration be that the hydrogen peroxide solution of 30% is until become glassy yellow; Use 1M hydrochloric acid soln washing 2-3 time, obtain graphene oxide aqueous dispersions for subsequent use;
2) by graphene oxide aqueous dispersions ultrasonic 10-50min in ultrasonator, after Graphene aqueous dispersions to be oxidized is uniformly dispersed, the FeCl of 1-10 mass parts is added
3, magnetic agitation, is placed with afterwards in teflon-lined reactor, is heated to 150-230 DEG C, reaction 2-10h, and cooling, is 7 with deionized water wash to pH value, obtains Graphene-Fe
3o
4the aqueous solution;
3) by the polytetrahydrofuran diol vacuum hydro-extraction of 10-100 mass parts, the '-diphenylmethane diisocyanate adding 4-50 mass parts mixes, performed polymer is obtained by reacting at 80-100 DEG C, the dihydroxypropionic acid adding 2-20 mass parts introduces hydrophilic group, reaction 2h is cooled to 50 DEG C, the triethylamine adding 1-10 mass parts continues to stir, and adds the Graphene-Fe of 0.1-1 mass parts
3o
4the deionized water of the aqueous solution, 30-300 mass parts and the quadrol emulsification of 0.1-1 mass parts, obtain Graphene-Fe
3o
4/ aqueous polyurethane emulsion, dry in Teflon mould at 70-100 DEG C, obtain Graphene-Fe
3o
4/ aqueous polyurethane composite membrane.
Step 3) described in Graphene-Fe
3o
4the aqueous solution in add silane coupling agent, polyvinyl alcohol or the polyvinylpyrrolidone that mass percentage concentration is 0.1%-2%.
The nanoparticle of gained of the present invention be uniformly dispersed in emulsion and there is satisfactory stability, nano composite material has good electromagnetic shielding effect, can be applicable to the electromagnetic shielding field of phone housing, clothes, industrial engineering.
accompanying drawing illustrates:
Fig. 1 is the stereoscan photograph (SEM) of graphene oxide prepared by embodiment 2;
Fig. 2 is embodiment 2 Graphene-Fe3O4 and aqueous polyurethane in-situ composite digital photograph figure;
Fig. 3 is embodiment 2 Graphene-Fe3O4 and aqueous polyurethane in-situ composite scanning electron microscope (SEM) figure.
embodiment:
Content of the present invention is further illustrated below in conjunction with example:
Embodiment 1:
1) graphite of 1 mass parts is joined dispersed with stirring in the vitriol oil of 5 mass parts even, be cooled to less than 0 DEG C; Slowly add the potassium permanganate of 5 mass parts, then be warming up to 40 DEG C and keep 6h; Slowly add deionized water, then the mass percentage concentration adding 5 mass parts is that 30% hydrogen peroxide solution is until become glassy yellow; Use 1M hydrochloric acid soln to wash 2 times, obtain graphene oxide aqueous dispersions for subsequent use;
2) by graphene oxide aqueous dispersions ultrasonic 10min in ultrasonator, after Graphene aqueous dispersions to be oxidized is uniformly dispersed, 1 mass parts FeCl is added
3, magnetic agitation, is placed with in teflon-lined reactor afterwards, is heated to 230 DEG C, reaction 2h, and cooling, is 7 with deionized water wash to pH value, obtains Graphene-Fe
3o
4the aqueous solution, adds the silane coupling agent of 0.1%;
3) by the polytetrahydrofuran diol vacuum hydro-extraction of 10 mass parts, the '-diphenylmethane diisocyanate adding 4 mass parts mixes, performed polymer is obtained by reacting at 100 DEG C, the dihydroxypropionic acid adding 2 mass parts introduces hydrophilic group, reaction 2h is cooled to 50 DEG C, the triethylamine adding 1 mass parts continues to stir, and adds the Graphene-Fe of 0.1 mass parts
3o
4the deionized water of the aqueous solution, 30-300 mass parts and the quadrol emulsification of 0.1 mass parts, obtain Graphene-Fe
3o
4/ aqueous polyurethane emulsion, dry in Teflon mould at 70 DEG C, obtain Graphene-Fe
3o
4/ aqueous polyurethane composite membrane.
Embodiment 2:
1) graphite of 10 mass parts is joined dispersed with stirring in the vitriol oil of 100 mass parts even, be cooled to less than 0 DEG C; Slowly add the potassium permanganate of 100 mass parts, then be warming up to 25 DEG C and keep 2h; Slowly add deionized water, then the mass percentage concentration adding 100 mass parts is that 30% hydrogen peroxide solution is until become glassy yellow; Use 1M hydrochloric acid soln to wash 3 times, obtain graphene oxide aqueous dispersions for subsequent use;
2) by graphene oxide aqueous dispersions ultrasonic 50min in ultrasonator, after Graphene aqueous dispersions to be oxidized is uniformly dispersed, 10 mass parts FeCl are added
3, magnetic agitation, is placed with in teflon-lined reactor afterwards, is heated to 150 DEG C, reaction 10h, and cooling, is 7 with deionized water wash to pH value, obtains Graphene-Fe
3o
4the aqueous solution, adds the silane coupling agent of 2%.
3) by the polytetrahydrofuran diol vacuum hydro-extraction of 100 mass parts, the '-diphenylmethane diisocyanate adding 50 mass parts mixes, performed polymer is obtained by reacting at 80 DEG C, the dihydroxypropionic acid adding 20 mass parts introduces hydrophilic group, reaction 2h is cooled to 50 DEG C, the triethylamine adding 10 mass parts continues to stir, and adds the Graphene-Fe of 1 mass parts
3o
4the deionized water of the aqueous solution, 300 mass parts and the quadrol emulsification of 1 mass parts, obtain Graphene-Fe
3o
4/ aqueous polyurethane emulsion, dry, obtain Graphene-Fe
3o
4/ aqueous polyurethane composite membrane.
Embodiment 3:
1) graphite of 2 mass parts is joined dispersed with stirring in the vitriol oil of 40 mass parts even, be cooled to less than 0 DEG C; Slowly add the potassium permanganate of 20 mass parts, then be warming up to 30 DEG C and keep 4h; Slowly add deionized water, then the mass percentage concentration adding 20 mass parts is that 30% hydrogen peroxide solution is until become glassy yellow; Use 1M hydrochloric acid soln to wash 2 times, obtain graphene oxide aqueous dispersions for subsequent use;
2) by graphene oxide aqueous dispersions ultrasonic 30min in ultrasonator, after Graphene aqueous dispersions to be oxidized is uniformly dispersed, 5 mass parts FeCl are added
3, magnetic agitation, is placed with in teflon-lined reactor afterwards, is heated to 180 DEG C, reaction 6h, and cooling, is 7 with deionized water wash to pH value, obtains Graphene-Fe
3o
4the aqueous solution, adds the silane coupling agent of 0.5%;
3) by the polytetrahydrofuran diol vacuum hydro-extraction of 30 mass parts, the '-diphenylmethane diisocyanate adding 20 mass parts mixes, performed polymer is obtained by reacting at 90 DEG C, the dihydroxypropionic acid adding 6 mass parts introduces hydrophilic group, reaction 2h is cooled to 50 DEG C, the triethylamine adding 3 mass parts continues to stir, and adds the Graphene-Fe of 0.3 mass parts
3o
4the deionized water of the aqueous solution, 60 mass parts and the quadrol emulsification of 0.5 mass parts, obtain Graphene-Fe
3o
4/ aqueous polyurethane emulsion, dry, obtain Graphene-Fe
3o
4/ aqueous polyurethane composite membrane.
Above-described embodiment is used for explaining and the present invention is described, instead of limits the invention, and in the protection domain of spirit of the present invention and claim, any amendment make the present invention and change, all fall into protection scope of the present invention.
Claims (1)
1. one kind has the Graphene-Fe of electro-magnetic screen function
3o
4the preparation method of/aqueous polyurethane nano matrix material, is characterized in that comprising the steps:
1) graphite of 1-10 mass parts is joined dispersed with stirring in the vitriol oil of 5-100 mass parts even, be cooled to less than 0 DEG C; Slowly add the potassium permanganate of 5-100 mass parts, then be warming up to 25-40 DEG C and keep 2-6h; Slowly add deionized water, then to add 5-100 mass parts mass percentage concentration be that the hydrogen peroxide solution of 30% is until become glassy yellow; Use 1M hydrochloric acid soln washing 2-3 time, obtain graphene oxide aqueous dispersions for subsequent use;
2) by graphene oxide aqueous dispersions ultrasonic 10-50min in ultrasonator, after Graphene aqueous dispersions to be oxidized is uniformly dispersed, the FeCl of 1-10 mass parts is added
3, magnetic agitation, is placed with afterwards in teflon-lined reactor, is heated to 150-230 DEG C, reaction 2-10h, and cooling, is 7 with deionized water wash to pH value, obtains Graphene-Fe
3o
4the aqueous solution;
3) by the polytetrahydrofuran diol vacuum hydro-extraction of 10-100 mass parts, the '-diphenylmethane diisocyanate adding 4-50 mass parts mixes, performed polymer is obtained by reacting at 80-100 DEG C, the dihydroxypropionic acid adding 2-20 mass parts introduces hydrophilic group, reaction 2h is cooled to 50 DEG C, the triethylamine adding 1-10 mass parts continues to stir, and adds the Graphene-Fe of 0.1-1 mass parts
3o
4the deionized water of the aqueous solution, 30-300 mass parts and the quadrol emulsification of 0.1-1 mass parts, obtain Graphene-Fe
3o
4/ aqueous polyurethane emulsion, dry in Teflon mould at 70-100 DEG C, obtain Graphene-Fe
3o
4/ aqueous polyurethane composite membrane;
Step 3) described in Graphene-Fe
3o
4the aqueous solution in add silane coupling agent, polyvinyl alcohol or the polyvinylpyrrolidone that mass percentage concentration is 0.1%-2%.
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| CN201410006051.5A CN103772722B (en) | 2014-01-07 | 2014-01-07 | There is the Graphene-Fe of electro-magnetic screen function 3o 4the preparation method of/aqueous polyurethane nano matrix material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104592477B (en) * | 2015-02-16 | 2017-03-01 | 中北大学 | High performance magnetic polyurethane elastic composite preparation method |
| CN104962185B (en) * | 2015-06-03 | 2017-08-11 | 陕西科技大学 | Graphene-supported nanometer Fe3O4/ aqueous polyurethane composite magnetic conductive wave-absorbing coating material and preparation method thereof |
| CN106317728A (en) * | 2015-07-03 | 2017-01-11 | 上海伟星新型建材有限公司 | High-efficiency and high-strength composite material with far infrared radiation heating and preparation method thereof |
| CN105131563B (en) * | 2015-09-30 | 2017-09-05 | 中北大学 | A kind of preparation method of Fe3O4/ graphene oxides/Waterborne PU Composite |
| CN105713519B (en) * | 2016-03-01 | 2017-12-26 | 山东农业大学 | The method of the inorganic nano particle modified water-borne wood coating of two dimensional oxidation graphene hydridization zero dimension |
| CN105625049A (en) * | 2016-03-19 | 2016-06-01 | 晋江市众信超纤科技有限公司 | Preparation method for synthetic leather with electromagnetic shielding function and polyurethane foamed slurry of synthetic leather |
| CN109776749B (en) * | 2019-01-14 | 2021-03-26 | 长春工业大学 | Lignin-based flexible electromagnetic shielding material |
| CN113121982B (en) * | 2021-04-20 | 2022-05-31 | 浙江优可丽新材料有限公司 | Absorption loss type gradient structure composite electromagnetic shielding material and preparation method thereof |
| CN114525028B (en) * | 2021-09-26 | 2023-02-21 | 北京理工大学 | Adjustable polymer-based porous electromagnetic shielding material, and preparation method and application thereof |
| CN113895051A (en) * | 2021-10-08 | 2022-01-07 | 北京化工大学 | Preparation method of high-load-bearing polymer functional composite material based on 3D printing technology |
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| CN103408718A (en) * | 2013-08-05 | 2013-11-27 | 江苏大学 | Preparation method and application of graphene oxide-polyurethane foam material |
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Inventor after: Li Youliang Inventor after: Chen Guogui Inventor after: Gao Chao Inventor after: Feng Jinmao Inventor before: Li Youliang Inventor before: Chen Guogui Inventor before: Gao Chao Inventor before: Feng Xinmao |
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