CN115678393B - Preparation method of polypyrrole/polyurea with electromagnetic shielding effect - Google Patents
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- 229920002396 Polyurea Polymers 0.000 title claims abstract description 92
- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 230000000694 effects Effects 0.000 title claims abstract description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002042 Silver nanowire Substances 0.000 claims abstract description 41
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011248 coating agent Substances 0.000 claims abstract description 29
- 238000000576 coating method Methods 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 24
- 239000000839 emulsion Substances 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 150000002009 diols Chemical class 0.000 claims abstract description 11
- 229920000728 polyester Polymers 0.000 claims abstract description 11
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 235000011187 glycerol Nutrition 0.000 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 150000004985 diamines Chemical class 0.000 claims description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- KCLIFOXATBWLMW-UHFFFAOYSA-M sodium;ethane-1,2-diamine;ethanesulfonate Chemical compound [Na+].NCCN.CCS([O-])(=O)=O KCLIFOXATBWLMW-UHFFFAOYSA-M 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 102100024133 Coiled-coil domain-containing protein 50 Human genes 0.000 claims description 5
- 101000910772 Homo sapiens Coiled-coil domain-containing protein 50 Proteins 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 3
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000002019 doping agent Substances 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 7
- 238000009826 distribution Methods 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a preparation method of polypyrrole/polyurea with electromagnetic shielding effect, belonging to the technical field of high polymer materials. Firstly, preparing an aqueous polyurea component, providing a hydrophilic chain by adding nonionic polyester diol, then adding pyrrole into polyurea emulsion, initiating in-situ polymerization of the pyrrole by taking ferric chloride as an oxidant and a doping agent, and then doping an aqueous solution, silver nanowires and a small amount of graphene, so that the prepared coating has certain conductivity and good electromagnetic shielding effect. The method can prepare the polypyrrole/polyurea aqueous solution with good dispersion stability, and the silver nanowire/graphene/polypyrrole/polyurea coating has higher conductivity and electromagnetic shielding effectiveness by doping the silver nanowire and the graphene and relying on the conductivity and electromagnetic shielding performance of the silver nanowire and the graphene, the film forming performance of the polyurea and the stability of the polypyrrole, so that the silver nanowire/graphene/polypyrrole/polyurea coating has application prospects in various application aspects.
Description
Technical Field
The invention relates to a preparation method of polypyrrole/polyurea with electromagnetic shielding effect, belonging to the technical field of high polymer materials.
Background
The high-speed development of the current electronic equipment generates a great deal of electromagnetic pollution, which interferes with the normal operation of the electronic equipment and affects the health of human beings. Therefore, the preparation of a coating capable of shielding electromagnetic pollution on the surface of a device can be widely used in various fields.
Generally, the higher the electromagnetic shielding effect is, the better the conductivity is, and polypyrrole is an important material in the field of electromagnetic shielding as a conductive polymer, but can be adhered to the surface of a substrate, and the adhesion and film forming property of polypyrrole are all poor, so that a coating layer having good dispersion stability with polypyrrole and simultaneously achieving good film forming property and stability on the surface of the substrate is required.
Polyurea is a common film-forming resin, has good adhesive force and film-forming property, and can be well mixed with other reagents, so that the polyurea is very suitable as a main part of film formation.
Silver nanowires are used as a conductive material with a one-dimensional structure, and have large length-diameter ratio and high conductivity, so that the silver nanowires have wider application in the field of electromagnetic shielding. Graphene, which is a special 2D material, can be staggered in a coating layer due to its excellent chemical stability, is also used on a large scale in the field of electromagnetic shielding, and is a very excellent electromagnetic shielding material.
By mixing polyurea, polypyrrole, silver nanowires and graphene, a silver nanowire/graphene/polypyrrole/polyurea coating with certain conductivity and electromagnetic shielding effectiveness is prepared, which can form a film on a substrate, so that the polymer can be developed in leather and textiles.
Disclosure of Invention
The invention aims to promote the dispersibility of polypyrrole in a polyurea aqueous solution through in-situ polymerization of pyrrole in a polyurea emulsion, and simultaneously disperse silver nanowires and a small amount of graphene in the polyurea solution, and provides a preparation method with an electromagnetic shielding coating, which provides feasibility of the polyurea in terms of electromagnetic shielding performance, and expands the application field of the electromagnetic shielding polyurea coating through good physical properties of the polyurea.
The technical scheme of the invention is that the preparation method of polypyrrole/polyurea with electromagnetic shielding effect comprises the following steps:
(1) Preparation of polyurea component: mixing diisocyanate, nonionic polyester diol and polyether amine 2000 according to a metering ratio, dropwise adding a catalyst, and reacting under a high-temperature nitrogen condition; then adding diamine with small molecular weight for chain extension, reacting at high temperature, and then adding ethylenediamine ethanesulfonic acid sodium salt with a metering ratio for reacting to obtain polyurea component;
(2) Preparation of polypyrrole/polyurea aqueous emulsion: heating the polyurea component prepared in the step (1) to react, adding a solvent to reduce the viscosity of emulsion, adding metered pyrrole to react at a high temperature, then cooling to normal temperature, and adding deionized water to stir at a high speed; placing the reaction in an ice-water bath, adding ferric chloride solution with the same molar weight as pyrrole, and reacting under an acidic condition to prepare polypyrrole/polyurea aqueous emulsion;
(3) Preparation of silver nanowires: dissolving quantitative polyvinylpyrrolidone in glycerol, stirring at high temperature until the polyvinylpyrrolidone is dissolved, cooling, adding silver nitrate and a mixture of sodium chloride, water and glycerol, heating and stirring until the solution turns into a grey green, cooling, adding deionized water, standing for more than one week, centrifuging and washing, and finally obtaining silver nanowires;
(4) Preparation of the coating: taking the polypyrrole/polyurea aqueous solution prepared in the step (2), simultaneously weighing graphene and the silver nanowire prepared in the step (3), mixing, performing ultrasonic treatment, then pouring into a mold, and drying in an oven to obtain the polypyrrole/polyurea coating with the electromagnetic shielding function.
Further, the diisocyanate in the step (1) is isophorone diisocyanate (IPDI) and/or Hexamethylene Diisocyanate (HDI).
Further, the molecular weight of the nonionic polyester diol in step (1) is 1000.
Further, the low molecular weight diamine in the step (1) is butanediamine and/or hexanediamine.
Further, the addition amount of the pyrrole in the step (2) is not more than 20% of the mass of the polyurea.
Further, the acidic condition in step (2) is between ph=2-5.
Further, the preparation process of the step (1) is as follows: taking 0.033-0.037mol of diisocyanate, 0.008-0.012mol of nonionic polyester diol Ymer N120 and 0.008-0.012mol of polyether amine 2000 in a three-neck flask, heating to 58-62 ℃, reacting for 1-3h under the condition of nitrogen, then adding 0.008-0.012mol of small molecular weight diamine for reacting for 20-40min, then adding 0.01-0.014mol of ethylenediamine ethanesulfonic acid sodium salt, and reacting for 20-40min to obtain a polyurea component.
Further, the preparation process of the step (2) is as follows: reacting the polyurea component prepared in the step (1) at 75-85 ℃, adding pyrrole with the weight of 15-18% of the polyurea mass, reacting for 1-2 hours at 75-85 ℃, cooling to normal temperature, adding 100-150mL of deionized water, and stirring at high speed for 1-2 hours; and (3) placing the reaction solution in an ice-water bath, adding ferric chloride solution with the same molar quantity as pyrrole, regulating the pH to 2-5, and reacting for 10-14h to obtain the polypyrrole/polyurea aqueous emulsion.
Further, the preparation process of the step (3) is as follows: dissolving 5.76-5.96g polyvinylpyrrolidone in 200mL glycerin, stirring at 80-100 ℃ until the polyvinylpyrrolidone is dissolved, cooling, adding a mixture of 1.48-1.68g silver nitrate, 0.06g sodium chloride, 0.5mL water and 10mL glycerin, heating and stirring until the temperature is 195-205 ℃, changing the solution into a grey green, cooling to 45-55 ℃, adding 200mL deionized water, standing for more than one week, centrifuging and washing for 10min at 6000-7000r/min, and drying at 60 ℃ for 24h to obtain the silver nanowires.
Further, the preparation process of the step (4) is as follows: mixing 5%, 10%, 20%, 30%, 40% of silver nanowires and 1% of graphene by mass of the polypyrrole/polyurea aqueous solution, performing ultrasonic treatment for 30min at 30KHz, pouring into a mold, and drying for 24h in an oven at 55-65 ℃ to obtain the polypyrrole/polyurea coating with the electromagnetic shielding function.
According to the invention, through in-situ polymerization of pyrrole in the polyurea emulsion, the dispersion stability of polypyrrole in the polyurea emulsion is improved, so that the prepared aqueous solution is more uniform, electromagnetic shielding is effective on each part of the coating, and in addition, the addition of graphene and silver nanowires provides higher conductivity and better electromagnetic shielding performance, so that the coating has more application in multiple fields.
The invention has the beneficial effects that: the method can prepare the polypyrrole/polyurea aqueous solution with good dispersion stability, and the silver nanowire/graphene/polypyrrole/polyurea coating has higher conductivity and electromagnetic shielding effectiveness by doping the silver nanowire and the graphene and relying on the conductivity and electromagnetic shielding performance of the silver nanowire and the graphene, the film forming performance of the polyurea and the stability of the polypyrrole, so that the silver nanowire/graphene/polypyrrole/polyurea coating has application prospects in various application aspects.
Drawings
FIG. 1 is an emulsion particle size distribution of an aqueous polyurea solution and an aqueous polypyrrole/polyurea solution.
FIG. 2 is a schematic diagram of electromagnetic performance comparison; a. aqueous polyureas and aqueous polypyrrole/polyureas; b. 1% graphene and silver nanowires with different proportions.
Figure 3 is a conductivity comparison of aqueous polypyrrole/polyurea doped with silver nanowires in different proportions.
Detailed Description
Example 1
(1) Preparation of polyurea component: 7.78g (0.035 mol) of IPDI, 10g (0.01 mol) of nonionic polyester diol Ymer N120 and 20g (0.01 mol) of polyether amine 2000 are taken in a three-neck flask, heated to 60 ℃ and reacted for 2 hours under the condition of nitrogen, then 1.16g (0.01 mol) of hexamethylenediamine is added for 30 minutes, then 4.56g (0.012 mol) of ethylenediamine sodium ethanesulfonate aqueous solution with the mass concentration of 50% is added for 30 minutes, and a polyurea component is obtained.
(2) Preparation of polypyrrole/polyurea aqueous emulsion: reacting the polyurea component at 80 ℃, adding 8.24g (weight percent of polyurea mass) of pyrrole, reacting for 1h at 80 ℃, cooling to normal temperature, adding 150ml of deionized water, and stirring for 1h at high speed; the reaction was placed in an ice-water bath, 88.25g of a 20wt% ferric chloride solution (equimolar amount of ferric chloride to pyrrole) was added and reacted for 12h at ph=4 acidic conditions. The polypyrrole/polyurea aqueous emulsion is prepared.
(3) Preparation of silver nanowires: dissolving 5.86g of polyvinylpyrrolidone in 200mL of glycerin, stirring at 90 ℃ until the polyvinylpyrrolidone is dissolved, cooling, adding a mixture of 1.58g of silver nitrate, 0.06g of sodium chloride, 0.5mL of water and 10mL of glycerin, heating and stirring until the temperature of the mixture is 200 ℃ and the solution turns into a grey green, then cooling to about 50 ℃, adding 200mL of deionized water, standing for more than one week, centrifugally washing for 10min at 6500r/min, and drying for 24h at 60 ℃ to obtain the silver nanowires.
(4) Preparation of the coating: taking 5 parts of polypyrrole/polyurea aqueous solution, respectively 10g, adding 0.1g of graphene into each part, mixing, respectively weighing 0.05g, 0.1g, 0.2g, 0.3g and 0.4g of silver nanowires into the aqueous solution, mixing, performing ultrasonic treatment for 30min at 30KHz, then pouring into a mould, and drying at 60 ℃ for 24h in an oven to obtain the polypyrrole/polyurea coating with the electromagnetic shielding function.
Taking the polyurea solution (figure 1-a) prepared in the step (1) and the polypyrrole/polyurea aqueous emulsion (figure 1-b) prepared in the step (2), and respectively detecting the particle size distribution of the polyurea solution and the polypyrrole/polyurea aqueous emulsion, wherein the particle size distribution is shown in the specification. It can be seen that both particle size distributions are below 100nm, the latter being larger than the former, probably due to the hydrophobic nature of polypyrrole; in addition, the particle size difference between the two particles is not large, and the particles are uniformly dispersed, which indicates that the agglomeration phenomenon is avoided.
And (3) comparing electromagnetic shielding effectiveness by taking the polyurea solution prepared in the step (1) with the polypyrrole/polyurea aqueous emulsion prepared in the step (2), wherein the electromagnetic shielding effectiveness is shown in a figure 2-a. From the graph (a), the addition of polypyrrole can improve the electromagnetic shielding effectiveness of the aqueous polyurea to 15dB.
And (3) taking the coating doped with 1% graphene and silver nanowires with different proportions prepared in the step (4) to detect electromagnetic shielding effectiveness, wherein the electromagnetic shielding effectiveness is shown in a figure 2-b. From the graph (b), it can be derived that the electromagnetic shielding effectiveness is not improved much when only 1% of graphene is added, and the electromagnetic shielding effectiveness of the coating is gradually increased along with the addition of the silver nanowires, and when the addition amount reaches 40%, 64.2dB can be reached, which proves that the addition of the silver nanowires has a great improvement effect on the electromagnetic shielding effectiveness of the coating.
And (3) taking the aqueous polypyrrole/polyurea coating doped with the silver nanowires with different proportions in the step (4), and detecting the conductivity of the aqueous polypyrrole/polyurea coating, wherein the specific conductivity is shown in figure 3. It can be seen that with the addition of silver nanowires, the conductivity of the coating increases rapidly, especially when 40% of the silver nanowires are added, from 7.3 x 10 -9 s/m increases sharply to 1026.1s/m, which indicates silverThe nanowires form a conductive path in the coating that causes a steep increase in conductivity.
Example 2
(1) Preparation of polyurea component: taking 0.033mol of diisocyanate, 0.008mol of nonionic polyester diol Ymer N120 and 0.008mol of polyether amine 2000 in a three-neck flask, heating to 58 ℃, reacting for 3 hours under the condition of nitrogen, then adding 0.008mol of small molecular weight diamine for reacting for 20 minutes, then adding 0.01mol of ethylenediamine ethanesulfonic acid sodium salt, and reacting for 20 minutes to obtain a polyurea component.
The diisocyanate is hexamethylene diisocyanate HDI; the molecular weight of the nonionic polyester diol is 1000; the low molecular weight diamine is hexamethylenediamine;
(2) Preparation of polypyrrole/polyurea aqueous emulsion: reacting the polyurea component prepared in the step (1) at 75 ℃, adding pyrrole with 15wt% of the polyurea mass, reacting for 2 hours at 75 ℃, cooling to normal temperature, adding 100mL of deionized water, and stirring for 2 hours at a high speed; and (3) placing the reaction solution in an ice-water bath, adding ferric chloride solution with the same molar quantity as pyrrole, adjusting the pH to 2, and reacting for 10 hours to obtain the polypyrrole/polyurea aqueous emulsion.
(3) Preparation of silver nanowires: 5.76g of polyvinylpyrrolidone is dissolved in 200mL of glycerin, stirred at 80 ℃ until the polyvinylpyrrolidone is dissolved, cooled, added with 1.48g of silver nitrate and a mixture of 0.06g of sodium chloride, 0.5mL of water and 10mL of glycerin, heated and stirred until the temperature is 195 ℃ and the solution turns to be grey green, then cooled to 45 ℃, added with 200mL of deionized water for more than one week, centrifugally washed for 10min at 6000r/min, and dried for 24h at 60 ℃ to obtain the silver nanowires.
(4) Preparation of the coating: mixing 5%, 10%, 20%, 30%, 40% of silver nanowires and 1% of graphene by mass of the polypyrrole/polyurea aqueous solution, performing ultrasonic treatment for 30min at 30KHz, pouring into a mold, and drying at 55 ℃ for 24h in an oven to obtain the polypyrrole/polyurea coating with the electromagnetic shielding function.
Example 3
(1) Preparation of polyurea component: taking 0.037mol of diisocyanate, 0.012mol of nonionic polyester diol Ymer N120 and 0.012mol of polyether amine 2000 in a three-neck flask, heating to 62 ℃, reacting for 1h under the condition of nitrogen, then adding 0.012mol of small molecular weight diamine for reacting for 40min, then adding 0.014mol of ethylenediamine ethanesulfonic acid sodium salt, and reacting for 40min to obtain a polyurea component.
The diisocyanate is isophorone diisocyanate IPDI and hexamethylene diisocyanate HDI; the molecular weight of the nonionic polyester diol is 1000; the low molecular weight diamine is butanediamine;
(2) Preparation of polypyrrole/polyurea aqueous emulsion: reacting the polyurea component prepared in the step (1) at 85 ℃, adding pyrrole with the mass of 18wt% of the polyurea, reacting for 1h at 85 ℃, cooling to normal temperature, adding 150mL of deionized water, and stirring for 1h at a high speed; and (3) placing the reaction solution in an ice-water bath, adding ferric chloride solution with the same molar quantity as pyrrole, adjusting the pH to 5, and reacting for 14 hours to obtain the polypyrrole/polyurea aqueous emulsion.
(3) Preparation of silver nanowires: 5.96g of polyvinylpyrrolidone is dissolved in 200mL of glycerin, stirred at 100 ℃ until the polyvinylpyrrolidone is dissolved, cooled, added with 1.68g of silver nitrate and a mixture of 0.06g of sodium chloride, 0.5mL of water and 10mL of glycerin, heated and stirred until the temperature of the mixture is 205 ℃ and turns into a grey green, then cooled to 55 ℃, added with 200mL of deionized water for more than one week, centrifugally washed for 10min at 7000r/min, and dried for 24h at 60 ℃ to obtain the silver nanowires.
(4) Preparation of the coating: mixing 5%, 10%, 20%, 30%, 40% of silver nanowires and 1% of graphene by mass of the polypyrrole/polyurea aqueous solution, performing ultrasonic treatment for 30min at 30KHz, pouring into a mold, and drying at 65 ℃ for 24h in an oven to obtain the polypyrrole/polyurea coating with the electromagnetic shielding function.
Claims (4)
1. A preparation method of polypyrrole/polyurea with electromagnetic shielding effect is characterized by comprising the following steps:
(1) Preparation of polyurea component: taking 0.033-0.037mol of diisocyanate, 0.008-0.012mol of nonionic polyester diol Ymer N120 and 0.008-0.012mol of polyether amine 2000 in a three-neck flask, heating to 58-62 ℃, reacting for 1-3h under the condition of nitrogen, then adding 0.008-0.012mol of small molecular weight diamine for reacting for 20-40min, then adding 0.01-0.014mol of ethylenediamine ethanesulfonic acid sodium salt, and reacting for 20-40min to obtain a polyurea component;
(2) Preparation of polypyrrole/polyurea aqueous emulsion: reacting the polyurea component prepared in the step (1) at 75-85 ℃, adding pyrrole with the weight of 15-18% of the polyurea mass, reacting for 1-2 hours at 75-85 ℃, cooling to normal temperature, adding 100-150mL of deionized water, and stirring at high speed for 1-2 hours; placing the reaction solution in an ice-water bath, adding ferric chloride solution with the same molar weight as pyrrole, adjusting the pH to 2-5, and reacting for 10-14h to obtain polypyrrole/polyurea aqueous emulsion;
(3) Preparation of silver nanowires: dissolving 5.76-5.96g polyvinylpyrrolidone in 200mL glycerin, stirring at 80-100 ℃ until the polyvinylpyrrolidone is dissolved, cooling, adding a mixture of 1.48-1.68g silver nitrate, 0.06g sodium chloride, 0.5mL water and 10mL glycerin, heating and stirring until the temperature is 195-205 ℃, changing the solution into a grey green, cooling to 45-55 ℃, adding 200mL deionized water, standing for more than one week, centrifuging and washing for 10min at 6000-7000r/min, and drying at 60 ℃ for 24h to obtain silver nanowires;
(4) Preparation of the coating: and (3) respectively taking 5%, 10%, 20%, 30% and 40% of silver nanowires and 1% of graphene, which are obtained by the step (2), of the mass of the prepared polypyrrole/polyurea aqueous solution, mixing the silver nanowires and the graphene with the mass of the polypyrrole/polyurea aqueous solution, performing ultrasonic treatment for 30min at 30KHz, pouring the mixture into a mold, and drying the mixture in an oven at 55-65 ℃ for 24 hours to obtain the polypyrrole/polyurea coating with the electromagnetic shielding function.
2. The method for preparing polypyrrole/polyurea with electromagnetic shielding effectiveness according to claim 1, wherein: the diisocyanate in the step (1) is isophorone diisocyanate (IPDI) and/or Hexamethylene Diisocyanate (HDI).
3. The method for preparing polypyrrole/polyurea with electromagnetic shielding effectiveness according to claim 1, wherein: the molecular weight of the nonionic polyester diol in step (1) is 1000.
4. The method for preparing polypyrrole/polyurea with electromagnetic shielding effectiveness according to claim 1, wherein: the low molecular weight diamine in the step (1) is butanediamine and/or hexanediamine.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006321840A (en) * | 2005-05-17 | 2006-11-30 | Shin Etsu Polymer Co Ltd | Electrically conductive polymer solution and electrically conductive coating film |
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| US10468152B2 (en) * | 2013-02-21 | 2019-11-05 | Global Graphene Group, Inc. | Highly conducting and transparent film and process for producing same |
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