CN114230975A - Light anti-scorching conductive shielding material and preparation method thereof - Google Patents
Light anti-scorching conductive shielding material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a light anti-scorching conductive shielding material and a preparation method thereof, and relates to the technical field of electromagnetic shielding materials. The invention takes hollow spiral metal copper nano fiber as a framework, soaks a matrix solution containing a self-made additive to be solidified, then foams the matrix solution into a foam hole structure by utilizing gas, and coats a self-conducting polymer on the inner surface of a micropore to prepare a conducting shielding material; the self-made additive is prepared from butylaminoacetamide dibutanol, methyl dichlorophosphate and aminoethyl biphenyl borate, so that the conductive shielding material realizes excellent flame-retardant and corrosion-resistant functions; the self-conducting polymer is prepared by coupling and polymerizing bromide ions of bromo-diheptyl indole carbazole and dibromo-dinitrodiazosulfide, and the conductivity of the conducting shielding material is effectively improved. The light anti-scorching conductive shielding material prepared by the invention has the effects of flame retardance, corrosion resistance and high electromagnetic shielding property.
Description
Technical Field
The invention relates to the technical field of electromagnetic shielding materials, in particular to a light anti-scorching conductive shielding material and a preparation method thereof.
Background
With the rapid development of modern society, more and more electronic equipment and electronic devices appear around us, and generate a large amount of electromagnetic radiation while bringing convenience to our lives, thereby having great influence on our lives. The induced current generated by the electromagnetic radiation in the propagation process can interfere with some electronic devices, thereby affecting the normal use of the electronic devices; on the other hand, the penetration of a large amount of high intensity electromagnetic waves into the human body also has adverse effects on human cells, which may cause cell mutation to form tumors. In order to eliminate the influence of undesirable electromagnetic radiation, high-performance electromagnetic shielding materials need to be prepared.
At present, the electromagnetic shielding material adopts conductive filler to realize the shielding effect, the traditional metal material has good conductive performance, but the application of the traditional metal material is limited to a certain extent due to the defects of high density, poor corrosion resistance and the like, meanwhile, the flame retardant property of the electromagnetic shielding material on the market is often not ideal, and even accidents caused by fire frequently occur. Therefore, in order to meet the development requirements in the fields of modern electronic and electrical appliance communication and the like, the production of the electromagnetic shielding material with light weight, flame retardance and good electromagnetic shielding effect is very urgent.
Disclosure of Invention
The invention aims to provide a light anti-scorching conductive shielding material and a preparation method thereof, which aim to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: the light anti-scorching conductive shielding material is characterized by mainly comprising, by weight, 50-80 parts of metal copper nanofibers, 5-10 parts of a self-made additive, 3-8 parts of a self-conducting polymer, 60-100 parts of epoxy resin and 1-3 parts of a curing agent.
Further, the homemade additive is prepared from butylaminoacetamide dibutyl alcohol, methyl dichlorophosphate and aminoethyl biphenyl borate.
Furthermore, the self-conducting polymer is prepared by coupling and polymerizing bromide ions of bromo-diheptyl indole carbazole and dibromo-dinitro-benzothiadiazole.
Further, the curing agent is one or a mixture of more of aminoethyl piperazine, isophorone diamine, m-phenylenediamine or ethylenediamine. .
Further, the conductive shielding material comprises the following raw material components in parts by weight: 65 parts of metal copper nano fiber, 7 parts of self-made additive, 4 parts of self-conducting polymer, 78 parts of epoxy resin and 2 parts of curing agent.
Further, a preparation method of the light anti-scorching conductive shielding material is characterized by mainly comprising the following preparation steps:
(1) adding 3.6 times of acetonitrile in mass of butyric acid amino acetamide dibutyl alcohol and butyric acid amino acetamide dibutyl alcohol into a three-neck flask, stirring and dissolving, adding 0.7 times of methyl dichlorophosphate in mass of butyric acid amino acetamide dibutyl alcohol at a speed of 0.15-0.2 mL/min, reacting at 15-20 ℃ for 1h, heating to 150 ℃, reacting for 9h, cooling to room temperature, distilling at 0.06MPa and 82 ℃ under reduced pressure for 10-14 min, washing with dichloromethane for 3-5 times, and vacuum drying at 250-300 Pa and 60 ℃ for 3-4 h to obtain butyric acid amino acetamide dibutyl phosphate;
(2) adding amino ethyl biphenyl boric acid ester, butyric acid amino acetamide dibutyl phosphate with 3.7 times of the mass of the amino ethyl biphenyl boric acid ester and toluene with 4.9 times of the mass of the amino ethyl biphenyl boric acid ester into a three-neck flask, stirring at the speed of 100rpm, heating to 250 ℃, reacting for 5-6 h, carrying out reduced pressure distillation at the temperature of 0.06MPa and 115 ℃ for 3-5 min, washing for 5-7 times with tetrahydrofuran, and carrying out vacuum drying at the temperature of 50 ℃ and 250-300 Pa for 3-4 h to obtain an additive;
(3) adding diphenoxybenzothiadiazole, dibromodinitrobenzothiadiazole with the mass of 0.5 time of diphenoxydinaphthalene diboronate, bromodiheptylindole carbazole with the mass of 1.2 times of diphenoxydinaphthalene diboronate and potassium carbonate/toluene solution with the mass of 3.6 times of diphenoxydinaphthalene diboronate into a three-mouth bottle, wherein the mass ratio of potassium carbonate to toluene in the potassium carbonate/toluene solution is 2:3, stirring uniformly, adding tetrakis (triphenylphosphine) palladium with the mass of 0.165 time of diphenoxydinaphthalene diboronate and tetra-n-butylammonium fluoride with the mass of 0.002 time of diphenoxydinoate, stirring and reacting at 90 ℃ under the speed of 100rpm under the atmosphere, cooling to room temperature, steaming at 200rpm and 115 ℃ for 20-30 min, adding trichloromethane with the mass of 2.1 times of diphenoxydinaphthalene diboronate, extracting for 6-8 times, steaming at 200rpm and 80 ℃ for 10-15 min, suction filtration from a conducting polymer;
(4) putting copper powder with the particle size of 3 mu m, dioctyl phthalate with the mass of 0.005 time of the copper powder, polyvinylpyrrolidone with the mass of 0.016 time of the copper powder and methyl pyrrolidone with the mass of 0.27 time of the copper powder into a wide-mouthed bottle, stirring for 30min at 200rpm, adding oxidized polysilicate iron with the mass of 0.021 time of the copper powder into the wide-mouthed bottle every 2h, adding the mixture for 3 times, and stirring for 3h at the same speed to obtain a casting solution; transferring the casting solution into a spinning tank, sealing the spinning tank, vacuumizing for 1h, spraying the casting solution from a spinning head under the nitrogen atmosphere, simultaneously, punching a deionized water core solution from an inner hole of a spinning nozzle, soaking the spinning nozzle in a tap water external solidification solution for 24h, straightening and drying at room temperature to obtain a precursor; fixing one end of the precursor on a rotating head on a rotating motor by using glue, bonding the other end of the precursor on a freely movable weight by using the glue, pulling the weight far away from the motor by 20cm, and rotating the motor for 2min at the speed of 300rpm to obtain the metal copper nanofiber;
(5) adding metal copper nanofibers and a self-made additive into a mold according to the formula amount under the nitrogen atmosphere, adding epoxy resin and a curing agent according to the formula amount at 60 ℃, keeping the pressure for 10min under 0.1MPa, keeping the pressure for 10min under 0.2MPa, heating to 90 ℃, curing for 4h, demolding, placing into an intermittent foaming high-pressure reaction kettle, foaming for 25-45 s under the conditions of 125 ℃ and the carbon dioxide gas adsorption pressure of 12MPa, rapidly cooling to room temperature, soaking in an auto-conductive polymer aqueous solution with the mass of 0.2-0.5 time of that of the metal copper nanofibers for 3-5 h, drying for 5-7 h at room temperature, and obtaining the conductive shielding material.
Further, the preparation method of butyric acid amino acetamide dibutyl alcohol in the step (1) comprises the following steps: adding methyl butyrate and ethylenediamine butanol with the mass of 2.2 times of that of the methyl butyrate into a three-necked bottle, stirring at the speed of 100rpm, heating to 100 ℃, adding sodium methoxide with the mass of 0.013 times of that of the methyl butyrate, controlling the temperature to be 115-125 ℃, reacting for 2-3 hours, cooling to room temperature, adding petroleum ether with the mass of 4.5 times of that of the methyl butyrate, uniformly stirring, performing suction filtration, adding deionized water with the mass of 3.2 times of that of the methyl butyrate, stirring at the speed of 50rpm, heating until the solution is viscous, filtering, cooling to room temperature, performing vacuum filtration under the pressure of 0.05MPa, washing with the deionized water for 2-3 times, and drying at the temperature of 30-40 ℃ for 3-5 hours to obtain the butylaminoacetamide dibutyl alcohol.
Further, the preparation method of the bromo-diheptyl indole carbazole in the step (3) comprises the following steps:
a. adding indole, p-bromobenzaldehyde with the mass of 1.6 times of that of the indole and acetonitrile with the mass of 33.7 times of that of the indole into a round-bottom flask, stirring until the indole is dissolved, adding hydroiodic acid solution with the mass fraction of 57% with the mass of 1.4 times of that of the indole at the speed of 5-6 drops/min, reacting for 24 hours, cooling to room temperature, performing suction filtration, and washing for 2-3 times with the acetonitrile to obtain a yellow solid; adding a yellow solid and acetonitrile with 22.4 times of indole mass into a round-bottom flask, stirring at 80 ℃ and 100rpm for reaction for 24 hours, carrying out rotary evaporation at 200rpm and 60 ℃ for 10-15 min, carrying out suction filtration, and washing with acetonitrile for 3 times to obtain a yellow crude product;
b. adding a yellow crude product, ethylhexyl bromide which is 1.4 times of the mass of the yellow crude product, tetrabutylammonium bromide which is 0.056 times of the mass of the yellow crude product, dimethyl sulfoxide which is 15.4 times of the mass of the yellow crude product, and a sodium hydroxide solution which is 12.8 times of the mass of the yellow crude product and has a mass fraction of 50% into a round-bottomed flask, stirring at 50 ℃ and 120rpm for 24 hours, adding saturated saline which is 79.8 times of the mass of the yellow crude product, adding hydrochloric acid with a mass fraction of 10% until the pH of the solution is 6-7, extracting, adding anhydrous sodium sulfate which is 3.5 times of the mass of the yellow crude product, drying for 1-2 hours, filtering, and evaporating under reduced pressure at 0.01MPa and 110 ℃ until the water is evaporated to obtain the bromo-diheptyl indole carbazole.
Further, the spinning temperature in the step (4) is 26 ℃, the core liquid flow rate is 7.2mL/min, and the spinning pressure is 0.12 MPa.
Compared with the prior art, the invention has the following beneficial effects:
the invention takes the hollow spiral metal copper nano fiber as a framework, soaks a matrix solution containing a self-made additive to be solidified, foams the matrix solution into a foam-hole-shaped structure by utilizing gas, and coats a self-conducting polymer on the inner surface of a micropore to prepare a conducting shielding material so as to realize the effects of flame retardance, corrosion resistance and high electromagnetic shielding property.
Firstly, the self-made additive is prepared by the reaction of hydroxyl of butyric acid amino acetamide dibutyl alcohol and chloride ions of methyl dichlorophosphate and the reaction of hydroxyl of butyric acid amino acetamide dibutyl alcohol and amino of amino ethyl biphenyl boric acid ester; the addition of the self-made additive enables a carbon layer to be formed on the surface of the conductive shielding material when the conductive shielding material is burnt, the heat insulation and the oxygen transmission are insulated, the dripping can be prevented, and the flame retardant property is good; the butyric acid amino acetamide dibutyl alcohol and the amino ethyl biphenyl boric acid ester are easy to decompose into flame-retardant gas by heat, so that the flame retardance of the conductive shielding material is enhanced, meanwhile, the reaction activity of phosphorus atoms in methyl dichlorophosphate can be excited, the reaction rate and the release rate of phosphorus-oxygen acid generated by pyrolysis of the phosphorus atoms are improved, a carbon layer is generated by the action of the phosphorus atoms and the flame-retardant gas, the carbon forming rate is improved, the existence of pores in the carbon layer is reduced, the air transfer is effectively blocked, and the flame retardance of the conductive shielding material is improved; in addition, the heteroatom in the self-made additive is adsorbed on the surface of the metal copper nanofiber, and preferentially reacts with an acid-base substance to inhibit the corrosion of the metal copper fiber, so that the conductive shielding material has a corrosion resistance effect.
Secondly, the self-conducting polymer is prepared by performing Suzuki coupling polymerization reaction on bromide ions of bromo-diheptyl indole carbazole and bromide ions of dibromo-dinitrodiazosulfide to form a donor and acceptor staggered connection structure, and a plurality of aromatic rings are introduced into a main chain to strengthen a conjugated pi electron system, so that the self-conducting polymer has high conductivity; the dibromo-dinitrodiazosulfide has a strong electron-withdrawing effect, can reduce the energy band gap of the self-conducting polymer, improves the coplanar degree of a main chain framework, enhances the conjugation effect and increases the conductivity; the cellular structure of the conductive shielding material enables electromagnetic waves to be multiply scattered and reflected in the material so as to attenuate the electromagnetic waves, thereby realizing the effect of shielding the electromagnetic waves; the metal copper nano-fiber and the self-conducting polymer form a conducting network, so that the conductivity of the material is improved, a large number of free electrons exist on the surface, the surface can interact with an electromagnetic wave field, most of electromagnetic waves are reflected, the transmittance is reduced, and the shielding performance of the conducting shielding material is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
To more clearly illustrate the method of the present invention, the following examples are provided, and the method for testing the indexes of the light scorch-resistant conductive shielding material prepared in the following examples is as follows:
flame retardancy: the combustion grade of the shielding material was determined by the vertical combustion method with reference to the IPC-TM-650 test method.
Corrosion resistance: according to the experimental method of GB/T1690, a shielding material sample is soaked in hydrochloric acid with the mass fraction of 30% and sodium hydroxide with the mass fraction of 40% at room temperature for 10 days respectively, the weight loss rate is calculated, and the smaller the weight loss rate is, the stronger the corrosion resistance is; the weight loss ratio is the weight after soaking/initial weight.
High electromagnetic shielding performance: and (3) adopting an N5247APNA vector network analyzer to characterize the electromagnetic shielding performance of the conductive shielding material.
Example 1
A light anti-scorching conductive shielding material mainly comprises the following components in parts by weight: 65 parts of metal copper nano fiber, 7 parts of self-made additive, 4 parts of self-conducting polymer, 78 parts of epoxy resin and 2 parts of curing agent.
A preparation method of a light anti-scorching conductive shielding material mainly comprises the following preparation steps:
(1) adding butyric acid amino acetamide dibutyl alcohol and acetonitrile which is 3.6 times of the mass of butyric acid amino acetamide dibutyl alcohol into a three-neck flask, stirring and dissolving, adding dichloro methyl phosphate which is 0.7 times of the mass of butyric acid amino acetamide dibutyl alcohol at the speed of 0.15mL/min, reacting for 1h at 18 ℃, heating to 150 ℃, reacting for 9h, cooling to room temperature, carrying out reduced pressure distillation at the temperature of 0.06MPa and 82 ℃ for 12min, washing for 5 times by using dichloromethane, and carrying out vacuum drying at the temperature of 265Pa and 60 ℃ for 4h to obtain butyric acid amino acetamide dibutyl methyl phosphate;
(2) adding amino ethyl biphenyl boric acid ester, butyric acid amino acetamide dibutyl phosphate with 3.7 times of the mass of the amino ethyl biphenyl boric acid ester and toluene with 4.9 times of the mass of the amino ethyl biphenyl boric acid ester into a three-neck flask, stirring at 100rpm, heating to 250 ℃, reacting for 6 hours, carrying out reduced pressure distillation at 0.06MPa and 115 ℃ for 5 minutes, washing for 7 times with tetrahydrofuran, and carrying out vacuum drying at 50 ℃ and 300Pa for 3 hours to obtain an additive;
(3) adding diphenoxypinacol diborate, dibromo dinitrobenzothiadiazole with the mass of 0.5 time of that of the diphenoxypinacol diborate, bromo diheptyl indole carbazole with the mass of 1.2 times of that of the diphenoxypinacol diborate, and potassium carbonate/toluene solution with the mass of 3.6 times of that of the diphenoxypinacol diborate into a three-mouth bottle, the mass ratio of potassium carbonate to toluene in the potassium carbonate/toluene solution is 2:3, after uniform stirring, adding tetrakis (triphenylphosphino) palladium with the mass of 0.165 time of that of the dipivalonic acid and tetra-n-butylammonium fluoride with the mass of 0.002 time of that of the dipivalonic acid, stirring and reacting at 90 ℃ under argon atmosphere and 100rpm for 48h, cooling to room temperature, rotary steaming at 200rpm and 115 deg.C for 30min, adding trichloromethane 2.1 times of dipivalonic acid and extracting for 8 times, performing rotary evaporation at 200rpm and 80 ℃ for 15min, and performing suction filtration to obtain a conductive polymer;
(4) putting copper powder with the particle size of 3 mu m, dioctyl phthalate with the mass of 0.005 time of the copper powder, polyvinylpyrrolidone with the mass of 0.016 time of the copper powder and methyl pyrrolidone with the mass of 0.27 time of the copper powder into a wide-mouthed bottle, stirring for 30min at 200rpm, adding oxidized polysilicate iron with the mass of 0.021 time of the copper powder into the wide-mouthed bottle every 2h, adding the mixture for 3 times, and stirring for 3h at the same speed to obtain a casting solution; transferring the casting solution into a spinning tank, sealing the spinning tank, vacuumizing for 1h, spraying the casting solution from a spinning head under the nitrogen atmosphere, simultaneously, punching a deionized water core solution from an inner hole of a spinning nozzle, soaking the spinning nozzle in a tap water external solidification solution for 24h, straightening and drying at room temperature to obtain a precursor; fixing one end of the precursor on a rotating head on a rotating motor by using glue, bonding the other end of the precursor on a freely movable weight by using the glue, pulling the weight far away from the motor by 20cm, and rotating the motor for 2min at the speed of 300rpm to obtain the metal copper nanofiber;
(5) adding metal copper nano-fiber and a self-made additive into a mould according to the formula amount under the nitrogen atmosphere, adding epoxy resin and a curing agent according to the formula amount at 60 ℃, keeping the pressure for 10min at 0.1MPa, keeping the pressure for 10min at 0.2MPa, heating to 90 ℃, curing for 4h, demoulding, placing into an intermittent foaming high-pressure reaction kettle, foaming for 30s at 125 ℃ under the condition of absorbing carbon dioxide gas pressure of 12MPa, rapidly cooling to room temperature, soaking in an auto-conductive polymer aqueous solution with the mass of 0.4 time of the metal copper nano-fiber for 4h, enabling the auto-conductive polymer in the auto-conductive polymer aqueous solution to be 1:5.7, and drying for 5h at room temperature to obtain the conductive shielding material.
Further, the preparation method of butyric acid amino acetamide dibutyl alcohol in the step (1) comprises the following steps: adding methyl butyrate and ethylenediamine butanol with the mass of 2.2 times of that of the methyl butyrate into a three-necked bottle, stirring at the speed of 100rpm, heating to 100 ℃, adding sodium methoxide with the mass of 0.013 times of that of the methyl butyrate, controlling the temperature at 120 ℃, reacting for 2 hours, cooling to room temperature, adding petroleum ether with the mass of 4.5 times of that of the methyl butyrate, uniformly stirring, performing suction filtration, adding deionized water with the mass of 3.2 times of that of the methyl butyrate, stirring at the speed of 50rpm, heating until the solution is viscous, filtering, cooling to room temperature, performing vacuum filtration under the pressure of 0.05MPa, washing with the deionized water for 3 times, and drying at the temperature of 37 ℃ for 4 hours to obtain the butylaminoacetamide dibutyl alcohol.
Further, the preparation method of the bromo-diheptyl indole carbazole in the step (3) comprises the following steps:
a. adding indole, p-bromobenzaldehyde with the mass of 1.6 times of that of the indole and acetonitrile with the mass of 33.7 times of that of the indole into a round-bottom flask, stirring until the indole is dissolved, adding hydroiodic acid solution with the mass fraction of 57 percent, which is 1.4 times of that of the indole, at the speed of 6 drops/min, reacting for 24 hours, cooling to room temperature, performing suction filtration, and washing for 3 times by using the acetonitrile to obtain a yellow solid; adding the yellow solid and acetonitrile with 22.4 times of indole mass into a round-bottom flask, stirring at 80 ℃ and 100rpm for reaction for 24h, then carrying out rotary evaporation at 200rpm and 60 ℃ for 13min, carrying out suction filtration, and washing with acetonitrile for 3 times to obtain a yellow crude product;
b. adding a yellow crude product, ethylhexyl bromide which is 1.4 times of the mass of the yellow crude product, tetrabutylammonium bromide which is 0.056 times of the mass of the yellow crude product, dimethyl sulfoxide which is 15.4 times of the mass of the yellow crude product, and a sodium hydroxide solution which is 12.8 times of the mass of the yellow crude product and has the mass fraction of 50% into a round-bottomed flask, stirring at 50 ℃ and 120rpm for 24 hours, adding saturated saline which is 79.8 times of the mass of the yellow crude product, adding hydrochloric acid with the mass fraction of 10% until the pH of the solution is 7, extracting, adding anhydrous sodium sulfate which is 3.5 times of the mass of the yellow crude product, drying for 2 hours, filtering, and evaporating under reduced pressure at 0.01MPa and 110 ℃ until the water is evaporated to obtain the bromo-diheptyl indole carbazole.
Further, the spinning temperature in the step (4) is 26 ℃, the core liquid flow rate is 7.2mL/min, and the spinning pressure is 0.12 MPa.
Example 2
A light anti-scorching conductive shielding material mainly comprises the following components in parts by weight: 65 parts of metal copper nano fiber, 4 parts of self-conducting polymer, 78 parts of epoxy resin and 2 parts of curing agent.
A preparation method of a light anti-scorching conductive shielding material mainly comprises the following preparation steps:
(1) adding diphenoxypinacol diborate, dibromo dinitrobenzothiadiazole with the mass of 0.5 time of that of the diphenoxypinacol diborate, bromo diheptyl indole carbazole with the mass of 1.2 times of that of the diphenoxypinacol diborate, and potassium carbonate/toluene solution with the mass of 3.6 times of that of the diphenoxypinacol diborate into a three-mouth bottle, the mass ratio of potassium carbonate to toluene in the potassium carbonate/toluene solution is 2:3, after uniform stirring, adding tetrakis (triphenylphosphino) palladium with the mass of 0.165 time of that of the dipivalonic acid and tetra-n-butylammonium fluoride with the mass of 0.002 time of that of the dipivalonic acid, stirring and reacting at 90 ℃ under argon atmosphere and 100rpm for 48h, cooling to room temperature, rotary steaming at 200rpm and 115 deg.C for 30min, adding trichloromethane 2.1 times of dipivalonic acid and extracting for 8 times, performing rotary evaporation at 200rpm and 80 ℃ for 15min, and performing suction filtration to obtain a conductive polymer;
(2) putting copper powder with the particle size of 3 mu m, dioctyl phthalate with the mass of 0.005 time of the copper powder, polyvinylpyrrolidone with the mass of 0.016 time of the copper powder and methyl pyrrolidone with the mass of 0.27 time of the copper powder into a wide-mouthed bottle, stirring for 30min at 200rpm, adding oxidized polysilicate iron with the mass of 0.021 time of the copper powder into the wide-mouthed bottle every 2h, adding the mixture for 3 times, and stirring for 3h at the same speed to obtain a casting solution; transferring the casting solution into a spinning tank, sealing the spinning tank, vacuumizing for 1h, spraying the casting solution from a spinning head under the nitrogen atmosphere, simultaneously, punching a deionized water core solution from an inner hole of a spinning nozzle, soaking the spinning nozzle in a tap water external solidification solution for 24h, straightening and drying at room temperature to obtain a precursor; fixing one end of the precursor on a rotating head on a rotating motor by using glue, bonding the other end of the precursor on a freely movable weight by using the glue, pulling the weight far away from the motor by 20cm, and rotating the motor for 2min at the speed of 300rpm to obtain the metal copper nanofiber;
(3) under the atmosphere of nitrogen, controlling the temperature at 60 ℃, adding epoxy resin and a curing agent according to the formula amount, maintaining the pressure at 0.1MPa for 10min, maintaining the pressure at 0.2MPa for 10min, heating to 90 ℃, curing for 4h, demolding, placing in an intermittent foaming high-pressure reaction kettle, foaming for 30s under the conditions of 125 ℃ and the pressure of absorbing carbon dioxide gas being 12MPa, rapidly cooling to room temperature, soaking in an auto-conductive polymer aqueous solution with the mass of 0.4 time of that of the metal copper nano-fiber for 4h, carrying out the mass ratio of the auto-conductive polymer to deionized water in the auto-conductive polymer aqueous solution of 1:5.7, and drying for 5h at room temperature to obtain the conductive shielding material.
Further, the preparation method of the bromo-diheptyl indole carbazole in the step (1) comprises the following steps:
a. adding indole, p-bromobenzaldehyde with the mass of 1.6 times of that of the indole and acetonitrile with the mass of 33.7 times of that of the indole into a round-bottom flask, stirring until the indole is dissolved, adding hydroiodic acid solution with the mass fraction of 57 percent, which is 1.4 times of that of the indole, at the speed of 6 drops/min, reacting for 24 hours, cooling to room temperature, performing suction filtration, and washing for 3 times by using the acetonitrile to obtain a yellow solid; adding the yellow solid and acetonitrile with 22.4 times of indole mass into a round-bottom flask, stirring at 80 ℃ and 100rpm for reaction for 24h, then carrying out rotary evaporation at 200rpm and 60 ℃ for 13min, carrying out suction filtration, and washing with acetonitrile for 3 times to obtain a yellow crude product;
b. adding a yellow crude product, ethylhexyl bromide which is 1.4 times of the mass of the yellow crude product, tetrabutylammonium bromide which is 0.056 times of the mass of the yellow crude product, dimethyl sulfoxide which is 15.4 times of the mass of the yellow crude product, and a sodium hydroxide solution which is 12.8 times of the mass of the yellow crude product and has the mass fraction of 50% into a round-bottomed flask, stirring at 50 ℃ and 120rpm for 24 hours, adding saturated saline which is 79.8 times of the mass of the yellow crude product, adding hydrochloric acid with the mass fraction of 10% until the pH of the solution is 7, extracting, adding anhydrous sodium sulfate which is 3.5 times of the mass of the yellow crude product, drying for 2 hours, filtering, and evaporating under reduced pressure at 0.01MPa and 110 ℃ until the water is evaporated to obtain the bromo-diheptyl indole carbazole.
Further, the spinning temperature in the step (2) is 26 ℃, the core liquid flow rate is 7.2mL/min, and the spinning pressure is 0.12 MPa.
Example 3
A light anti-scorching conductive shielding material mainly comprises the following components in parts by weight: 65 parts of metal copper nano fiber, 7 parts of self-made additive, 78 parts of epoxy resin and 2 parts of curing agent.
A preparation method of a light anti-scorching conductive shielding material mainly comprises the following preparation steps:
(1) adding butyric acid amino acetamide dibutyl alcohol and acetonitrile which is 3.6 times of the mass of butyric acid amino acetamide dibutyl alcohol into a three-neck flask, stirring and dissolving, adding dichloro methyl phosphate which is 0.7 times of the mass of butyric acid amino acetamide dibutyl alcohol at the speed of 0.15mL/min, reacting for 1h at 18 ℃, heating to 150 ℃, reacting for 9h, cooling to room temperature, carrying out reduced pressure distillation at the temperature of 0.06MPa and 82 ℃ for 12min, washing for 5 times by using dichloromethane, and carrying out vacuum drying at the temperature of 265Pa and 60 ℃ for 4h to obtain butyric acid amino acetamide dibutyl methyl phosphate;
(2) adding amino ethyl biphenyl boric acid ester, butyric acid amino acetamide dibutyl phosphate with 3.7 times of the mass of the amino ethyl biphenyl boric acid ester and toluene with 4.9 times of the mass of the amino ethyl biphenyl boric acid ester into a three-neck flask, stirring at 100rpm, heating to 250 ℃, reacting for 6 hours, carrying out reduced pressure distillation at 0.06MPa and 115 ℃ for 5 minutes, washing for 7 times with tetrahydrofuran, and carrying out vacuum drying at 50 ℃ and 300Pa for 3 hours to obtain an additive;
(3) putting copper powder with the particle size of 3 mu m, dioctyl phthalate with the mass of 0.005 time of the copper powder, polyvinylpyrrolidone with the mass of 0.016 time of the copper powder and methyl pyrrolidone with the mass of 0.27 time of the copper powder into a wide-mouthed bottle, stirring for 30min at 200rpm, adding oxidized polysilicate iron with the mass of 0.021 time of the copper powder into the wide-mouthed bottle every 2h, adding the mixture for 3 times, and stirring for 3h at the same speed to obtain a casting solution; transferring the casting solution into a spinning tank, sealing the spinning tank, vacuumizing for 1h, spraying the casting solution from a spinning head under the nitrogen atmosphere, simultaneously, punching a deionized water core solution from an inner hole of a spinning nozzle, soaking the spinning nozzle in a tap water external solidification solution for 24h, straightening and drying at room temperature to obtain a precursor; fixing one end of the precursor on a rotating head on a rotating motor by using glue, bonding the other end of the precursor on a freely movable weight by using the glue, pulling the weight far away from the motor by 20cm, and rotating the motor for 2min at the speed of 300rpm to obtain the metal copper nanofiber;
(4) adding the metal copper nanofiber and the self-made additive into a mold according to the formula amount under the nitrogen atmosphere, adding the epoxy resin and the curing agent according to the formula amount at 60 ℃, maintaining the pressure for 10min at 0.1MPa, maintaining the pressure for 10min at 0.2MPa, heating to 90 ℃, curing for 4h, demolding, placing in an intermittent foaming high-pressure reaction kettle, foaming for 30s at 125 ℃ under the condition of absorbing carbon dioxide gas pressure of 12MPa, and rapidly cooling to room temperature to obtain the conductive shielding material.
Further, the preparation method of butyric acid amino acetamide dibutyl alcohol in the step (1) comprises the following steps: adding methyl butyrate and ethylenediamine butanol with the mass of 2.2 times of that of the methyl butyrate into a three-necked bottle, stirring at the speed of 100rpm, heating to 100 ℃, adding sodium methoxide with the mass of 0.013 times of that of the methyl butyrate, controlling the temperature at 120 ℃, reacting for 2 hours, cooling to room temperature, adding petroleum ether with the mass of 4.5 times of that of the methyl butyrate, uniformly stirring, performing suction filtration, adding deionized water with the mass of 3.2 times of that of the methyl butyrate, stirring at the speed of 50rpm, heating until the solution is viscous, filtering, cooling to room temperature, performing vacuum filtration under the pressure of 0.05MPa, washing with the deionized water for 3 times, and drying at the temperature of 37 ℃ for 4 hours to obtain the butylaminoacetamide dibutyl alcohol.
Further, the spinning temperature in the step (3) is 26 ℃, the core liquid flow rate is 7.2mL/min, and the spinning pressure is 0.12 MPa.
Example 4
A light anti-scorching conductive shielding material mainly comprises the following components in parts by weight: 65 parts of copper powder, 7 parts of self-made additives, 4 parts of self-conducting polymers, 78 parts of epoxy resin and 2 parts of curing agents.
A preparation method of a light anti-scorching conductive shielding material mainly comprises the following preparation steps:
(1) adding butyric acid amino acetamide dibutyl alcohol and acetonitrile which is 3.6 times of the mass of butyric acid amino acetamide dibutyl alcohol into a three-neck flask, stirring and dissolving, adding dichloro methyl phosphate which is 0.7 times of the mass of butyric acid amino acetamide dibutyl alcohol at the speed of 0.15mL/min, reacting for 1h at 18 ℃, heating to 150 ℃, reacting for 9h, cooling to room temperature, carrying out reduced pressure distillation at the temperature of 0.06MPa and 82 ℃ for 12min, washing for 5 times by using dichloromethane, and carrying out vacuum drying at the temperature of 265Pa and 60 ℃ for 4h to obtain butyric acid amino acetamide dibutyl methyl phosphate;
(2) adding amino ethyl biphenyl boric acid ester, butyric acid amino acetamide dibutyl phosphate with 3.7 times of the mass of the amino ethyl biphenyl boric acid ester and toluene with 4.9 times of the mass of the amino ethyl biphenyl boric acid ester into a three-neck flask, stirring at 100rpm, heating to 250 ℃, reacting for 6 hours, carrying out reduced pressure distillation at 0.06MPa and 115 ℃ for 5 minutes, washing for 7 times with tetrahydrofuran, and carrying out vacuum drying at 50 ℃ and 300Pa for 3 hours to obtain an additive;
(3) adding diphenoxypinacol diborate, dibromo dinitrobenzothiadiazole with the mass of 0.5 time of that of the diphenoxypinacol diborate, bromo diheptyl indole carbazole with the mass of 1.2 times of that of the diphenoxypinacol diborate, and potassium carbonate/toluene solution with the mass of 3.6 times of that of the diphenoxypinacol diborate into a three-mouth bottle, the mass ratio of potassium carbonate to toluene in the potassium carbonate/toluene solution is 2:3, after uniform stirring, adding tetrakis (triphenylphosphino) palladium with the mass of 0.165 time of that of the dipivalonic acid and tetra-n-butylammonium fluoride with the mass of 0.002 time of that of the dipivalonic acid, stirring and reacting at 90 ℃ under argon atmosphere and 100rpm for 48h, cooling to room temperature, rotary steaming at 200rpm and 115 deg.C for 30min, adding trichloromethane 2.1 times of dipivalonic acid and extracting for 8 times, performing rotary evaporation at 200rpm and 80 ℃ for 15min, and performing suction filtration to obtain a conductive polymer;
(4) adding copper powder and a self-made additive into a mold according to the formula amount under the nitrogen atmosphere, adding epoxy resin and a curing agent according to the formula amount at 60 ℃, maintaining the pressure for 10min at 0.1MPa and then at 0.2MPa for 10min, heating to 90 ℃, curing for 4h, and demolding to obtain the conductive shielding material.
Further, the preparation method of butyric acid amino acetamide dibutyl alcohol in the step (1) comprises the following steps: adding methyl butyrate and ethylenediamine butanol with the mass of 2.2 times of that of the methyl butyrate into a three-necked bottle, stirring at the speed of 100rpm, heating to 100 ℃, adding sodium methoxide with the mass of 0.013 times of that of the methyl butyrate, controlling the temperature at 120 ℃, reacting for 2 hours, cooling to room temperature, adding petroleum ether with the mass of 4.5 times of that of the methyl butyrate, uniformly stirring, performing suction filtration, adding deionized water with the mass of 3.2 times of that of the methyl butyrate, stirring at the speed of 50rpm, heating until the solution is viscous, filtering, cooling to room temperature, performing vacuum filtration under the pressure of 0.05MPa, washing with the deionized water for 3 times, and drying at the temperature of 37 ℃ for 4 hours to obtain the butylaminoacetamide dibutyl alcohol.
Further, the preparation method of the bromo-diheptyl indole carbazole in the step (3) comprises the following steps:
a. adding indole, p-bromobenzaldehyde with the mass of 1.6 times of that of the indole and acetonitrile with the mass of 33.7 times of that of the indole into a round-bottom flask, stirring until the indole is dissolved, adding hydroiodic acid solution with the mass fraction of 57 percent, which is 1.4 times of that of the indole, at the speed of 6 drops/min, reacting for 24 hours, cooling to room temperature, performing suction filtration, and washing for 3 times by using the acetonitrile to obtain a yellow solid; adding the yellow solid and acetonitrile with 22.4 times of indole mass into a round-bottom flask, stirring at 80 ℃ and 100rpm for reaction for 24h, then carrying out rotary evaporation at 200rpm and 60 ℃ for 13min, carrying out suction filtration, and washing with acetonitrile for 3 times to obtain a yellow crude product;
b. adding a yellow crude product, ethylhexyl bromide which is 1.4 times of the mass of the yellow crude product, tetrabutylammonium bromide which is 0.056 times of the mass of the yellow crude product, dimethyl sulfoxide which is 15.4 times of the mass of the yellow crude product, and a sodium hydroxide solution which is 12.8 times of the mass of the yellow crude product and has the mass fraction of 50% into a round-bottomed flask, stirring at 50 ℃ and 120rpm for 24 hours, adding saturated saline which is 79.8 times of the mass of the yellow crude product, adding hydrochloric acid with the mass fraction of 10% until the pH of the solution is 7, extracting, adding anhydrous sodium sulfate which is 3.5 times of the mass of the yellow crude product, drying for 2 hours, filtering, and evaporating under reduced pressure at 0.01MPa and 110 ℃ until the water is evaporated to obtain the bromo-diheptyl indole carbazole.
Comparative example
A light anti-scorching conductive shielding material mainly comprises the following components in parts by weight: 65 parts of copper powder, 78 parts of epoxy resin and 2 parts of curing agent.
A preparation method of a light anti-scorching conductive shielding material mainly comprises the following preparation steps: under the atmosphere of nitrogen, controlling the temperature at 60 ℃, adding copper powder, epoxy resin and a curing agent according to the formula amount, keeping the pressure at 0.1MPa for 10min, keeping the pressure at 0.2MPa for 10min, heating to 90 ℃, curing for 4h, and demolding to obtain the conductive shielding material.
Examples of effects
Table 1 below gives the results of performance analysis of the lightweight scorch-resistant conductive shielding materials using examples 1 to 4 of the present invention and comparative examples.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example | |
| Flame retardant rating | V-0 | HB | V-0 | V-0 | HB |
| Percentage of weight loss in pickling (%) | 15.9 | 60.6 | 16.1 | 16.0 | 61.3 |
| Percentage of weight loss in caustic soda (%) | 13.8 | 58.9 | 14.0 | 14.1 | 58.7 |
| Electromagnetic shielding performance (dB) | 68 | 66 | 40 | 32 | 25 |
Compared with the experimental data of the comparative example, the experimental data of the embodiment 1 shows that the corrosion resistance and the flame retardance of the product can be effectively improved by adding the self-made additive into the product, the product is made into a foam hole shape by taking the spiral hollow metal copper nano fiber as a framework, and the self-conducting polymer is coated in the micropores, so that the conductivity of the product is effectively improved, and the high electromagnetic shielding performance of the product is realized; compared with the experimental data of the embodiment 1 and the embodiment 2, the experiment data shows that the self-made additive is not used, so that the product combustion process is caused, a compact carbon layer cannot be formed, the flame retardance of the product is influenced, the metal copper nano fiber cannot be protected, the corrosion of acid and alkali substances cannot be prevented, and the corrosion resistance of the product is reduced; from the comparison of the experimental data of the embodiment 1 and the embodiment 3, it can be found that the conductive network can not be formed with the metal copper nano-fiber without using the self-conductive polymer, and the conductivity of the product is influenced, so that the electromagnetic shielding performance of the product is reduced; from the comparison of the experimental data of the embodiment 1 and the embodiment 4, it can be found that the product is not made into a bubble shape, and cannot reflect electromagnetic waves, and meanwhile, the conductive substance inside the product cannot form a conductive network due to no addition of the helical hollow metal copper nanofiber, thereby affecting the electromagnetic shielding performance of the product.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (9)
1. The light anti-scorching conductive shielding material is characterized by mainly comprising, by weight, 50-80 parts of metal copper nanofibers, 5-10 parts of a self-made additive, 3-8 parts of a self-conducting polymer, 60-100 parts of epoxy resin and 1-3 parts of a curing agent.
2. The lightweight scorch resistant conductive shielding material of claim 1, wherein the homemade additive is prepared from butylaminoacetamide dibutanol, methyl dichlorophosphate, and aminoethylbiphenyl borate.
3. The light-weight scorch-resistant conductive shielding material according to claim 2, wherein the self-conducting polymer is prepared by coupling and polymerizing bromide of bromo-diheptyl indole carbazole and dibromo-bis-nitro-benzothiadiazole.
4. The light-weight scorch-resistant conductive shielding material according to claim 3, wherein the curing agent is one or a mixture of aminoethyl piperazine, isophorone diamine, m-phenylenediamine or ethylenediamine.
5. The light-weight scorch-resistant conductive shielding material according to claim 4, wherein the conductive shielding material comprises the following raw material components in parts by weight: 65 parts of metal copper nano fiber, 7 parts of self-made additive, 4 parts of self-conducting polymer, 78 parts of epoxy resin and 2 parts of curing agent.
6. A preparation method of a light anti-scorching conductive shielding material is characterized by mainly comprising the following preparation steps:
(1) adding 3.6 times of acetonitrile in mass of butyric acid amino acetamide dibutyl alcohol and butyric acid amino acetamide dibutyl alcohol into a three-neck flask, stirring and dissolving, adding 0.7 times of methyl dichlorophosphate in mass of butyric acid amino acetamide dibutyl alcohol at a speed of 0.15-0.2 mL/min, reacting at 15-20 ℃ for 1h, heating to 150 ℃, reacting for 9h, cooling to room temperature, distilling at 0.06MPa and 82 ℃ under reduced pressure for 10-14 min, washing with dichloromethane for 3-5 times, and vacuum drying at 250-300 Pa and 60 ℃ for 3-4 h to obtain butyric acid amino acetamide dibutyl phosphate;
(2) adding amino ethyl biphenyl boric acid ester, butyric acid amino acetamide dibutyl phosphate with 3.7 times of the mass of the amino ethyl biphenyl boric acid ester and toluene with 4.9 times of the mass of the amino ethyl biphenyl boric acid ester into a three-neck flask, stirring at the speed of 100rpm, heating to 250 ℃, reacting for 5-6 h, carrying out reduced pressure distillation at the temperature of 0.06MPa and 115 ℃ for 3-5 min, washing for 5-7 times with tetrahydrofuran, and carrying out vacuum drying at the temperature of 50 ℃ and 250-300 Pa for 3-4 h to obtain an additive;
(3) adding diphenoxy phenyl diboronate, dibromo dinitro benzothiadiazole with the mass of 0.5 time of that of diphenoxy phenyl diboronate, bromo diheptyl indole carbazole with the mass of 1.2 times of that of diphenoxy phenyl diboronate, potassium carbonate/toluene solution with the mass of 3.6 times of that of diphenoxy phenyl diboronate into a three-mouth bottle, wherein the mass ratio of potassium carbonate to toluene in the potassium carbonate/toluene solution is 2:3, stirring uniformly, adding tetrakis (triphenylphosphine) palladium with the mass of 0.165 time of that of diphenoxy phenyl diboronate and tetra-n-butylammonium fluoride with the mass of 0.002 time of that of diphenoxy phenyl diboronate, stirring and reacting at the speed of 100rpm under the temperature of 90 ℃ under the argon atmosphere, cooling to room temperature, steaming for 20-30 min at the speed of 200rpm and 115 ℃, adding trichloromethane with the mass of 2.1 time of diphenoxy phenyl diboronate, extracting for 6-8 times, steaming at the temperature of 200rpm and 80 ℃ for 10-15 min, and filtering, derived from a conducting polymer;
(4) putting copper powder with the particle size of 3 mu m, dioctyl phthalate with the mass of 0.005 time of the copper powder, polyvinylpyrrolidone with the mass of 0.016 time of the copper powder and methyl pyrrolidone with the mass of 0.27 time of the copper powder into a wide-mouthed bottle, stirring for 30min at 200rpm, adding oxidized polysilicate iron with the mass of 0.021 time of the copper powder into the wide-mouthed bottle every 2h, adding the mixture for 3 times, and stirring for 3h at the same speed to obtain a casting solution; transferring the casting solution into a spinning tank, sealing the spinning tank, vacuumizing for 1h, spraying the casting solution from a spinning head under the nitrogen atmosphere, simultaneously, punching a deionized water core solution from an inner hole of a spinning nozzle, soaking the spinning nozzle in a tap water external solidification solution for 24h, straightening and drying at room temperature to obtain a precursor; fixing one end of the precursor on a rotating head on a rotating motor by using glue, bonding the other end of the precursor on a freely movable weight by using the glue, pulling the weight far away from the motor by 20cm, and rotating the motor for 2min at the speed of 300rpm to obtain the metal copper nanofiber;
(5) adding metal copper nanofibers and a self-made additive into a mold according to the formula amount under the nitrogen atmosphere, adding epoxy resin and a curing agent according to the formula amount at 60 ℃, keeping the pressure for 10min under 0.1MPa, keeping the pressure for 10min under 0.2MPa, heating to 90 ℃, curing for 4h, demolding, placing into an intermittent foaming high-pressure reaction kettle, foaming for 25-45 s under the conditions of 125 ℃ and the carbon dioxide gas adsorption pressure of 12MPa, rapidly cooling to room temperature, soaking in an auto-conductive polymer aqueous solution with the mass of 0.2-0.5 time of that of the metal copper nanofibers for 3-5 h, drying for 5-7 h at room temperature, and obtaining the conductive shielding material.
7. The method for preparing a light scorch-resistant conductive shielding material according to claim 6, wherein the method for preparing butyric aminoacetamide dibutanol in step (1) comprises: adding methyl butyrate and ethylenediamine butanol with the mass of 2.2 times of that of the methyl butyrate into a three-necked bottle, stirring at the speed of 100rpm, heating to 100 ℃, adding sodium methoxide with the mass of 0.013 times of that of the methyl butyrate, controlling the temperature to be 115-125 ℃, reacting for 2-3 hours, cooling to room temperature, adding petroleum ether with the mass of 4.5 times of that of the methyl butyrate, uniformly stirring, performing suction filtration, adding deionized water with the mass of 3.2 times of that of the methyl butyrate, stirring at the speed of 50rpm, heating until the solution is viscous, filtering, cooling to room temperature, performing vacuum filtration under the pressure of 0.05MPa, washing with the deionized water for 2-3 times, and drying at the temperature of 30-40 ℃ for 3-5 hours to obtain the butylaminoacetamide dibutyl alcohol.
8. The method for preparing a lightweight scorch-resistant conductive shielding material according to claim 7, wherein the bromo-diheptyl indole carbazole in the step (3) is prepared by:
a. adding indole, p-bromobenzaldehyde with the mass of 1.6 times of that of the indole and acetonitrile with the mass of 33.7 times of that of the indole into a round-bottom flask, stirring until the indole is dissolved, adding hydroiodic acid solution with the mass fraction of 57% with the mass of 1.4 times of that of the indole at the speed of 5-6 drops/min, reacting for 24 hours, cooling to room temperature, performing suction filtration, and washing for 2-3 times with the acetonitrile to obtain a yellow solid; adding a yellow solid and acetonitrile with 22.4 times of indole mass into a round-bottom flask, stirring at 80 ℃ and 100rpm for reaction for 24 hours, carrying out rotary evaporation at 200rpm and 60 ℃ for 10-15 min, carrying out suction filtration, and washing with acetonitrile for 3 times to obtain a yellow crude product;
b. adding a yellow crude product, ethylhexyl bromide which is 1.4 times of the mass of the yellow crude product, tetrabutylammonium bromide which is 0.056 times of the mass of the yellow crude product, dimethyl sulfoxide which is 15.4 times of the mass of the yellow crude product, and a sodium hydroxide solution which is 12.8 times of the mass of the yellow crude product and has a mass fraction of 50% into a round-bottomed flask, stirring at 50 ℃ and 120rpm for 24 hours, adding saturated saline which is 79.8 times of the mass of the yellow crude product, adding hydrochloric acid with a mass fraction of 10% until the pH of the solution is 6-7, extracting, adding anhydrous sodium sulfate which is 3.5 times of the mass of the yellow crude product, drying for 1-2 hours, filtering, and evaporating under reduced pressure at 0.01MPa and 110 ℃ until the water is evaporated to obtain the bromo-diheptyl indole carbazole.
9. The method for preparing a light-weight anti-scorching conductive shielding material according to claim 8, wherein the spinning temperature in step (4) is 26 ℃, the core liquid flow rate is 7.2mL/min, and the spinning pressure is 0.12 MPa.
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