CN113956606A - Carbon nano composite wave-absorbing heat-insulating phenolic foam material and preparation method thereof - Google Patents
Carbon nano composite wave-absorbing heat-insulating phenolic foam material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to carbon-based electromagnetic protection materials and heat-insulating functional materials, and particularly relates to a carbon nano composite wave-absorbing heat-insulating phenolic foam material and a preparation method thereof, wherein the carbon nano composite wave-absorbing heat-insulating phenolic foam material comprises the following raw materials in percentage by mass: 100 parts of phenolic resin, 10-20 parts of foaming agent, 2-15 parts of curing agent, 1-30 parts of wave absorbing agent, 5-15 parts of surfactant, 2-10 parts of flame retardant, 1-5 parts of filler and 10-20 parts of modifier. The invention gives full play to the formulation composition and design advantages of the phenolic resin foam and carbon nano tube composite material, and the addition amount is obviously reduced due to the high specific surface area and the nano effect of the nano carbon material, thereby showing obvious difference in formulation design.
Description
The invention belongs to carbon-based electromagnetic protection materials and heat-insulating functional materials, and particularly relates to a carbon nano composite wave-absorbing heat-insulating phenolic foam material and a preparation method thereof.
Background
In the information age, with the continuous improvement of the informatization degree, various electronic devices and systems, and various household appliances are rapidly popularized; the rapid development of urban transportation and power systems such as automobiles, electric cars, subways, electric railways and the like causes the rapid rise of environmental electromagnetic radiation and electromagnetic interference, so that the electromagnetic pollution becomes the fourth pollution following water pollution, air pollution and noise pollution. The ubiquitous electromagnetic radiation not only brings the problems of electromagnetic interference and electromagnetic compatibility of equipment and a system, but also brings potential threats to the physical and mental health of human beings. Electromagnetic waves radiated by electronic information instruments and equipment during working can interfere the normal work of peripheral instruments and equipment, influence the reduction of system performance, cause the failure of an automatic control system, information transmission errors and the like, and cause unpredictable catastrophic results. Electromagnetic radiation has different degrees of influence on human vision, endocrine, reproduction and heredity, body immune function, central nervous system and the like, and particularly after high-frequency waves and a strong electromagnetic field act on a human body, the human body unconsciously causes the reduction of energy and physical strength, makes human biological clocks disordered, lowers the memory, thinking and judgment abilities and the like, and even causes certain pathological changes. Increasingly complex electromagnetic environments and the influence on human life are very important for all countries in the world, and in order to protect the environment, human health and guarantee electronic information safety, electromagnetic radiation must be protected, and the protection of electromagnetic radiation pollution is very slow. The rational use of electromagnetic shielding materials is the most fundamental way to address electromagnetic radiation contamination.
On the other hand, in addition to the electromagnetic environment, the electronic devices and systems are in a complex internal and external climate environment, which easily causes a rapid change in internal and external temperature difference, and also brings a harsh environment to the internal electronic devices and instruments, thereby reducing the service life or causing a failure. Taking a vehicle as an example, during the operation period, the climate type is multiple, the change of the environmental temperature and the solar radiation intensity is large when the vehicle crosses geographical areas with various climate conditions in China, and the climate environment is more variable when the vehicle passes through high-temperature and high-cold environments, such as environments crossing oceans, sky, space and the like. Therefore, it is necessary to provide heat insulation performance. The traditional heat-insulating material is mainly made of foam plastics such as polyurethane and the like, and the material does not have the function of protecting electromagnetic radiation.
Based on the background of the application requirements, electromagnetic shielding material researches mainly for electromagnetic wave reflection are firstly carried out at home and abroad. Firstly, a surface conductive film is used for a high polymer material substrate, but once the conductive film is damaged, the shielding effect of the conductive film is influenced; then, the conductive filler is compounded in the process of processing and forming the high polymer material, so that the processing and shielding of the high polymer material are completed at one time, but the influence factors are more complex, including the properties, the forms, the filling amounts, the dispersion degrees and the like of the conductive filler and the matrix material, and are closely related to the shielding effect of the high polymer composite material.
In addition, the material products mainly comprise thermoplastic resin matrixes. Such as Nippon Bell textile, Nippon Hitachi chemical, American cyanamide, Mitsubishi rayon, etc., respectively carry out conductive modification on resin matrixes such as polycarbonate, ABS, nylon 6, polypropylene, polyvinyl chloride, polystyrene, ABS, polypropylene, etc., and modifiers mainly comprise Al, Fe fibers, stainless steel fibers, Cu fibers, nickel-plated graphite fibers, ultrafine carbon black, etc., so that the modified resin matrixes show certain shielding performance against electromagnetic radiation. However, since metal materials are mainly used, they have disadvantages such as high density, heavy weight, and easy corrosion.
Since the discovery of novel carbon nano materials such as Carbon Nanotubes (CNTs) and graphene, the carbon nano materials have excellent strength, hardness, elasticity, and good thermal and electrical properties due to their special structural characteristics, and are widely used as functional additives for preparing high-performance composite materials, such as in the fields of applications and energy storage, and also in the fields of electromagnetic protection, such as shielding and absorption of electromagnetic waves, the carbon nano materials have significant advantages. In addition, in recent years, research, development and application of graphene materials are also receiving more and more extensive attention, and graphene shows certain advantages in the aspect of electromagnetic radiation protection due to the excellent structural characteristics of graphene. However, around the performance research of carbon nano materials, carbon nano powder materials are mainly used. The combined research of the carbon nano material and the resin foam is rarely reported. And in mature products, the compounding of carbon black and polyurethane foam is also mainly performed.
Disclosure of Invention
Aiming at the technical problems, the invention provides a carbon nano composite wave-absorbing and heat-insulating phenolic foam material and a preparation method thereof, which modify a phenolic matrix to ensure that the phenolic matrix has the characteristics of heat insulation and electromagnetic wave-absorbing function so as to play the synergistic function of wave absorption and heat insulation.
In order to solve the technical problems, the invention adopts the technical scheme that:
a carbon nano composite wave-absorbing heat-insulating phenolic foam material comprises the following raw materials in percentage by mass: 100 parts of phenolic resin, 10-20 parts of foaming agent, 2-15 parts of curing agent, 1-30 parts of wave absorbing agent, 5-15 parts of surfactant, 2-10 parts of flame retardant, 1-5 parts of filler and 10-20 parts of modifier.
The phenolic resin may be replaced with 100 parts of resole.
The phenolic resin comprises the following raw materials: phenol, formaldehyde, catalyst and hydrochloric acid; the mol ratio of the raw materials is 5: 5-15: 0.05-05: 0.1 to 0.5; the hydrochloric acid may be replaced by sulfuric acid.
The catalyst adopts any one of sodium hydroxide, potassium hydroxide and barium hydroxide.
The foaming agent is any one of petroleum ether, ethane, n-butane and sodium bicarbonate;
the curing agent is any one of hydrochloric acid, sulfuric acid, phosphoric acid and benzene sulfonic acid;
the wave absorbing agent is any one or more of carbon nano tube, graphene and carbon aerogel;
the surfactant is any one of fatty alcohol-polyoxyethylene ether, polyoxyethylene sorbitan fatty acid ester and an organic silicon compound containing polyoxyethylene ether;
the flame retardant is one or a combination of aluminum hydroxide and magnesium hydroxide;
the filler is calcium carbonate filler;
the modifier is any one of ethylene glycol, polyethylene glycol, polyamide, polystyrene and nitrile rubber.
A preparation method of a carbon nano composite wave-absorbing heat-insulating phenolic foam material comprises the following steps:
s1, weighing the following raw materials: phenolic resin, a foaming agent, a curing agent, a wave absorbing agent, a surfactant, a flame retardant, a filler and a modifier;
s2, dispersing and mixing: dispersing and mixing the raw materials weighed in the S1 to obtain a material;
s3, injection into a mold cavity and foaming molding: and (4) placing the material obtained in the step (S2) in a mould, moving the mould into a constant temperature box, and foaming to obtain the carbon nano composite wave-absorbing heat-insulating phenolic foam material.
In said S2: sequentially placing the medium phenolic resin, the surfactant, the wave absorbing agent, the flame retardant, the foaming agent and the curing agent in a stirrer, and fully and uniformly mixing the medium phenolic resin, the surfactant, the wave absorbing agent, the flame retardant, the foaming agent and the curing agent by high-speed stirring or a ball mill at room temperature below 30 ℃; and during high-speed stirring, ball milling and dispersing the carbon nano wave absorbing agent in advance, wherein the ball milling rotation speed is 500-1000 rpm, the temperature is controlled at 10-25 ℃, and the time is 10-60 min.
In said S3: controlling the temperature to be 30-90 ℃ and the time to be 60-120 min, and foaming.
The phenolic resin in the S1 is prepared by adopting the following method: placing phenol and formaldehyde into a reaction vessel, and heating to 50-60 ℃ in a water bath; and then adding a catalyst, continuously heating to 70-90 ℃, reacting for 50-90 min, stopping heating, cooling to 40-60 ℃, gradually adding dilute acid to neutralize acid and alkali until the pH value of the mixed solution reaches 6.5-7.5, and performing reduced pressure dehydration to obtain the phenolic resin.
By repeating the steps from S1 to S3, the preparation of double-layer or multi-layer carbon nano composite wave-absorbing heat-insulating phenolic foam materials can be carried out, and all the layers of the carbon nano composite wave-absorbing heat-insulating phenolic foam materials are bonded through epoxy glue.
Compared with the prior art, the invention has the following beneficial effects:
the invention carries out the design of a phenolic resin foam modification formula based on a carbon nano tube and graphene composite wave absorbing agent, and the wave absorbing agent is well dispersed in a phenolic resin foam matrix through the overall design of components and proportions such as resin, a curing agent, the wave absorbing agent, a modifying agent, a foaming agent, a surfactant and the like, so as to obtain the optimal foaming composite process conditions, and mainly realize the uniform dispersion of the carbon nano tube and graphene composite wave absorbing agent and the electromagnetic wave absorbing and heat insulating functions after the carbon nano tube and graphene composite wave absorbing agent is compounded with phenolic resin foam.
Carbon black, carbon nanotubes and graphene in the carbon material can be used as a wave absorbing agent and are often used independently. In the existing products, carbon black is mainly used as a wave absorbing agent, and the wave absorbing foam material is mainly obtained by preparing the carbon black into wave absorbing slurry and then carrying out secondary compounding with polyurethane foam by an impregnation method; carbon nano tubes and graphene as wave absorbing agents stay in the stage of basic research paper publication, and mainly the wave absorbing performance is obtained by mixing carbon nano powder materials and paraffin and calculating through extracting electromagnetic parameters.
After the resin material is comprehensively compared, the obtained phenolic resin has good carbonization flame-retardant effect, and the flame-retardant effect of the resin is further improved by adding the synergistic flame retardant of aluminum hydroxide and magnesium hydroxide; the wave absorbing agent is made of carbon nano materials such as carbon nano tubes, graphene or carbon aerogel, and the microstructure of the wave absorbing agent is further improved in the aspect of wave absorbing performance due to the spherical nano particles of the carbon black.
The invention provides a multifunctional phenolic resin foam, and obtains good wave absorbing performance through the introduction of a wave absorbing agent on the basis of heat insulation performance, and the wave absorbing agent shows a light weight characteristic.
The invention gives full play to the formulation composition and design advantages of the phenolic resin foam and carbon nano tube composite material, and the addition amount is obviously reduced due to the high specific surface area and the nano effect of the nano carbon material, thereby showing obvious difference in formulation design.
By means of the preparation process and optimization of the phenolic resin and the foaming system thereof, the problems of dispersibility and multi-functionalization of the carbon nano material in a resin matrix are solved to a certain extent, and the carbon nano composite wave-absorbing heat-insulating phenolic foam material is developed. According to the structural characteristics and the formula composition, the electromagnetic wave-absorbing performance with reflectivity less than or equal to-10 dB can be realized, and the frequency range of 1 GHz-40 GHz can be covered.
Drawings
FIG. 1 is a flow chart of the preparation of the present invention;
FIG. 2 is a schematic structural diagram of a flat carbon nanocomposite wave-absorbing heat-insulating phenolic foam material prepared by the method;
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
A carbon nano composite wave-absorbing heat-insulating phenolic foam material comprises the following raw materials in percentage by mass: 100 parts of phenolic resin, 10-20 parts of foaming agent, 2-15 parts of curing agent, 1-30 parts of wave absorbing agent, 5-15 parts of surfactant, 2-10 parts of flame retardant, 1-5 parts of filler and 10-20 parts of modifier.
Further, the phenolic resin may be replaced with 100 parts of resole.
Further, the phenolic resin comprises the following raw materials: phenol, formaldehyde, catalyst and hydrochloric acid; the mol ratio of the raw materials is 5: 5-15: 0.05-05: 0.1 to 0.5; the hydrochloric acid can be replaced by sulfuric acid.
Further, the catalyst is any one of sodium hydroxide, potassium hydroxide and barium hydroxide.
Further, any of petroleum ether, ethane, n-butane, and sodium hydrogen carbonate is used as the blowing agent.
Further, the curing agent is any one of hydrochloric acid, sulfuric acid, phosphoric acid and benzene sulfonic acid.
Further, the wave absorbing agent adopts any one or more of carbon nano tube, graphene and carbon aerogel; preferably: the carbon nano tube, the graphene and the carbon aerogel can be combined according to the mixture ratio of 1 (1-3) to 1-2.
Further, the surfactant is any one of fatty alcohol-polyoxyethylene ether, polyoxyethylene sorbitan fatty acid ester and an organic silicon compound containing polyoxyethylene ether.
Further, the flame retardant is any one or a combination of two of aluminum hydroxide and magnesium hydroxide.
Furthermore, calcium carbonate is used as the filler.
Further, the modifier is any one of ethylene glycol, polyethylene glycol, polyamide, polystyrene and nitrile rubber.
As shown in fig. 1, a method for preparing a carbon nano composite wave-absorbing and heat-insulating phenolic foam material comprises the following steps of taking a composite wave-absorbing agent such as a carbon nano tube, graphene and carbon aerogel as a functional auxiliary agent, compounding phenolic resin, and gradually adding various auxiliary agents in the process to realize that a carbon nano material with a specific structure and composition is distributed in a phenolic resin foam matrix, so as to finally obtain the carbon nano composite wave-absorbing and heat-insulating phenolic foam material:
(1) weighing the ingredients (in mol ratio): 100 parts of phenol and 100-300 parts of formaldehyde which are basic raw materials are measured, 1-10 parts of sodium hydroxide, potassium hydroxide or barium hydroxide and the like are measured to be used as catalysts, and 2-10 parts of hydrochloric acid or sulfuric acid and the like are measured. 0.05 mol is one portion
(2) Placing the phenol and formaldehyde weighed in the step (1) into a reaction vessel, installing a condenser, a stirrer and a thermometer, heating in water bath to 50-60 ℃, adding a sodium hydroxide, potassium hydroxide or barium hydroxide aqueous solution of phenol with a molar ratio of 1-10, continuing to heat to 70-90 ℃, reacting for 50-90 min, stopping heating, cooling to 40-60 ℃, gradually adding dilute acid to neutralize the acid and the alkali until the pH value of the mixed solution reaches 6.5-7.5, and performing reduced pressure dehydration to obtain the phenolic resin.
(3) Weighing the ingredients (by mass): weighing 100 parts of the phenolic resin in the step (2), or directly weighing 100 parts of resol; weighing 10-20 parts of foaming agents such as petroleum ether, ethane, n-butane or sodium bicarbonate and the like; weighing 2-15 parts of curing agents such as hydrochloric acid, sulfuric acid, phosphoric acid or benzenesulfonic acid; weighing 1-30 parts of carbon nano wave absorbers such as carbon nano tubes, graphene or carbon aerogel; weighing 5-15 parts of nonionic surfactants such as fatty alcohol-polyoxyethylene ether, polyoxyethylene sorbitan fatty acid ester (Tween), organic silicon compound containing polyoxyethylene ether and the like; weighing 2-10 parts of aluminum hydroxide, magnesium hydroxide or a combination of the aluminum hydroxide and the magnesium hydroxide as a flame retardant; weighing 1-5 parts of calcium carbonate filler; weighing 10-20 parts of modifying agents such as ethylene glycol or polyethylene glycol, polyamide, polystyrene, nitrile rubber and the like.
(4) Placing the phenolic resin, the surfactant, the wave absorbing agent, the flame retardant, the foaming agent and the curing agent in the step (3) in a stirrer in sequence, and stirring at a high speed or fully mixing uniformly by a ball mill at room temperature below 30 ℃; and during high-speed stirring, ball milling and dispersing the carbon nano wave absorbing agent in advance, wherein the ball milling rotation speed is 500-1000 rpm, the temperature is controlled at 10-25 ℃, and the time is 10-60 min.
(5) And (4) placing the uniformly mixed material in the step (4) into a mold, moving the mold into a constant temperature box, controlling the temperature to be 30-90 ℃ and the time to be 60-120 min, and foaming.
(6) According to the performance requirement, the steps (1) to (5) can be selected and repeated to carry out the preparation process of the double-layer or multi-layer carbon nano composite wave-absorbing heat-insulating phenolic foam material.
Finally, the carbon nano composite wave-absorbing heat-insulating phenolic foam material is obtained.
As shown in fig. 2, the prepared product is a flat plate type material, and the typical dimensions are length × width 18cm × 180cm, 30cm × 30cm, height: 1 cm-5 cm. Of course, the formula and the preparation method of the invention can be used for processing and preparing plane type and special-shaped structure products with different size specifications beyond the typical size specification according to requirements.
Example one
(1) Weighing and proportioning: weighing 470g of phenol and 150-450 g of formaldehyde, weighing 2-20 g of sodium hydroxide as a catalyst, and weighing 2-18 g of hydrochloric acid.
(2) Placing the phenol and formaldehyde weighed in the step (1) into a reaction vessel, installing a condenser, a stirrer and a thermometer, heating in water bath to 50-60 ℃, adding 2-20 g of sodium hydroxide, continuously heating to 70-90 ℃, reacting for 50-90 min, stopping heating, cooling to 40-60 ℃, gradually adding dilute acid to neutralize acid and alkali until the pH value of the mixed solution reaches 6.5-7.5, and performing reduced pressure dehydration to obtain the phenolic resin.
(3) Weighing and proportioning: weighing 100g of phenolic resin in the step (2); weighing 10-20 g of n-butane; weighing 2-15 g of hydrochloric acid; weighing 1-3 g of carbon nano tube or graphene and 1-2 parts of graphene; weighing 5-10 g of polyoxyethylene sorbitan fatty acid ester (Tween); weighing 2-6 g of aluminum hydroxide and 1-4 g of magnesium hydroxide; weighing 1-2 g of calcium carbonate filler; 10-15 g of ethylene glycol is weighed.
(4) Placing the phenolic resin, the tween, the n-butane, the hydrochloric acid, the aluminum hydroxide, the magnesium hydroxide and the calcium carbonate in the step (3) in a stirrer in sequence, and stirring at a high speed or fully mixing uniformly by a ball mill at room temperature below 30 ℃; during high-speed stirring, the carbon nano tubes or graphene are ball-milled and dispersed in advance and then added into a stirrer containing the mixture, the ball-milling rotating speed is 500-800 rpm, the temperature is controlled at 10-25 ℃, and the time is 20-30 min. (the adding sequence is that the liquid materials are mixed firstly, then the solid materials including aluminum hydroxide, magnesium hydroxide, calcium carbonate and carbon nano materials such as carbon nano tubes or graphene which are dispersed in advance are added step by step)
(5) And (4) placing the uniformly mixed material in the step (4) into a mold, moving the mold into a constant temperature box, controlling the temperature to be 30-60 ℃ and the time to be 80-120 min, and foaming.
Finally, the carbon nano composite wave-absorbing heat-insulating phenolic foam material is obtained.
Example two
(1) Weighing and proportioning: weighing 470g of phenol and 150-450 g of formaldehyde, weighing 3-30 g of potassium hydroxide as a catalyst, and weighing 2-20 g of hydrochloric acid.
(2) Placing the phenol and formaldehyde weighed in the step (1) into a reaction vessel, installing a condenser, a stirrer and a thermometer, heating in water bath to 50-60 ℃, adding 3-30 g of potassium hydroxide, continuously heating to 70-90 ℃, reacting for 60-80 min, stopping heating, cooling to 40-50 ℃, gradually adding dilute acid to neutralize acid and alkali until the pH value of the mixed solution reaches 6.5-7.5, and performing reduced pressure dehydration to obtain the phenolic resin.
(3) Weighing and proportioning: weighing 100g of phenolic resin in the step (2); weighing 10-20 g of n-butane; weighing 2-15 g of hydrochloric acid; weighing 1-5 g of carbon nanotubes and 2-5 g of graphene; weighing 5-10 g of polyoxyethylene sorbitan fatty acid ester (Tween); weighing 2-6 g of aluminum hydroxide and 1-4 g of magnesium hydroxide; 10-15 g of ethylene glycol is weighed.
(4) Placing the phenolic resin, tween, n-butane, ethylene glycol, hydrochloric acid, aluminum hydroxide and magnesium hydroxide in the step (3) in a stirrer in sequence, and stirring at a high speed or fully mixing by a ball mill under the condition of room temperature below 30 ℃; during high-speed stirring, the carbon nano tubes and the graphene are ball-milled and dispersed in advance and then are stirred and mixed with the materials in the stirrer, the ball-milling speed is 600-800 rpm, the temperature is controlled at 10-25 ℃, and the time is 30-50 min.
(5) And (4) placing the uniformly mixed material in the step (4) into a mold, moving the mold into a constant temperature box, controlling the temperature to be 40-80 ℃ and the time to be 60-100 min, and foaming.
Finally, the carbon nano composite wave-absorbing heat-insulating phenolic foam material is obtained.
EXAMPLE III
(1) Weighing and proportioning: directly weighing 100g of resol liquid; weighing 10-15 g of foaming agents such as sodium bicarbonate and the like; weighing 2-15 g of hydrochloric acid; weighing 5-10 g of carbon nano tube and graphene; weighing 5-15 g of fatty alcohol-polyoxyethylene ether; weighing 2-10 g of aluminum hydroxide; weighing 1-5 g of calcium carbonate; weighing 10-15 g of polyethylene glycol.
(2) Sequentially placing the resol, the fatty alcohol-polyoxyethylene ether, the polyethylene glycol, the carbon nano tube, the graphene, the sodium bicarbonate, the hydrochloric acid, the aluminum hydroxide and the calcium carbonate in the step (1) into a stirrer, and fully stirring at a high speed and uniformly mixing at room temperature below 30 ℃; the rotation speed is 500-600 rpm, and the time is 30-60 min.
(3) And (3) placing the uniformly mixed material in the step (2) in a mold, moving the mold into a constant temperature box, controlling the temperature to be 30-90 ℃ and the time to be 60-120 min, and foaming to finish the preparation of the first layer of foam material.
(4) Weighing and proportioning: directly weighing 100g of resol liquid; weighing 10-15 g of foaming agents such as sodium bicarbonate and the like; weighing 2-15 g of hydrochloric acid; weighing 1-5 g of carbon nano tube and graphene; weighing 5-15 g of fatty alcohol-polyoxyethylene ether; weighing 2-10 g of aluminum hydroxide; weighing 1-5 g of calcium carbonate; weighing 10-15 g of polyethylene glycol.
(5) Sequentially placing the resol, the fatty alcohol-polyoxyethylene ether, the polyethylene glycol, the carbon nano tube, the graphene, the sodium bicarbonate, the hydrochloric acid, the aluminum hydroxide and the calcium carbonate in the step (4) into a stirrer, and fully stirring at a high speed and uniformly mixing at room temperature below 30 ℃; the rotation speed is 500-600 rpm, and the time is 30-60 min.
(6) And (3) placing the uniformly mixed material in the step (5) in a mold, moving the mold into a constant temperature box, controlling the temperature to be 30-90 ℃ and the time to be 60-120 min, and foaming to obtain a second layer of foam material.
(7) And (3) respectively coating epoxy glue on the upper surface of the first layer and the lower surface of the second layer to finish the bonding of the double-layer material.
Finally obtaining the double-layer carbon nano composite wave-absorbing heat-insulating phenolic foam material. The number of layers may be specifically set according to the functional requirements and application.
The invention prepares a carbon nano composite wave-absorbing and heat-insulating phenolic foam material, which has high-efficiency heat insulation, flame retardance and electromagnetic wave absorption performance, and is mainly characterized in that wave absorbers such as carbon nano tubes, graphene and carbon aerogel materials and the like, and flame retardants such as aluminum hydroxide and magnesium hydroxide and the like are introduced, so that phenolic resin has typical electromagnetic wave-absorbing performance and keeps high flame retardance, the high-efficiency compounding of the phenolic resin and the carbon nano wave-absorbing agent is realized by combining the ball-milling dispersion of the carbon nano material wave absorbers and the optimized process procedures such as high-speed stirring of the phenolic resin and auxiliary agents, different functional agents are introduced at different stages, the compatibility of each agent and a phenolic resin system is ensured, the carbon nano composite wave-absorbing and heat-insulating phenolic foam material has the characteristics of light weight, flame retardance and strong environment resistance in the aspect of use, and the carbon nano composite wave-absorbing and heat-insulating phenolic foam material is used for the electromagnetic radiation protection in the field of increasingly serious electronic information and the energy-saving and heat-insulating phenolic foam material in the construction of a new generation information infrastructure The multiple problems of consumption reduction and electromagnetic radiation protection provide a novel functional integrated electromagnetic/thermal protection material support.
Although only the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art, and all changes are encompassed in the scope of the present invention.
Claims (10)
1. The carbon nano composite wave-absorbing heat-insulating phenolic foam material is characterized by comprising the following raw materials in percentage by mass: 100 parts of phenolic resin, 10-20 parts of foaming agent, 2-15 parts of curing agent, 1-30 parts of wave absorbing agent, 5-15 parts of surfactant, 2-10 parts of flame retardant, 1-5 parts of filler and 10-20 parts of modifier.
2. The carbon nano composite wave-absorbing heat-insulating phenolic foam material as claimed in claim 1, is characterized in that: the phenolic resin may be replaced with 100 parts of resole.
3. The carbon nano composite wave-absorbing heat-insulating phenolic foam material as claimed in claim 1, is characterized in that: the phenolic resin comprises the following raw materials: phenol, formaldehyde, catalyst and hydrochloric acid; the mol ratio of the raw materials is 5: 5-15: 0.05-05: 0.1 to 0.5; the hydrochloric acid may be replaced by sulfuric acid.
4. The carbon nano composite wave-absorbing heat-insulating phenolic foam material as claimed in claim 3, wherein: the catalyst adopts any one of sodium hydroxide, potassium hydroxide and barium hydroxide.
5. The carbon nano composite wave-absorbing heat-insulating phenolic foam material as claimed in claim 1, is characterized in that:
the foaming agent is any one of petroleum ether, ethane, n-butane and sodium bicarbonate;
the curing agent is any one of hydrochloric acid, sulfuric acid, phosphoric acid and benzene sulfonic acid;
the wave absorbing agent is any one or more of carbon nano tube, graphene and carbon aerogel;
the surfactant is any one of fatty alcohol-polyoxyethylene ether, polyoxyethylene sorbitan fatty acid ester and an organic silicon compound containing polyoxyethylene ether;
the flame retardant is one or a combination of aluminum hydroxide and magnesium hydroxide;
the filler is calcium carbonate filler;
the modifier is any one of ethylene glycol, polyethylene glycol, polyamide, polystyrene and nitrile rubber.
6. The preparation method of the carbon nano composite wave-absorbing heat-insulating phenolic foam material of the phenolic foam material according to claim 1 is characterized by comprising the following steps of:
s1, weighing the following raw materials: phenolic resin, a foaming agent, a curing agent, a wave absorbing agent, a surfactant, a flame retardant, a filler and a modifier;
s2, dispersing and mixing: dispersing and mixing the raw materials weighed in the S1 to obtain a material;
s3, injection into a mold cavity and foaming molding: and (4) placing the material obtained in the step (S2) in a mould, moving the mould into a constant temperature box, and foaming to obtain the carbon nano composite wave-absorbing heat-insulating phenolic foam material.
7. The method for preparing the carbon nano composite wave-absorbing heat-insulating phenolic foam material according to claim 6, wherein in S2: sequentially placing the medium phenolic resin, the surfactant, the wave absorbing agent, the flame retardant, the foaming agent and the curing agent in a stirrer, and fully and uniformly mixing the medium phenolic resin, the surfactant, the wave absorbing agent, the flame retardant, the foaming agent and the curing agent by high-speed stirring or a ball mill at room temperature below 30 ℃; and during high-speed stirring, ball milling and dispersing the carbon nano wave absorbing agent in advance, wherein the ball milling rotation speed is 500-1000 rpm, the temperature is controlled at 10-25 ℃, and the time is 10-60 min.
8. The method for preparing the carbon nano composite wave-absorbing heat-insulating phenolic foam material according to claim 6, wherein in S3: controlling the temperature to be 30-90 ℃ and the time to be 60-120 min, and foaming.
9. The preparation method of the carbon nano composite wave-absorbing heat-insulating phenolic foam material as claimed in claim 6, wherein the phenolic resin in S1 is prepared by the following method: placing phenol and formaldehyde into a reaction vessel, and heating to 50-60 ℃ in a water bath; and then adding a catalyst, continuously heating to 70-90 ℃, reacting for 50-90 min, stopping heating, cooling to 40-60 ℃, gradually adding dilute acid to neutralize acid and alkali until the pH value of the mixed solution reaches 6.5-7.5, and performing reduced pressure dehydration to obtain the phenolic resin.
10. The preparation method of the carbon nano composite wave-absorbing heat-insulating phenolic foam material according to claim 6, characterized by comprising the following steps: by repeating the steps from S1 to S3, the preparation of double-layer or multi-layer carbon nano composite wave-absorbing heat-insulating phenolic foam materials can be carried out, and all the layers of the carbon nano composite wave-absorbing heat-insulating phenolic foam materials are bonded through epoxy glue.
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