CN112961462A - Epoxy resin foam plastic and preparation method and application thereof - Google Patents

Epoxy resin foam plastic and preparation method and application thereof Download PDF

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Publication number
CN112961462A
CN112961462A CN202110164410.XA CN202110164410A CN112961462A CN 112961462 A CN112961462 A CN 112961462A CN 202110164410 A CN202110164410 A CN 202110164410A CN 112961462 A CN112961462 A CN 112961462A
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epoxy resin
parts
agent
curing
resin foam
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CN112961462B (en
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王军鹏
齐涛
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Jiangxi Rare Earth Research Institute Chinese Academy Of Sciences
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Jiangxi Rare Earth Research Institute Chinese Academy Of Sciences
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Abstract

The invention provides an epoxy resin foam plastic and a preparation method and application thereof. The epoxy resin foamed plastic comprises the following raw material components in parts by weight: 100 parts of epoxy resin, 5-130 parts of curing agent, 0.5-25 parts of foaming agent, 8-15 parts of heat conducting agent, 0.5-5 parts of coupling agent and 5-20 parts of flame retardant; the heat conducting agent is a mixed solution comprising hexagonal boron nitride nanosheets and polyvinyl alcohol. The preparation method comprises the following steps: and curing the epoxy resin, the curing agent, the foaming agent, the coupling agent, the heat conducting agent and the flame retardant to obtain the epoxy resin foam plastic. The epoxy resin foamed plastic prepared by the invention has better mechanical property and higher thermal conductivity, and is suitable for preparing light sandwich structure composite materials.

Description

Epoxy resin foam plastic and preparation method and application thereof
Technical Field
The invention belongs to the technical field of foamed plastics, and particularly relates to an epoxy resin foamed plastic and a preparation method and application thereof.
Background
The foamed plastic is a kind of high molecular material formed by dispersing a great deal of air hole micropores in solid plastic, and the interior of the foamed plastic is covered with countless communicated or non-communicated micropores so as to obviously reduce apparent density, and has the characteristics of light weight, heat insulation, sound absorption, shock absorption and the like, and the dielectric property is superior to that of matrix resin, so that the foamed plastic has wide application range. Common foams include polyurethane, polystyrene, polyvinyl chloride, polyethylene, epoxy, phenolic foam, and the like. The epoxy resin has excellent mechanical property, thermal property, electrical insulation property, adhesive property, acid and alkali resistance and the like, and is the most commonly used high polymer resin material. The foam material prepared from the epoxy resin not only can exert the original characteristics of the epoxy resin, but also has the characteristics of low density, high strength and damage tolerance, good heat resistance, low moisture absorption rate, small shrinkage rate and the like. Epoxy foam materials are commonly used for manufacturing composite material structures with light weight and high strength sandwich structures, and have wide application in the fields of missile protection, aircraft manufacturing, military vessels, ammunition boxes, packing boxes, aircrafts, offshore structures and the like.
The preparation method of the common epoxy resin foam material comprises three methods, namely a physical foaming method, a chemical foaming method and a hollow microsphere curing and forming method (also called composite foam). The chemical foaming method is a method for preparing foamed plastic by foaming resin by using bubbles generated by substance decomposition or gas generated by chemical reaction among chemical components. Commonly used foaming agents include inorganic foaming agents such as carbonates, water glass, silicon carbide, carbon black and the like, and organic foaming agents such as azo chemicals, hydrazine compounds, nitroso compounds and the like. For the preparation of epoxy resin foam plastics by a chemical foaming method, as the thermal conductivity coefficient of epoxy resin is very small, heat released in the decomposition process of an inorganic foaming agent or an organic foaming agent cannot be effectively transmitted to the outside, so that heat accumulation is caused, temperature runaway in the foaming process is easily caused, the finally obtained epoxy foam is yellowed, the size of air cells is not uniform, the pore diameter distribution is wide, even a plurality of macropores are generated, and the mechanical properties of the epoxy foam materials are reduced and the product batches are unstable.
CN108752871A discloses an epoxy resin foam and a preparation method thereof. The epoxy resin foam comprises the following components in parts by mass: 100 parts of epoxy resin, 5-25 parts of curing agent and 1-20 parts of foaming agent; the molecular structure of the foaming agent contains silicon-nitrogen bonds and silicon-hydrogen bonds; the curing agent is polyamine room temperature curing agent. The epoxy resin foam also comprises: 0-25 parts of diluent, 1-10 parts of surfactant, and 0-5 parts of nano filler and/or chopped fiber. Although the epoxy resin foam provided by the technical scheme has the advantage of low foaming temperature, in the foaming process, heat generated by the reaction between the polyamine room-temperature curing agent and the foaming agent cannot be effectively transmitted to the outside, so that heat accumulation is caused, the epoxy resin foam is yellowed and the air bubble holes are uneven, and the mechanical property and the flame retardance of the epoxy resin foam are poor.
CN104530463A discloses a preparation method of epoxy resin foam plastic. The preparation method comprises the following steps: (1) preheating epoxy resin to 50-70 ℃; (2) adding a foam stabilizer, a foaming agent, an antioxidant and a curing agent into the preheated epoxy resin, and uniformly stirring to obtain a premix; (3) continuously heating the obtained premix to 100-120 ℃ under the condition of stirring; (4) when the premix has the sign of initiation, quickly pouring the premix into a preheated mold, and foaming to form the epoxy resin foam plastic; the foaming agent is water. The technical scheme has the advantages that the foaming temperature is high, and heat cannot be effectively transferred to the outside in the foaming process, so that the prepared epoxy resin foam plastic has uneven bubble holes, poor mechanical property and poor flame retardance.
Therefore, how to provide an epoxy resin foam plastic with good mechanical properties and high thermal conductivity has become a technical problem to be solved urgently at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an epoxy resin foam plastic and a preparation method and application thereof. According to the invention, the mixed solution containing the hexagonal boron nitride nanosheets and the polyvinyl alcohol is used as the heat conducting agent, and the polyvinyl alcohol and the coupling agent are used in a matched manner, so that the prepared epoxy resin foamed plastic has good mechanical property and high thermal conductivity.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an epoxy resin foam plastic, which comprises the following raw material components in parts by weight: 100 parts of epoxy resin, 5-130 parts of curing agent, 0.5-25 parts of foaming agent, 8-15 parts of heat conducting agent, 0.5-5 parts of coupling agent and 5-20 parts of flame retardant;
the heat conducting agent is a mixed solution of hexagonal boron nitride nanosheets and polyvinyl alcohol.
According to the invention, the mixed solution containing the hexagonal boron nitride nanosheets and the polyvinyl alcohol is used as the heat conducting agent, and the hexagonal boron nitride nanosheets are stably dispersed in the mixed solution through Van der Waals force between hydroxyl groups in a polyvinyl alcohol molecular chain and the hexagonal boron nitride nanosheets, so that the agglomeration of the hexagonal boron nitride nanosheets is effectively prevented. In the preparation process of the epoxy resin foamed plastic, the hexagonal boron nitride nanosheet can be used as a good heat conduction passage to effectively transfer heat generated during decomposition of the foaming agent to the outside, so that the problems of uneven size and distribution and poor mechanical property of air cells in the epoxy resin foamed plastic due to heat accumulation are solved.
In the invention, further through the matching use of the polyvinyl alcohol and the coupling agent, the hexagonal boron nitride nanosheet can be stably dispersed in the epoxy resin foam plastic, and the epoxy resin foam plastic has better mechanical property.
In the present invention, the curing agent is 5 to 130 parts by weight, for example, 5 parts, 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, or the like.
The foaming agent is 0.5 to 25 parts by weight, and may be, for example, 0.5 part, 1 part, 2 parts, 5 parts, 7 parts, 10 parts, 13 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, or the like.
The heat conducting agent is 8-15 parts by weight, for example, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts.
The coupling agent is 0.5 to 5 parts by weight, for example, 0.5 part, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts or 5 parts.
The flame retardant is 5 to 20 parts by weight, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the object and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
In a preferred embodiment of the present invention, the epoxy value of the epoxy resin is 0.2 to 0.6 (for example, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, or the like), and more preferably 0.3 to 0.54.
The curing temperature of the curing agent is preferably 100 to 300 ℃ (for example, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃, 240 ℃, 260 ℃, 280 ℃ or 300 ℃), and more preferably 150 to 250 ℃.
Preferably, the curing agent is selected from any one of or a combination of at least two of m-phenylenediamine, dicyandiamide, sebacic dihydrazide, maleic anhydride, phthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride or polyazelaic anhydride.
Preferably, the weight part of the curing agent in the raw material components of the epoxy resin foamed plastic is 30-80 parts, and may be 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts or 80 parts, for example.
In a preferred embodiment of the present invention, the foaming agent is selected from one or a combination of at least two of azodicarbonamide, azobisisobutyronitrile, N '-dinitrosopentamethylenetetramine, 4' -oxybis-benzenesulfonylhydrazide and p-toluenesulfonylhydrazide.
In a preferred embodiment of the present invention, the mass ratio of the hexagonal boron nitride nanosheets to the polyvinyl alcohol is (50-150): 1, and may be, for example, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, 110:1, 120:1, 130:1, 140:1, 150:1, or the like.
According to the invention, the mass ratio of the hexagonal boron nitride nanosheets to the polyvinyl alcohol is controlled within a specific ratio range of (50-150): 1, so that the prepared epoxy resin foamed plastic has good mechanical properties and high thermal conductivity. If the mass of the hexagonal boron nitride nanosheet and the polyvinyl alcohol is relatively small, the thermal conductivity of the prepared epoxy resin foamed plastic is relatively low; if the mass of the hexagonal boron nitride nanosheet and the polyvinyl alcohol is relatively large, the hexagonal boron nitride nanosheet is easy to agglomerate, so that the mechanical property of the prepared epoxy resin foamed plastic is poor.
Preferably, the number of layers of the hexagonal boron nitride nanosheets is 1-20, and may be, for example, 1, 2, 4, 6, 8, 10, 12, 14, 16, 18 or 20.
The polymerization degree of the polyvinyl alcohol is preferably 350 to 4500 (for example, 350, 500, 800, 1000, 1500, 2000, 2500, 3000, 3500, 4000, or 4500), and more preferably 500 to 2000.
Preferably, the concentration of the hexagonal boron nitride nanosheet in the mixed solution is 3 to 100mg/mL (e.g., 3mg/mL, 5mg/mL, 10mg/mL, 20mg/mL, 30mg/mL, 40mg/mL, 50mg/mL, 60mg/mL, 70mg/mL, 80mg/mL, 90mg/mL, 100mg/mL, etc.), and more preferably 5 to 20 mg/mL.
Preferably, the solvent of the mixed solution is water.
As a preferred technical scheme of the invention, the heat conducting agent is obtained by adopting a preparation method which comprises the following steps:
and carrying out ultrasonic treatment on hexagonal boron nitride powder, polyvinyl alcohol and water to obtain the heat conducting agent.
Preferably, the particle size of the hexagonal boron nitride powder is 1 to 30 μm, and may be, for example, 1 μm, 3 μm, 5 μm, 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, 22 μm, 25 μm, 27 μm, or 30 μm.
The preparation method comprises the steps of preparing the heat conducting agent by using hexagonal boron nitride powder with the particle size of 1-30 microns, wherein the hexagonal boron nitride powder, polyvinyl alcohol and water are subjected to ultrasonic treatment, and the hexagonal boron nitride powder is dissociated into hexagonal boron nitride nanosheets, so that the heat conducting agent is obtained finally.
Preferably, the power of ultrasonic treatment is 400-1500W, such as 400W, 500W, 600W, 700W, 800W, 900W, 1000W, 1100W, 1200W, 1300W, 1400W or 1500W.
Preferably, the time of the ultrasonic treatment is 1 to 24 hours (for example, 1 hour, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours or 24 hours), and more preferably 1 to 5 hours.
In a preferred embodiment of the present invention, the coupling agent is a silane coupling agent.
Preferably, the mass ratio of the coupling agent to the polyvinyl alcohol is (500-2200: 1), and may be, for example, 500:1, 700:1, 1000:1, 1200:1, 1400:1, 1600:1, 1800:1, 2000:1, 2200:1, or the like.
According to the invention, through the reaction of the coupling agent and hydroxyl groups in a polyvinyl alcohol molecular chain and further through controlling the mass ratio of the coupling agent to polyvinyl alcohol to be (500-2200): 1 within a specific proportion range, the hexagonal boron nitride nanosheets can be more uniformly dispersed in the epoxy resin foamed plastic, and the epoxy resin foamed plastic with good mechanical property and high thermal conductivity is obtained. If the mass of the coupling agent and the polyvinyl alcohol is smaller, the prepared epoxy resin foamed plastic has poor thermal conductivity; if the mass ratio of the coupling agent to the polyvinyl alcohol is large, the mechanical property of the prepared epoxy resin foam plastic is poor.
In order to calculate the mass ratio of the coupling agent to the polyvinyl alcohol, the density of the mixed solution of the hexagonal boron nitride nanosheet and the polyvinyl alcohol is considered to be 1g/mL in the present invention.
Preferably, the flame retardant is selected from any one of methyl dimethyl phosphate, tributyl phosphate, tris (2-chloroethyl) phosphate or cresyl diphenyl phosphate or a combination of at least two of the same.
In a second aspect, the present invention provides a method for preparing the epoxy resin foam according to the first aspect, the method comprising:
and curing the epoxy resin, the curing agent, the foaming agent, the coupling agent, the heat conducting agent and the flame retardant to obtain the epoxy resin foam plastic.
As a preferred embodiment of the present invention, the curing includes pre-curing and post-curing.
Preferably, the temperature of the pre-curing is 100 to 150 ℃, for example, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃ or 150 ℃ and the like.
Preferably, the pre-curing time is 2 to 6 hours, for example, 2 hours, 2.2 hours, 2.5 hours, 2.7 hours, 3 hours, 3.3 hours, 3.6 hours, 4 hours, 4.2 hours, 4.6 hours, 5 hours, 5.2 hours, 5.5 hours, 5.7 hours or 6 hours, etc.
Preferably, the post-curing temperature is 170 to 250 ℃, and may be, for example, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃ or 250 ℃.
Preferably, the post-curing time is 1 to 24 hours, for example, 1 hour, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours or 24 hours, etc.
Preferably, the method further comprises a pretreatment step before the curing.
Preferably, the pretreatment method comprises the following steps: uniformly mixing the epoxy resin, the curing agent, the foaming agent, the coupling agent, the heat conducting agent and the flame retardant.
As a preferred technical scheme of the invention, the preparation method specifically comprises the following steps:
uniformly mixing epoxy resin, a curing agent, a foaming agent, a coupling agent, a heat conducting agent and a flame retardant, precuring for 2-6 h at 100-150 ℃, then heating to 170-250 ℃, and post-curing for 1-24 h to obtain the epoxy resin foamed plastic.
In a third aspect, the present invention provides the use of an epoxy resin foam as described in the first aspect in a lightweight sandwich structural composite material.
Compared with the prior art, the invention has at least the following beneficial effects:
according to the invention, the mixed solution of hexagonal boron nitride nanosheets and polyvinyl alcohol is used as a heat conducting agent, and further through the matching use of polyvinyl alcohol and a coupling agent, and through controlling the mass ratio of the hexagonal boron nitride nanosheets to the polyvinyl alcohol and the mass ratio of the coupling agent to the polyvinyl alcohol within a specific proportion range, the prepared epoxy resin foamed plastic has good mechanical property and high thermal conductivity, the compression strength is 2.38-2.69 MPa, the tensile strength is 2.02-2.28 MPa, and the thermal conductivity is 1.51-1.89W/(m.K).
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The sources of some of the feed components in the examples and comparative examples are as follows:
epoxy resin: the New chemical materials of Lanxing company, Inc. has no tin resin factory;
hexagonal boron nitride powder: new Material incubator, Inc. of the institute of thawing Industrial, Tianyuan military;
polyvinyl alcohol: shanxi three-dimensional Shengtai New materials science and technology Co., Ltd;
graphite powder: qingdao morning positive graphite, Inc.
Example 1
The embodiment provides an epoxy resin foam plastic and a preparation method thereof, wherein the epoxy resin foam plastic comprises the following raw material components in parts by weight: 100 parts of epoxy resin, 40 parts of maleic anhydride, 20 parts of N, N' -dinitrosopentamethylenetetramine, 10 parts of heat conducting agent, 3 parts of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and 15 parts of methyl dimethyl phosphate;
the epoxy value of the epoxy resin is 0.3; the heat conducting agent is a mixed solution comprising hexagonal boron nitride nanosheets and polyvinyl alcohol; the concentration of the hexagonal boron nitride nanosheet is 20mg/mL, and the mass ratio of the hexagonal boron nitride nanosheet to the polyvinyl alcohol is 100: 1.
The preparation method of the heat conducting agent comprises the following steps:
and performing ultrasonic treatment on hexagonal boron nitride powder, polyvinyl alcohol and water for 2 hours under the power of 600W to obtain the heat-conducting agent.
The preparation method of the epoxy resin foam plastic comprises the following steps:
uniformly mixing epoxy resin, maleic anhydride, N' -dinitrosopentamethylenetetramine, gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, a heat conducting agent and methyl dimethyl phosphate, pre-curing for 3 hours at the temperature of 120 ℃, then heating to 200 ℃, and post-curing for 4 hours to obtain the epoxy resin foamed plastic.
Example 2
The embodiment provides an epoxy resin foam plastic and a preparation method thereof, wherein the epoxy resin foam plastic comprises the following raw material components in parts by weight: 100 parts of epoxy resin, 5 parts of dicyandiamide, 0.5 part of azodicarbonamide, 8 parts of heat conducting agent, 0.5 part of 3-aminopropyltriethoxysilane and 5 parts of dimethyl methyl phosphate;
the epoxy value of the epoxy resin is 0.54; the heat conducting agent is a mixed solution comprising hexagonal boron nitride nanosheets and polyvinyl alcohol; the concentration of the hexagonal boron nitride nanosheet is 12mg/mL, and the mass ratio of the hexagonal boron nitride nanosheet to the polyvinyl alcohol is 50: 1.
The preparation method of the heat conducting agent comprises the following steps:
and carrying out ultrasonic treatment on hexagonal boron nitride powder, polyvinyl alcohol and water for 1h under the power of 1500W to obtain the heat conducting agent.
The preparation method of the epoxy resin foam plastic comprises the following steps:
uniformly mixing epoxy resin, dicyandiamide, azodicarbonamide, 3-aminopropyltriethoxysilane, a heat conducting agent and dimethyl methylphosphonate, precuring for 2h at 100 ℃, then heating to 200 ℃, and post-curing for 1h to obtain the epoxy resin foam plastic.
Example 3
The embodiment provides an epoxy resin foam plastic and a preparation method thereof, wherein the epoxy resin foam plastic comprises the following raw material components in parts by weight: 100 parts of epoxy resin, 130 parts of dodecenyl succinic anhydride, 25 parts of azobisisobutyronitrile, 10 parts of heat conducting agent, 5 parts of 3-mercaptopropyl trimethoxy silane and 20 parts of tributyl phosphate;
the epoxy value of the epoxy resin is 0.5; the heat conducting agent is a mixed solution comprising hexagonal boron nitride nanosheets and polyvinyl alcohol; the concentration of the hexagonal boron nitride nanosheet is 100mg/mL, and the mass ratio of the hexagonal boron nitride nanosheet to the polyvinyl alcohol is 150: 1.
The preparation method of the heat conducting agent comprises the following steps:
and performing ultrasonic treatment on hexagonal boron nitride powder, polyvinyl alcohol and water for 3 hours under the power of 400W to obtain the heat-conducting agent.
The preparation method of the epoxy resin foam plastic comprises the following steps:
uniformly mixing epoxy resin, dodecenyl succinic anhydride, azobisisobutyronitrile, 3-mercaptopropyl trimethoxy silane, a heat conducting agent and tributyl phosphate, precuring for 6 hours at the temperature of 150 ℃, heating to 250 ℃, and post-curing for 24 hours to obtain the epoxy resin foamed plastic.
Example 4
The embodiment provides an epoxy resin foam plastic and a preparation method thereof, wherein the epoxy resin foam plastic comprises the following raw material components in parts by weight: 100 parts of epoxy resin, 80 parts of phthalic anhydride, 15 parts of 4, 4' -oxybis-benzenesulfonyl hydrazide, 15 parts of heat-conducting agent, 1 part of n-propyltriethoxysilane and 15 parts of tris (2-chloroethyl) phosphate;
the epoxy value of the epoxy resin is 0.2; the heat conducting agent is a mixed solution comprising hexagonal boron nitride nanosheets and polyvinyl alcohol; the concentration of the hexagonal boron nitride nanosheet is 5mg/mL, and the mass ratio of the hexagonal boron nitride nanosheet to the polyvinyl alcohol is 70: 1.
The preparation method of the heat conducting agent comprises the following steps:
and performing ultrasonic treatment on hexagonal boron nitride powder, polyvinyl alcohol and water for 2 hours under the power of 800W to obtain the heat-conducting agent.
The preparation method of the epoxy resin foam plastic comprises the following steps:
uniformly mixing epoxy resin, phthalic anhydride, 4' -oxybis-benzenesulfonylhydrazide, n-propyltriethoxysilane, a heat-conducting agent and tris (2-chloroethyl) phosphate, pre-curing for 3h at 120 ℃, then heating to 180 ℃, and post-curing for 8h to obtain the epoxy resin foam plastic.
Example 5
The embodiment provides an epoxy resin foam plastic and a preparation method thereof, wherein the epoxy resin foam plastic comprises the following raw material components in parts by weight: 100 parts of epoxy resin, 30 parts of sebacic dihydrazide, 15 parts of p-toluenesulfonyl hydrazide, 10 parts of a heat conducting agent, 2 parts of gamma-aminopropyltriethoxysilane and 15 parts of diphenyl toluate phosphate;
the epoxy value of the epoxy resin is 0.25; the heat conducting agent is a mixed solution comprising hexagonal boron nitride nanosheets and polyvinyl alcohol; the concentration of the hexagonal boron nitride nanosheet is 20mg/mL, and the mass ratio of the hexagonal boron nitride nanosheet to the polyvinyl alcohol is 120: 1.
The preparation method of the heat conducting agent comprises the following steps:
and performing ultrasonic treatment on hexagonal boron nitride powder, polyvinyl alcohol and water for 2 hours under the power of 1200W to obtain the heat-conducting agent.
The preparation method of the epoxy resin foam plastic comprises the following steps:
uniformly mixing epoxy resin, sebacic dihydrazide, p-toluenesulfonyl hydrazide, gamma-aminopropyl triethoxysilane, a heat conduction agent and cresyl diphenyl phosphate, precuring for 6 hours at the temperature of 100 ℃, heating to 170 ℃, and post-curing for 2 hours to obtain the epoxy resin foam plastic.
Example 6
The present embodiment provides an epoxy resin foam and a preparation method thereof, and the difference from embodiment 1 is that the mass ratio of hexagonal boron nitride nanosheets to polyvinyl alcohol in the thermal conductive agent is 50:1, and the other conditions are the same as those in embodiment 1.
Example 7
The present embodiment provides an epoxy resin foam and a preparation method thereof, and the difference from embodiment 1 is that the mass ratio of hexagonal boron nitride nanosheets to polyvinyl alcohol in the thermal conductive agent is 150:1, and the other conditions are the same as those in embodiment 1.
Example 8
The present embodiment provides an epoxy resin foam and a preparation method thereof, and the difference from embodiment 1 is that the mass ratio of hexagonal boron nitride nanosheets to polyvinyl alcohol in the thermal conductive agent is 30:1, and the other conditions are the same as those in embodiment 1.
Example 9
The present embodiment provides an epoxy resin foam and a preparation method thereof, and the difference from embodiment 1 is that the mass ratio of hexagonal boron nitride nanosheets to polyvinyl alcohol in the thermal conductive agent is 200:1, and the other conditions are the same as those in embodiment 1.
Example 10
This example provides an epoxy resin foam and a method for preparing the same, which is different from example 1 in that the weight part of gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane is 1 part, and the other conditions are the same as example 1.
Example 11
This example provides an epoxy resin foam and a method for preparing the same, which is different from example 1 in that the weight part of gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane is 4.4 parts, and the other conditions are the same as example 1.
Example 12
This example provides an epoxy resin foam and a method for preparing the same, which is different from example 1 in that the weight part of gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane is 0.8 part, and the other conditions are the same as example 1.
Example 13
This example provides an epoxy resin foam and a method for preparing the same, which is different from example 1 in that the weight part of gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane is 5 parts, and the other conditions are the same as example 1.
Example 14
This example provides an epoxy resin foam and a method for producing the same, which are different from example 1 in that 8 parts by weight of a heat conductive agent is used, and the other conditions are the same as example 1.
Example 15
This example provides an epoxy resin foam and a method for producing the same, which are different from example 1 in that the heat conductive agent is 15 parts by weight, and the other conditions are the same as example 1.
Comparative example 1
This comparative example provides an epoxy resin foam and a method for preparing the same, and is different from example 1 in that the heat conductive agent is 6 parts by weight, and the other conditions are the same as example 1.
Comparative example 2
This comparative example provides an epoxy resin foam and a method for preparing the same, and is different from example 1 in that the heat conductive agent is 18 parts by weight, and the other conditions are the same as example 1.
Comparative example 3
This comparative example provides an epoxy resin foam and a method for preparing the same, which are different from example 1 in that a thermal conductive agent is not contained in the epoxy resin foam, and the other conditions are the same as example 1.
Comparative example 4
This comparative example provides an epoxy resin foam and a method for preparing the same, and is different from example 1 in that a heat conductive agent is replaced with graphite powder, and the other conditions are the same as example 1.
Comparative example 5
The present comparative example provides an epoxy resin foam and a preparation method thereof, and differs from example 1 in that hexagonal boron nitride nanosheets in the thermal conductive agent are replaced with graphite powder, and other conditions are the same as in example 1.
Comparative example 6
This comparative example provides an epoxy resin foam and a method for preparing the same, and is different from example 1 in that polyvinyl alcohol in a thermal conductive agent is replaced with polyvinylpyrrolidone and other conditions are the same as those of example 1.
Comparative example 7
This comparative example provides an epoxy resin foam and a method for preparing the same, and is different from example 1 in that a heat conductive agent does not contain polyvinyl alcohol, and other conditions are the same as those of example 1.
Comparative example 8
The present comparative example provides an epoxy resin foam and a method for preparing the same, and differs from example 1 in that the heat conductive agent is a combination comprising hexagonal boron nitride powder and polyvinyl alcohol, i.e., the heat conductive agent contains no water; other conditions were the same as in example 1.
Comparative example 9
The comparison example provides an epoxy resin foam and a preparation method thereof, and is different from the example 1 in that the heat conducting agent is hexagonal boron nitride powder, and other conditions are the same as the example 1.
Comparative example 10
This comparative example provides an epoxy resin foam and a method for preparing the same, which is different from example 1 in that gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane is replaced with cetyltrimethylammonium bromide, and other conditions are the same as example 1.
The epoxy resin foams provided in the above examples and comparative examples were tested for their properties according to the following test standards:
compressive strength: GB/T8813 & lt 2008 & gt determination of compression Properties of rigid foams;
tensile strength: GB 9641-1988 rigid foam tensile property test method;
thermal conductivity: GB/T10297-.
The performance of the epoxy resin foam provided in the above examples and comparative examples is shown in the following table 1:
TABLE 1
Figure BDA0002937165680000151
Figure BDA0002937165680000161
As shown in Table 1, the epoxy resin foam plastic prepared by using the mixed solution of the hexagonal boron nitride nanosheets and the polyvinyl alcohol as the heat conducting agent, further using the polyvinyl alcohol and the coupling agent in a matched manner, and controlling the mass ratio of the hexagonal boron nitride nanosheets to the polyvinyl alcohol within a specific ratio range of (50-150): 1 and the mass ratio of the coupling agent to the polyvinyl alcohol within a specific ratio range of (500-2200): 1 has good mechanical property and high thermal conductivity, and has the compression strength of 2.38-2.69 MPa, the tensile strength of 2.02-2.28 MPa and the thermal conductivity of 1.51-1.89W/(m.K).
Compared with example 1, if the mass of the hexagonal boron nitride nanosheets and the polyvinyl alcohol is relatively small (example 8), that is, the dosage of the polyvinyl alcohol is relatively large, although the dispersibility of the hexagonal boron nitride nanosheets in the heat-conducting agent is relatively good, the hexagonal boron nitride nanosheets are wrapped by the polyvinyl alcohol due to the excessive dosage of the polyvinyl alcohol, and the thermal conductivity of the prepared epoxy resin foamed plastic is relatively low to 1.47W/(m · K); if the mass ratio of the hexagonal boron nitride nanosheet to the polyvinyl alcohol is large (example 9), the prepared epoxy resin foamed plastic has poor mechanical properties, the compressive strength is 2.12MPa, and the tensile strength is 1.98 MPa. Therefore, when the mass ratio of the hexagonal boron nitride nanosheet to the polyvinyl alcohol is not within a specific ratio range, the prepared epoxy resin foamed plastic cannot have good mechanical property and high thermal conductivity at the same time.
Compared with example 1, if the mass of the coupling agent and the polyvinyl alcohol is smaller (example 12), that is, the amount of the coupling agent is less, the dispersibility of the hexagonal boron nitride nanosheet in the epoxy resin foam plastic is poor, and the thermal conductivity of the prepared epoxy resin foam plastic is lower than 1.49W/(m.K); if the mass of the coupling agent and the polyvinyl alcohol is relatively small (example 12), that is, the amount of the coupling agent is large, the mechanical property of the prepared epoxy resin foam plastic is poor, and the compressive strength is 2.04MPa and the tensile strength is 1.96 MPa. Therefore, when the mass ratio of the coupling agent to the polyvinyl alcohol is not within a specific ratio range, the prepared epoxy resin foam cannot have good mechanical properties and high thermal conductivity at the same time.
If the amount of the thermal conductive agent is small as compared with example 1 (comparative example 1), the thermal conductivity of the epoxy resin foam prepared is low as 0.98W/(m.K); if the amount of the heat-conducting agent is large (comparative example 2), the prepared epoxy resin foam plastic has high thermal conductivity of 1.92W/(m.K), but the compressive strength is low and is 2.28-2.69 MPa. It can be seen that if the amount of the thermal conductive agent is not within a specific range, the prepared epoxy resin foam cannot have both high compressive strength and high thermal conductivity.
Compared with the example 1, if the epoxy resin foam does not contain the heat-conducting agent (comparative example 3), the prepared epoxy resin foam has the advantages of lower heat conductivity of 0.12W/(m.K), poorer mechanical property, 1.49MPa of compressive strength and 1.29MPa of tensile strength; if the graphite powder is used as the heat conducting agent (comparative example 4), the prepared epoxy resin foam plastic has the advantages of low thermal conductivity of 0.24W/(m.K), poor mechanical property, compression strength of 1.55MPa and tensile strength of 1.34 MPa. Therefore, if the epoxy resin foam plastic does not contain a heat-conducting agent or other heat-conducting fillers are used for replacing the heat-conducting agent provided by the invention, the prepared epoxy resin has poor heat conductivity and mechanical property.
Compared with the example 1, if the hexagonal boron nitride nanosheets in the heat-conducting agent are replaced by other heat-conducting fillers such as graphite powder (comparative example 5), the prepared epoxy resin foamed plastic has the advantages of low thermal conductivity of 0.31W/(m.K), poor mechanical properties, compressive strength of 1.57MPa and tensile strength of 1.38 MPa; if polyvinyl alcohol in the thermal conductive agent is replaced by polyvinylpyrrolidone (comparative example 6), the thermal conductivity of the prepared epoxy resin foam is lower than 1.21W/(m.K); if the heat-conducting agent does not contain solvent polyvinyl alcohol (comparative example 7), the thermal conductivity of the prepared epoxy resin foam plastic is lower than 1.01W/(m.K); if the heat-conducting agent does not contain water (comparative example 8), the thermal conductivity of the prepared epoxy resin foam plastic is lower than 0.99W/(m.K), and the tensile strength is lower than 1.92 MPa; if the heat-conducting agent is hexagonal boron nitride powder (comparative example 9), the thermal conductivity of the prepared epoxy resin foam is lower than 0.97W/(m.K), and the tensile strength is lower than 1.89 MPa. Therefore, the epoxy resin foam plastic prepared by using the mixed solution of the hexagonal boron nitride nanosheet, the polyvinyl alcohol and the water as the heat conducting agent has high compressive strength and tensile strength and high heat conductivity.
Compared with example 1, if the coupling agent is replaced by cetyl trimethyl ammonium bromide (comparative example 10), the dissociated hexagonal boron nitride nanosheets have poor dispersibility in the epoxy resin foam, and the thermal conductivity of the prepared epoxy resin foam is lower than 1.42W/(m.K).
The applicant states that the present invention is illustrated by the detailed process flow of the present invention through the above examples, but the present invention is not limited to the above detailed process flow, that is, it does not mean that the present invention must rely on the above detailed process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. The epoxy resin foam plastic is characterized by comprising the following raw material components in parts by weight: 100 parts of epoxy resin, 5-130 parts of curing agent, 0.5-25 parts of foaming agent, 8-15 parts of heat conducting agent, 0.5-5 parts of coupling agent and 5-20 parts of flame retardant;
the heat conducting agent is a mixed solution comprising hexagonal boron nitride nanosheets and polyvinyl alcohol.
2. The epoxy resin foam according to claim 1, wherein the epoxy value of the epoxy resin is 0.2 to 0.6, and more preferably 0.3 to 0.54;
preferably, the curing temperature of the curing agent is 100-300 ℃, and further preferably 150-250 ℃;
preferably, the curing agent is selected from any one or a combination of at least two of m-phenylenediamine, dicyandiamide, sebacic dihydrazide, maleic anhydride, phthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride or polyazelaic anhydride;
preferably, the weight part of the curing agent in the raw material components of the epoxy resin foamed plastic is 30-80 parts.
3. The epoxy resin foam according to claim 1 or 2, wherein the blowing agent is selected from any one of azodicarbonamide, azobisisobutyronitrile, N '-dinitrosopentamethylenetetramine, 4' -oxybis-benzenesulfonylhydrazide or p-toluenesulfonylhydrazide or a combination of at least two thereof.
4. The epoxy resin foam according to any one of claims 1 to 3, wherein the mass ratio of the hexagonal boron nitride nanosheets to the polyvinyl alcohol is (50-150): 1;
preferably, the number of layers of the hexagonal boron nitride nanosheet is 1-20;
preferably, the polymerization degree of the polyvinyl alcohol is 350-4500, and more preferably 500-2000;
preferably, the concentration of the hexagonal boron nitride nanosheet in the mixed solution is 3-100 mg/mL, and further preferably 5-20 mg/mL;
preferably, the solvent of the mixed solution is water.
5. The epoxy resin foam according to any one of claims 1 to 4, wherein the thermal conductive agent is obtained by a production method comprising:
carrying out ultrasonic treatment on hexagonal boron nitride powder, polyvinyl alcohol and water to obtain the heat conducting agent;
preferably, the particle size of the hexagonal boron nitride powder is 1-30 μm;
preferably, the power of ultrasonic treatment is 400-1500W;
preferably, the time of ultrasonic treatment is 1-24 h, and further preferably 1-5 h.
6. The epoxy resin foam according to any one of claims 1 to 5, wherein the coupling agent is a silane coupling agent;
preferably, the mass ratio of the coupling agent to the polyvinyl alcohol is (500-2200) 1;
preferably, the flame retardant is selected from any one of methyl dimethyl phosphate, tributyl phosphate, tris (2-chloroethyl) phosphate or cresyl diphenyl phosphate or a combination of at least two of the same.
7. A process for the preparation of the epoxy resin foam according to any one of claims 1 to 6, characterized by the following steps:
and curing the epoxy resin, the curing agent, the foaming agent, the coupling agent, the heat conducting agent and the flame retardant to obtain the epoxy resin foam plastic.
8. The method of claim 7, wherein the curing comprises pre-curing and post-curing;
preferably, the temperature of the pre-curing is 100-150 ℃;
preferably, the pre-curing time is 2-6 h;
preferably, the post-curing temperature is 170-250 ℃;
preferably, the post-curing time is 1-24 h;
preferably, the method further comprises the step of pretreatment before curing;
preferably, the pretreatment method comprises the following steps: uniformly mixing the epoxy resin, the curing agent, the foaming agent, the coupling agent, the heat conducting agent and the flame retardant.
9. The preparation method according to claim 7 or 8, which is characterized by comprising the following steps:
uniformly mixing epoxy resin, a curing agent, a foaming agent, a coupling agent, a heat conducting agent and a flame retardant, precuring for 2-6 h at 100-150 ℃, then heating to 170-250 ℃, and post-curing for 1-24 h to obtain the epoxy resin foamed plastic.
10. Use of an epoxy resin foam as claimed in any one of claims 1 to 6 in a lightweight sandwich structural composite material.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115746404A (en) * 2022-11-16 2023-03-07 嘉兴学院 Surface-modified hexagonal boron nitride nanosheet, modification method thereof and epoxy composite material

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59223754A (en) * 1983-05-30 1984-12-15 Asahi Gosei Kagaku Kk Impregnating agent
JP2005298708A (en) * 2004-04-14 2005-10-27 Nissan Motor Co Ltd Foamable resin composition and method for reinforcing automobile body
JP2015151461A (en) * 2014-02-14 2015-08-24 コニカミノルタ株式会社 Method for manufacturing micro-foam molded article, and micro-foam molded article
US20150319856A1 (en) * 2012-12-12 2015-11-05 Lg Innotek Co., Ltd. Epoxy resin composition, and printed circuit board using same
WO2016086587A1 (en) * 2014-12-04 2016-06-09 中国科学院过程工程研究所 Thermally conductive and insulating epoxy resin composition and preparation method therefor and use thereof
WO2018236847A1 (en) * 2017-06-19 2018-12-27 Rogers Corporation Boron nitride foam, methods of manufacture thereof, and articles containing the boron nitride foam
CN111269533A (en) * 2020-02-25 2020-06-12 深圳赛兰仕科创有限公司 Epoxy composite material and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59223754A (en) * 1983-05-30 1984-12-15 Asahi Gosei Kagaku Kk Impregnating agent
JP2005298708A (en) * 2004-04-14 2005-10-27 Nissan Motor Co Ltd Foamable resin composition and method for reinforcing automobile body
US20150319856A1 (en) * 2012-12-12 2015-11-05 Lg Innotek Co., Ltd. Epoxy resin composition, and printed circuit board using same
JP2015151461A (en) * 2014-02-14 2015-08-24 コニカミノルタ株式会社 Method for manufacturing micro-foam molded article, and micro-foam molded article
WO2016086587A1 (en) * 2014-12-04 2016-06-09 中国科学院过程工程研究所 Thermally conductive and insulating epoxy resin composition and preparation method therefor and use thereof
WO2018236847A1 (en) * 2017-06-19 2018-12-27 Rogers Corporation Boron nitride foam, methods of manufacture thereof, and articles containing the boron nitride foam
CN111269533A (en) * 2020-02-25 2020-06-12 深圳赛兰仕科创有限公司 Epoxy composite material and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
XINWEI XU等: "3D boron nitride foam filled epoxy composites with significantly enhanced thermal conductivity by a facial and scalable approach", 《CHEMICAL ENGINEERING JOURNAL》 *
冷鑫钰等: "环氧树脂中3D氮化硼复合导热网络的构筑及性能", 《高分子材料科学与工程》 *
易敏等: "氮化硼纳米片作为抗原子氧腐蚀填料的应用", 《北京航空航天大学学报》 *
林正得等: "六方氮化硼导热复合材料研究进展", 《集成技术》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115746404A (en) * 2022-11-16 2023-03-07 嘉兴学院 Surface-modified hexagonal boron nitride nanosheet, modification method thereof and epoxy composite material
CN115746404B (en) * 2022-11-16 2023-11-21 嘉兴学院 Surface modified hexagonal boron nitride nanosheet, modification method thereof and epoxy composite material

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