CN111423699B - Preparation method of high-filling-amount hexagonal boron nitride/polymer blocky composite material - Google Patents
Preparation method of high-filling-amount hexagonal boron nitride/polymer blocky composite material Download PDFInfo
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Abstract
The invention relates to a preparation method of a high-filling-amount hexagonal boron nitride/polymer blocky composite material, which comprises the following steps: step 1: adding the hexagonal boron nitride and the polymer matrix into a mortar, and grinding and uniformly mixing to obtain a hexagonal boron nitride-polymer matrix mixture; the polymer matrix is liquid at normal temperature and normal pressure, and can be solidified under the condition of changing temperature and/or pressure; step 2: putting the mixture obtained in the step 1 into a ball milling tank, and uniformly ball milling to obtain a mixture which is further uniformly mixed and reacted and is obtained by reacting the hexagonal boron nitride with the polymer matrix; and step 3: putting the mixture obtained in the step (2) into a mould, and performing compression molding to obtain a block-shaped molding embryonic form of the polymer composite material; and 4, step 4: and (3) polymerizing and curing the block molding embryonic form of the polymer composite material obtained in the step (3) to obtain the block material of the high-filling-amount hexagonal boron nitride/polymer composite material. The composite material has ultrahigh mechanical property and huge heat management application potential.
Description
Technical Field
The invention belongs to the field of high-molecular composite materials, and particularly relates to a preparation method of a high-filling-amount hexagonal boron nitride/polymer blocky composite material.
Background
Heat dissipation is a critical issue for many important applications, particularly for electronic and electrical devices such as Light Emitting Diodes (LEDs) and integrated circuits, where heat build-up can lead to rapid aging and even failure of the core chip. Therefore, in order to ensure the working efficiency of electronic and electrical equipment and prolong the safe and normal service life of the electronic and electrical equipment, the development of new heat-conducting packaging materials and new processes with high performance and high heat conduction capability is a key scientific and technical problem which needs to be solved urgently in the academic and industrial fields at present.
The polymer composite heat conduction material is the preferred material for the most advanced electronic packaging process at present due to the advantages of light weight, easy processing, low cost and the like. However, the intrinsic thermal conductivity of the pure polymer matrix is relatively low (< 0.5W/m.K), and the method for optimally improving the thermal conductivity of the pure polymer matrix is to fill the pure polymer matrix with heat-conducting inorganic particles with high heat-conducting capacity, and form high phonon transmission channels of the heat-conducting particles in the polymer composite, so that the thermal conductivity of the polymer is effectively improved. Among all inorganic filler particles, high-quality hexagonal boron nitride is the material with the best heat conductivity, and the heat conductivity of a hot-pressed product is as high as-30W/m.K. Meanwhile, the hexagonal boron nitride has extremely high resistivity, shows the characteristic of ultrahigh insulation, and is a preferred filler for realizing a high-insulation heat-conducting packaging polymer composite material.
Theories and experiments prove that the fewer hexagonal boron nitride (0002) planar stacking layers are, the better the interlayer heat conduction performance is, and the better the macroscopic average heat conduction performance of heat conduction particles is, and research results show that the macroscopic heat conductivity of single-layer/few-layer hexagonal boron nitride nanosheets is as high as 300-3000W/m.K. Therefore, when high-content conventional hexagonal boron nitride heat-conducting particles are filled in the polymer, heat flow needs to pass through a thick transfer path stacked by (0002) crystal faces along the hexagonal boron nitride (0002) crystal faces, and due to poor heat conduction characteristics among hexagonal boron nitride layers, the heat conduction performance of the highly-filled hexagonal boron nitride heat-conducting particles in a composite system is difficult to obviously increase. If the stacking layer of the hexagonal boron nitride heat-conducting particles is remarkably thinned, a high-quality single-layer/few-layer boron nitride nanosheet is filled in the polymer at a high ratio, the transmission of heat flow between the hexagonal boron nitride layers is greatly reduced, and the heat transfer is remarkably improved. Therefore, high-quantity filling of the boron nitride nanosheet heat-conducting particles is realized in the polymer matrix, a heat flow channel with high phonon transmission can be efficiently increased, and the great increase of the heat conductivity of the composite system is promoted.
However, conventionally, the hexagonal boron nitride nanosheet/polymer composite material prepared by the blending composite process usually forms a random filling structure of the heat conducting particles after the filling amount is increased. Although the molding mode can also realize the filling of the hexagonal boron nitride nanosheets in a higher mass part, the hexagonal boron nitride nanosheet particles are distributed in the matrix in a seriously agglomerated form, the thermal conductivity of the composite system is not obviously improved due to the serious high internal consumption 'thermal reservoir effect', and the mechanical property of the composite system is seriously weakened along with the increase of the filling amount of the hexagonal boron nitride nanosheets. In recent years, although a vacuum filtration film forming technology is developed, a high proportion of hexagonal boron nitride nanosheets are successfully compounded into a polymer film type composite material, and the heat conductivity is improved, the method is not only complicated, but also only limited to preparation of an ultrathin film type hexagonal boron nitride nanosheet/polymer composite material, so that the heat dissipation efficiency of a composite system in a three-dimensional space is limited, and the large-scale industrial synthesis and application of the composite system are not facilitated. Therefore, the method aims to efficiently improve the uniform filling density of the hexagonal boron nitride nanosheets in the polymer, and is an important bottleneck problem in the development of high-thermal-conductivity and stable mechanical hexagonal boron nitride nanosheet/polymer composite materials at home and abroad.
Disclosure of Invention
The invention mainly solves the technical problems that: aiming at the problem that the uniform filling density of hexagonal boron nitride cannot be efficiently improved in a polymer matrix, the preparation method of the high-filling-amount hexagonal boron nitride/polymer bulk composite material is provided, and a liquid polymer is uniformly coated and reacted on the surface of the hexagonal boron nitride in an ultrathin layer mode by a mechanical ball milling mixing method. Particularly, when hexagonal boron nitride nanosheets are selected, polymer long-chain molecules and surface active sites, surface functional groups and dangling bonds of the boron nitride nanosheets are subjected to a strong bonding effect through a mechanical auxiliary mixing method, the polymer coated hexagonal boron nitride nanosheets are subjected to high-density contact and connection under pressure equipment through combination of pressure forming equipment, finally, a crosslinking reaction is performed between ultrathin polymer molecular layers on the surfaces of the hexagonal boron nitride nanosheets through a further curing process, a super-strong compact connection structure is formed between the hexagonal boron nitride nanosheets and a polymer matrix, and the high-filling type hexagonal boron nitride nanosheet/polymer block composite material is obtained.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for preparing a high-filling-quantity hexagonal boron nitride/polymer bulk composite material comprises the following steps:
step 1: adding the hexagonal boron nitride and the polymer matrix into a mortar, and grinding and uniformly mixing to obtain a hexagonal boron nitride-polymer matrix mixture; the mass of the hexagonal boron nitride accounts for more than 65 percent of the total mass of the material, the polymer matrix is in a liquid state at normal temperature and normal pressure, and can be solidified under the condition of changing the temperature and/or pressure;
step 2: putting the hexagonal boron nitride-polymer matrix mixture obtained in the step 1 into a ball milling tank, and uniformly mixing in a ball mill to obtain a mixture which is further uniformly mixed and reacted and is obtained by reacting the hexagonal boron nitride with the polymer matrix;
and step 3: putting the mixture of the hexagonal boron nitride and the polymer matrix in the step 2 into a mould, and performing compression molding in pressure molding equipment to obtain a block molding embryonic form of the polymer composite material;
and 4, step 4: and (3) polymerizing and curing the block molding embryonic form of the polymer composite material obtained in the step (3) to obtain the block material of the high-filling-amount hexagonal boron nitride/polymer composite material.
When the polymer matrix is a polymer containing auxiliary materials which are beneficial to solidification, the polymer main body and the hexagonal boron nitride are ground, ball-milled and mixed and reacted uniformly, then the auxiliary materials which are beneficial to solidification are added, the grinding and ball-milling processes are carried out, and finally pressing is carried out. Adjuvants which aid in solidification may also be added with the polymer body, reducing the speed and/or time of agitation. Of course, if the polymer body itself can be cured at elevated temperature or under a change in pressure, no auxiliary materials need to be added.
Preferably, the mortar in step 1 is a manual mortar or an electric mortar, and the mortar is made of agate, alumina, zirconia or the like.
Preferably, in step 2, the material of the ball milling pot is polytetrafluoroethylene, agate, alumina, zirconia or steel, and the material of the ball milling beads is polytetrafluoroethylene, agate, alumina, zirconia or steel.
Preferably, in step 2, the type of the ball mill is a planetary ball mill, a short barrel ball mill, a long barrel ball mill, a tube mill, a cone type mill or the like; the transmission mode of the ball mill is central transmission or peripheral (edge) transmission; the process operation mode of the ball mill is a batch type or a continuous type.
Preferably, in step 2, the rotation speed of the ball mill is 50-500rpm, such as 50rpm, 100rpm, 200rpm, 300rpm, 400rpm or 500rpm, but not limited to the enumerated values, and other unrecited values in the above numerical ranges are also applicable.
Preferably, in step 2, the ball milling time is 5-1800min, such as 5min, 100min, 500min, 800min, 1000min, 1500min or 1800min, but not limited to the recited values, and other values not recited in the above value ranges are also applicable.
Preferably, the rotation speed of the ball mill is 300-500rpm, and the ball milling time is 240-960min.
Preferably, in step 3, the pressure forming equipment is a piston type pressure forming machine, a screw type pressure forming machine or a mould pressing type forming machine; the driving type of the press molding apparatus is mechanical or hydraulic.
Preferably, in step 3, the die is a cylindrical, rectangular or square stainless steel metal or ceramic die with a diameter of 10, 20, 30, 50 mm.
Preferably, in step 3, the pressing pressure of the pressure forming device is 1-120MPa, such as 5MPa, 10MPa, 30MPa, 50MPa, 80MPa and 120MPa, but not limited to the values listed, and other values not listed in the above numerical ranges are also applicable.
Preferably, in step 3, the pressing time of the pressure forming device is 3-120min, such as 3min, 20min, 50min, 80min, 100min or 120min, but not limited to the recited values, and other values not recited in the above numerical ranges are also applicable.
A high-filling-quantity hexagonal boron nitride nanosheet/polymer bulk composite material comprises hexagonal boron nitride nanosheets and a polymer matrix. The mass percentages of the hexagonal boron nitride nanosheets and the polymer matrix are as follows: 65-95% of hexagonal boron nitride nanosheet and 5-35% of polymer matrix.
Preferably, the mass ratio of the hexagonal boron nitride nanosheets to the polymer matrix satisfies: 65-85% of hexagonal boron nitride and 15-35% of polymer matrix.
The hexagonal boron nitride micro-hexagonal boron nitride nanosheets or commercial hexagonal boron nitride powders.
Preferably, the hexagonal boron nitride nanosheets are any one, two, three or a combination of a plurality of hexagonal boron nitride nanosheets obtained by various mechanical stripping, chemical stripping and high-temperature synthesis methods; the hexagonal boron nitride nanosheet is any one, two, three or combination of a plurality of functionalized hexagonal boron nitride nanosheets obtained by various physical and chemical functionalization methods.
Preferably, the hexagonal boron nitride nanosheets are obtained by mechanical and chemical exfoliation using commercial hexagonal boron nitride powder; the diameter of the hexagonal boron nitride nanosheet is 10-1000nm.
Preferably, the hexagonal boron nitride nanosheets comprise: mixing the commercial hexagonal boron nitride powder with boric acid, and performing ball milling, centrifugal cleaning and freeze drying to obtain the product, wherein the product is named as: hexagonal boron nitride nanosheet-1; mixing the commercial hexagonal boron nitride powder with urea, and performing ball milling, centrifugal cleaning and freeze drying to obtain the product, wherein the product is named as: hexagonal boron nitride nanosheet-2; mixing the commercial hexagonal boron nitride powder with one, two or three of sodium hydroxide, potassium hydroxide or lithium hydroxide, performing ball milling, centrifugal cleaning and freeze drying to obtain the hexagonal boron nitride powder, wherein the hexagonal boron nitride powder is named as: hexagonal boron nitride nanosheet-3; the commercial hexagonal boron nitride powder is directly subjected to ball milling, centrifugal cleaning and freeze drying to obtain the hexagonal boron nitride powder, and the hexagonal boron nitride powder is named as: hexagonal boron nitride nanosheet-4.
Further, the polymer matrix can contain liquid monomers, cannot be polymerized and molded at normal temperature and normal pressure, can be polymerized and molded by itself under the condition of temperature rise or pressurization or can be polymerized and molded under the condition of temperature rise or pressurization in the presence of auxiliaries such as a curing agent, a catalyst or an initiator, and no small molecular substances are generated in the polymerization process. The polymer matrix may be a polymer formed by using methyl methacrylate, epoxy resin, unsaturated polyester, melamine formaldehyde resin, polybutadiene resin, furan resin, bismaleimide resin, etc. as a main material and adding a curing agent, a catalyst, an initiator, etc. as an auxiliary material contributing to curing, but the polymer matrix is not limited to the illustrated polymer matrix, and other polymer matrices satisfying the characteristics are also applicable.
Preferably, the polymer matrix is composed of bisphenol A epoxy resin, methyl tetrahydrophthalic anhydride (curing agent) and 2,4,6-tris (dimethylaminomethyl) phenol (catalyst), and the polymer matrix is sequentially heated and cured in a vacuum drying oven at two temperature ranges of 50-100 ℃ and 100-180 ℃ in the step 4. The temperature of the first temperature section can be 50 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃ and the like; the second temperature range may be 105 ℃, 130 ℃, 150 ℃, 165 ℃ or 180 ℃, but is not limited to the recited values, and other values not recited in the above numerical ranges are also applicable. The heating curing time of each temperature range is 1-12h, such as 1h, 2h, 3h, 4h, 5h, 6h, 7h or 12h, but is not limited to the values listed, and other values not listed in the above numerical ranges are also applicable.
Compared with the prior art, the invention has the beneficial effects that:
the product obtained by the invention is a three-dimensional block with a complete structure, as shown in figure 1. By a mechanical mixing method, in the ball milling mixing process, a liquid polymer is uniformly coated and reacted to the surface of the hexagonal boron nitride nanosheet in an ultrathin layer mode, and the long-chain molecules of the polymer and the surface active sites, surface functional groups and dangling bonds of the boron nitride nanosheets are enabled to generate a strong bonding effect. Polymer-coated hexagonal boron nitride nanosheets are caused to be in high-density contact and connection by further pressure forming under pressure forming equipment, a cross-linking reaction is caused between ultrathin polymer molecular layers on the surfaces of the hexagonal boron nitride nanosheets in a further curing process, and a super-strong compact connection structure is formed between the hexagonal boron nitride nanosheets and a polymer matrix, so that a composite system is not only filled with uniformly dispersed high-proportion boron nitride nanosheets (the filling amount of boron nitride nanosheet particles exceeds 65% of that of the composite system), but also a compact structural body is formed inside the composite material, as shown in the section morphology of the composite material in figure 2, and the filling mode enables the hexagonal boron nitride nanosheet/polymer composite system to have super-strong mechanical properties. Fig. 3 is a relationship between compressive stress and compressive strain of different boron nitride types with the same filling amount, and as shown by a statistical graph of compressive strength and modulus of the composite material in fig. 4 and 5, the prepared composite material has a compressive strength up to 92MPa and a compressive modulus up to 2GPa, which indirectly indicates that a strong composite structure with a good complete cross-linked network is formed by the boron nitride nanosheets with a high filling amount and the epoxy resin matrix, and maintains excellent mechanical properties under the condition of a high filling amount of the boron nitride nanosheets, because apart from a strong bond formed between the boron nitride nanosheet filler particles and polymer molecules, the uniform dispersibility of the filler in the polymer frame should achieve a good effect, because severe agglomeration of the filler particles directly leads to sharp reduction of mechanical properties, and the agglomeration phenomenon of the particles with uneven dispersion is generally an inherent factor or origin of mechanical property failure of the composite structure. As can be seen from the linear thermal expansion curves of the composite material and the pure epoxy resin in fig. 6, the linear thermal expansion coefficient of the prepared composite material is obviously reduced, which is attributed to the fact that stronger bonding is formed between the boron nitride nanosheet filler particles and the polymer molecules and the uniform dispersibility of the filler in the polymer matrix, the migration of the polymer molecular chain is limited, and the thermal expansion coefficient of the composite material is reduced; for thermoset polymer composites, the glass transition temperature is the upper limit of their use temperature. Therefore, it is important in practical applications that the composite material has a high glass transition temperature. As can be seen from the statistical graphs of the glass transition temperatures of the composite material and the pure epoxy resin in fig. 7, the glass transition temperatures of all the composite materials are significantly increased compared to the pure epoxy resin, and the glass transition temperature of the composite material is increased from 114 ℃ to 192 ℃ as the filling amount of the boron nitride nanosheets is increased. The motion of polymer molecular chains is limited due to the addition of the boron nitride nanosheet filler, and the side surface reflects the good dispersibility of the filler in a polymer matrix; through an infrared thermal imaging photo in FIG. 8 and temperature collection and summary of the highest temperature point of the upper surface of the sample in the processes of temperature rise and temperature drop, the composite material prepared by the invention has great heat management application potential. In addition, the obtained composite material has the characteristic of easy processing and cutting, and can meet the actual requirements. Meanwhile, the high-filling-amount boron nitride nanosheet composite material provided by the invention is simple in preparation process, wide in raw material source and beneficial to large-scale implementation.
Drawings
FIG. 1 is a picture of samples of hexagonal boron nitride nanosheets/epoxy resin composites obtained in various examples;
FIG. 2 is an SEM image of a cross section of a hexagonal boron nitride nanosheet/epoxy composite of example 1;
FIG. 3 is a representative stress-strain curve for hexagonal boron nitride nanosheet/epoxy bulk composite (BNNSs/EP) prepared in example 7 and a commercial hexagonal boron nitride powder/epoxy bulk composite (BN/EP) prepared in example 14;
fig. 4 is a bar graph of the compressive strength of hexagonal boron nitride nanosheet/epoxy composite prepared in examples 1-7 and a commercial boron nitride powder/epoxy bulk composite prepared in example 14;
fig. 5 is a histogram of the compressive modulus of hexagonal boron nitride nanosheet/epoxy composite prepared in examples 1-7 and a commercial boron nitride powder/epoxy bulk composite prepared in example 14;
FIG. 6 is a linear thermal expansion coefficient curve for the hexagonal boron nitride nanosheet/epoxy bulk composite prepared in example 7 and the neat epoxy prepared in comparative example 1;
FIG. 7 is a statistical plot of the glass transition temperatures of hexagonal boron nitride nanosheet/epoxy composite prepared in examples 1-7 and of the neat epoxy prepared in comparative example 1;
fig. 8 is a graph showing the monitoring of the heat transfer capacity of the hexagonal boron nitride nanosheet/epoxy bulk composite prepared in example 7, the commercial boron nitride powder/epoxy bulk composite prepared in example 14, and the pure epoxy prepared in comparative example 1 using a thermal infrared imager: the method comprises the following steps of (a) detecting a real-time photo of a thermal infrared imager; (b) The temperature of the highest temperature point of the upper surface of the sample in the temperature rising and reducing processes is collected and summarized.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be 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.
Example 1
(1): adding 15g of hexagonal boron nitride nanosheet-1 with the average transverse dimension of 700nm, 4.32g of bisphenol A epoxy resin, 3.67g of methyl tetrahydrophthalic anhydride (curing agent) and 0.08g of 2,4, 6-tris (dimethylaminomethyl) phenol (catalyst) into an agate manual mortar, and grinding and uniformly mixing to obtain a hexagonal boron nitride nanosheet-epoxy resin mixture, wherein the liquid substance content is very low, and the mixed mixture is in a wet powder state and has no flowability;
(2): putting the hexagonal boron nitride nanosheet-epoxy resin mixture obtained in the step (1) into a polytetrafluoroethylene ball mill, and uniformly mixing in a planetary ball mill, wherein the rotating speed of the ball mill is 500rpm, and the ball milling time is 600min, so as to obtain a uniformly mixed and reacted hexagonal boron nitride nanosheet-epoxy resin mixture;
(3): and (3) putting the uniformly mixed and reacted hexagonal boron nitride nanosheet-epoxy resin mixture in the step (2) into a cylindrical stainless steel metal die with the diameter of 20mm, applying pressure for 30min through a piston type pressure forming machine, rapidly increasing the pressure to 20MPa within 1min, keeping the pressure constant, slowly releasing the pressure after 29min, and taking out the block to obtain a block forming prototype of the polymer composite material.
(4): and (4) obliquely putting the formed prototype of the composite material obtained in the step (3) into a vacuum drying oven for heating and curing, heating for 2h and 4h at 80 ℃ and 150 ℃, naturally cooling to room temperature, and opening the vacuum drying oven to obtain the high-filling-amount boron nitride nanosheet/epoxy resin blocky composite material which is named as 65BNNSs/EP.
Examples 2, 3, 4, 5, 6, 7
The amount of the epoxy resin mixture in step (1) of example 1 was changed to make the mass percent of the boron nitride nanosheets in the epoxy resin composite material 70%, 75%, 80%, 85%, 90%, 95%, and the other operations were the same as those in example 1 and were respectively named 70BNNSs/EP, 75BNNSs/EP, 80BNNSs/EP, 85BNNSs/EP, 90BNNSs/EP, and 95BNNSs/EP. The compressive strength of the composite materials prepared in examples 1 to 7 is shown in FIG. 5, and the compressive modulus thereof is shown in FIG. 6.
Example 8
(1): adding 10g of hexagonal boron nitride nanosheet-1 with the average transverse dimension of 700nm, 2.29g of bisphenol A epoxy resin, 1.87g of methyl tetrahydrophthalic anhydride (curing agent) and 0.04g of 2,4, 6-tris (dimethylaminomethyl) phenol (catalyst) into an agate manual mortar, and grinding and uniformly mixing to obtain a hexagonal boron nitride nanosheet-epoxy resin mixture, wherein the liquid substance content is very low, and the mixed mixture is in a wet powder state and has no flowability;
(2): putting the hexagonal boron nitride nanosheet-epoxy resin mixture obtained in the step (1) into a polytetrafluoroethylene ball milling tank, and uniformly mixing in a planetary ball mill, wherein the rotating speed of the ball mill is 500rpm, and the ball milling time is 800min, so as to obtain a uniformly mixed and reacted hexagonal boron nitride nanosheet-epoxy resin mixture;
(3): and (3) putting the mixture obtained in the step (2) into a cylindrical stainless steel metal die with the diameter of 40mm, applying pressure for 60min by a piston type pressure forming machine, rapidly increasing the pressure to 60MPa within 5min, keeping the pressure constant, slowly releasing the pressure after 65min, and taking out the block to obtain a block forming embryonic form of the polymer composite material.
(4): and (4) vertically placing the formed embryonic form of the composite material obtained in the step (3) into a forced air drying oven for heating and curing, heating for 0.5h, 2h and 4h at 40 ℃, 60 ℃, 80 ℃ and 150 ℃, respectively, naturally cooling to room temperature, and opening the forced air drying oven to obtain the boron nitride nanosheet/epoxy resin blocky composite material with high filling amount.
Example 9
(1): adding 15g of hexagonal boron nitride nanosheet-1 with the average transverse dimension of 700nm, 4.32g of bisphenol A epoxy resin and 3.67g of methyl tetrahydrophthalic anhydride (curing agent) into an agate manual mortar, grinding and uniformly mixing to obtain a boron nitride-epoxy resin mixture, wherein the mixed mixture is in a wet powder state and does not have fluidity due to little liquid substance content;
(2): putting the hexagonal boron nitride nanosheet-epoxy resin mixture obtained in the step (1) into a polytetrafluoroethylene ball milling tank, and uniformly mixing in a planetary ball mill, wherein the rotating speed of the ball mill is 500rpm, and the ball milling time is 600min, so as to obtain a uniformly mixed and reacted hexagonal boron nitride nanosheet-epoxy resin mixture;
(3): putting the hexagonal boron nitride nanosheet-epoxy resin mixture uniformly mixed and reacted in the step (2) and 0.08g of 2,4, 6-tris (dimethylaminomethyl) phenol (catalyst) into an agate manual mortar, and uniformly grinding;
(4): putting the mixture obtained in the step (3) into a polytetrafluoroethylene ball milling tank, and uniformly mixing in a planetary ball mill, wherein the rotating speed of the ball mill is 500rpm, and the ball milling time is 600min, so as to obtain a further uniformly mixed and reacted hexagonal boron nitride nanosheet-epoxy resin mixture;
(5): and (3) putting the mixture obtained in the step (4) into a cylindrical stainless steel metal die with the diameter of 20mm, applying pressure for 45min by a piston type pressure forming machine, rapidly increasing the pressure to 20MPa within 1min, keeping the pressure constant, slowly releasing the pressure after 44min, and taking out the block to obtain a block forming embryonic form of the polymer composite material.
(6): and (4) obliquely placing the formed prototype of the composite material obtained in the step (5) into a vacuum drying oven for heating and curing, heating for 2 hours and 4 hours at 80 ℃ and 150 ℃, naturally cooling to room temperature, and opening the vacuum drying oven to obtain the high-filling-quantity boron nitride nanosheet/epoxy resin blocky composite material.
Example 10
(1): adding 15g of hexagonal boron nitride nanosheet-1 with the average transverse dimension of 700nm, 2g of bisphenol A epoxy resin, 1.7g of methyl tetrahydrophthalic anhydride (curing agent) and 0.05g of 2,4, 6-tris (dimethylaminomethyl) phenol (catalyst) into an agate manual mortar, grinding and uniformly mixing to obtain a hexagonal boron nitride nanosheet epoxy resin mixture, wherein the mixed mixture is in a wet powder state and does not have fluidity due to little liquid substance content;
(2): putting the hexagonal boron nitride nanosheet-epoxy resin mixture obtained in the step (1) into a steel ball milling tank, and uniformly mixing in a planetary ball mill, wherein the rotating speed of the ball mill is 200rpm, and the ball milling time is 600min, so as to obtain a uniformly mixed and reacted boron nitride nanosheet-epoxy resin mixture;
(3): and (3) putting the boron nitride nanosheet-epoxy resin mixture uniformly mixed and reacted in the step (2) into a cylindrical stainless steel metal die with the diameter of 20mm, applying pressure for 30min through a piston type pressure forming machine, rapidly increasing the pressure to 20MPa within 1min, keeping the pressure constant, slowly releasing the pressure after 29min, and taking out the block to obtain a block forming prototype of the polymer composite material.
(4): and (4) obliquely putting the formed embryonic form of the composite material obtained in the step (3) into a vacuum drying oven for heating and curing, heating for 2 hours and 4 hours at the temperature of 80 ℃ and 150 ℃, naturally cooling to room temperature, and opening the vacuum drying oven to obtain the high-filling-quantity boron nitride nanosheet/epoxy resin blocky composite material.
Example 11
(1): adding 15g of hexagonal boron nitride nanosheet-1 with the average transverse dimension of 700nm, 2g of bisphenol A epoxy resin, 1.7g of methyl tetrahydrophthalic anhydride (curing agent) and 0.05g of 2,4, 6-tris (dimethylaminomethyl) phenol (catalyst) into an agate manual mortar, grinding and uniformly mixing to obtain a hexagonal boron nitride nanosheet-epoxy resin mixture, wherein the liquid substance content is very low, and the mixed mixture is in a wet powder state and does not have fluidity;
(2): putting the boron nitride nanosheet-epoxy resin mixture obtained in the step (1) into an agate ball milling tank, and uniformly mixing in a planetary ball mill, wherein the rotating speed of the ball mill is 400rpm, and the ball milling time is 600min, so as to obtain the uniformly mixed and reacted boron nitride nanosheet-epoxy resin mixture;
(3): and (3) putting the boron nitride nanosheet-epoxy resin mixture uniformly mixed and reacted in the step (2) into a cylindrical stainless steel metal die with the diameter of 20mm, applying pressure for 30min through a piston type pressure forming machine, rapidly increasing the pressure to 20MPa within 1min, keeping the pressure constant, slowly releasing the pressure after 29min, and taking out the block to obtain a block forming prototype of the polymer composite material.
(4): and (4) obliquely placing the formed prototype of the composite material obtained in the step (3) into a vacuum drying oven for heating and curing, heating for 2 hours and 4 hours at 80 ℃ and 150 ℃, naturally cooling to room temperature, and opening the vacuum drying oven to obtain the high-filling-quantity boron nitride nanosheet/epoxy resin blocky composite material.
Example 12
(1): adding 15g of hexagonal boron nitride nanosheet-1 with the average transverse dimension of 700nm and 4.32g of bisphenol A epoxy resin into an agate manual mortar, grinding and uniformly mixing to obtain a hexagonal boron nitride nanosheet epoxy resin mixture, wherein the mixed mixture is in a wet powder state and does not have fluidity due to little liquid substance content;
(2): putting the hexagonal boron nitride nanosheet epoxy resin mixture obtained in the step (1) into a polytetrafluoroethylene ball milling tank, and uniformly mixing in a planetary ball mill, wherein the rotating speed of the ball mill is 500rpm, and the ball milling time is 1200min, so as to obtain a uniformly mixed and reacted boron nitride nanosheet-epoxy resin mixture;
(3): putting the boron nitride nanosheet-epoxy resin mixture mixed and reacted uniformly in the step (2), 3.67g of methyl tetrahydrophthalic anhydride (curing agent) and 0.08g of 2,4, 6-tris (dimethylaminomethyl) phenol (catalyst) into an agate manual mortar, and grinding uniformly;
(4): putting the mixture obtained in the step (3) into a polytetrafluoroethylene ball milling tank, and uniformly mixing in a planetary ball mill, wherein the rotating speed of the ball mill is 500rpm, and the ball milling time is 600min, so as to obtain a further uniformly mixed and reacted boron nitride nanosheet-epoxy resin mixture;
(5): and (3) putting the boron nitride nanosheet-epoxy resin mixture uniformly mixed and reacted in the step (4) into a cylindrical stainless steel metal die with the diameter of 20mm, applying pressure for 60min through a piston type pressure forming machine, rapidly increasing the pressure to 20MPa within 1min, keeping the pressure constant, slowly releasing the pressure after 59min, and taking out the block to obtain a block forming embryonic form of the polymer composite material.
(6): and (4) obliquely placing the formed prototype of the composite material obtained in the step (5) into a vacuum drying oven for heating and curing, heating for 2 hours and 4 hours at 80 ℃ and 150 ℃, naturally cooling to room temperature, and opening the vacuum drying oven to obtain the high-filling-quantity boron nitride nanosheet/epoxy resin blocky composite material.
Example 13
(1): adding 15g of hexagonal boron nitride nanosheet-1 with the average transverse dimension of 700nm, 8.44g of methyl methacrylate and 0.03g of benzoyl peroxide (initiator) into an agate manual mortar, grinding and uniformly mixing to obtain a hexagonal boron nitride nanosheet-methyl methacrylate mixture, wherein the mixed mixture is in a wet powder state due to little liquid substance content and has no fluidity;
(2): putting the mixture of the hexagonal boron nitride nanosheets and the epoxy resin in the step (1) into a polytetrafluoroethylene ball mill, and uniformly mixing in a planetary ball mill, wherein the rotating speed of the ball mill is 500rpm, and the ball milling time is 600min, so as to obtain a uniformly mixed and reacted mixture of the hexagonal boron nitride nanosheets and the methyl methacrylate;
(3): and (3) putting the uniformly mixed and reacted hexagonal boron nitride nanosheet-methyl methacrylate mixture in the step (2) into a cylindrical stainless steel metal die with the diameter of 20mm, applying pressure for 30min through a piston type pressure forming machine, rapidly increasing the pressure to 20MPa within 1min, keeping the pressure constant, slowly releasing the pressure after 29min, and taking out the block to obtain a block forming embryonic form of the polymer composite material.
(4): and (4) obliquely placing the formed prototype of the composite material obtained in the step (3) into a vacuum drying oven for heating and curing, heating for 24 hours and 1 hour at 50 ℃ and 100 ℃, naturally cooling to room temperature, and opening the vacuum drying oven to obtain the high-filling-amount boron nitride nanosheet/polymethyl methacrylate bulk composite material.
Example 14
The hexagonal boron nitride nanosheet with the average lateral dimension of 700nm in step (1) of example 7 was changed to commercial hexagonal boron nitride powder with the average lateral dimension of 1.5 μm, and all other operations were the same as in example 1 and named 95BN/EP.
Example 15
The 15g of hexagonal boron nitride nanosheet-1 with the average transverse dimension of 700nm in the step (1) of example 1 is changed to 7.5g of a mixed filler of hexagonal boron nitride nanosheet-1 with the average transverse dimension of 700nm and 7.5g of a hexagonal boron nitride nanosheet-2 with the average transverse dimension of 700nm, and the other operations are the same as those in example 1.
Example 16
(1): adding 15g of hexagonal boron nitride nanosheet-1 with the average transverse dimension of 700nm and 8.07g of bismaleimide into an agate artificial mortar, and grinding and uniformly mixing to obtain a hexagonal boron nitride nanosheet-bismaleimide mixture;
(2): putting the hexagonal boron nitride nanosheet-epoxy resin mixture obtained in the step (1) into a polytetrafluoroethylene ball milling tank, and uniformly mixing in a planetary ball mill, wherein the rotating speed of the ball mill is 500rpm, and the ball milling time is 600min, so as to obtain a uniformly mixed and reacted hexagonal boron nitride nanosheet-bismaleimide mixture;
(3): and (3) putting the uniformly mixed and reacted hexagonal boron nitride nanosheet-bismaleimide mixture in the step (2) into a cylindrical stainless steel metal mold with the diameter of 20mm, applying pressure for 30min through a piston type pressure forming machine, rapidly increasing the pressure to 20MPa within 1min, keeping the pressure constant, slowly releasing the pressure after 29min, and taking out the block to obtain a block forming embryonic form of the polymer composite material.
(4): and (4) obliquely putting the formed prototype of the composite material obtained in the step (3) into a vacuum drying oven for heating and curing, heating for 2h, 2h and 4h at 150 ℃, 170 ℃ and 200 ℃, naturally cooling to room temperature, and opening the vacuum drying oven to obtain the boron nitride nanosheet/bismaleimide resin block composite material with high filling amount.
Comparative example 1
Weighing 10g of bisphenol A epoxy resin, 8.5g of methyl tetrahydrophthalic anhydride (curing agent) and 0.5g of 2,4, 6-tri (dimethylaminomethyl) phenol (catalyst), vacuumizing for 10-15 minutes at normal temperature, pouring the mixed solution into a polytetrafluoroethylene mold with the inner surface coated with a release agent, defoaming in vacuum, putting the polytetrafluoroethylene mold into a vacuum drying oven for heating and curing, heating for 4 hours and 8 hours at 80 ℃ and 150 ℃ respectively, naturally cooling to room temperature, and opening the vacuum drying oven to obtain pure epoxy resin named as EP.
As can be seen from the preparation steps of examples 4, 10, and 11, in the process of ball milling and mixing, the use of ball milling pots made of different materials will greatly affect the rotation speed and time of ball milling, because the ball milling pots made of different materials have different internal collision strengths and different effects at the same rotation speed, and if the ball milling rotation speed is too slow and the ball milling time is too short, the polymer matrix cannot be uniformly coated on the surface of the boron nitride nanosheet; if the rotational speed of the ball mill is too fast, the ball milling time is too long, which may cause the polymer to polymerize during the ball milling process. Therefore, different ball milling rotating speeds and ball milling time are selected for different ball milling tanks, and the same effect can be achieved. As can be seen from examples 1, 9, and 12, the same effects as in example 1 can be achieved by mixing the epoxy resin and the curing agent with the boron nitride nanosheets and then adding the catalyst in example 9, and mixing the epoxy resin with the boron nitride nanosheets and then adding the curing agent and the catalyst in example 12, except that the rotation speed and the ball milling time of the ball milling need to be appropriately adjusted. As can be seen from examples 2 and 8, in the stage of curing and forming the composite material, different curing procedures, that is, curing temperatures and curing times, are required to be selected for thermosetting through different ovens, because the sample is placed in the forced air drying oven, and in the process of temperature rise, the surface of the sample is rapidly heated, temperature difference is formed between the surface of the sample and the interior of the sample, and cracking of the sample is easily caused, so that the sample needs to be heated and cured for a period of time in the low-temperature stage, and in addition, the placing position of the sample in the drying oven is extremely important, and the sample needs to be placed in the vacuum drying oven in an inclined manner, so that the contact area between the sample and the drying oven is reduced, because the temperature rise at the place where the sample is in contact with the drying oven is fast, and the sample is also easily cracked, and it is also noted that the sample cannot be taken out of the drying oven immediately after the curing stage is completed, and the temperature in the drying oven naturally drops to room temperature to be taken out, so that the sample is prevented from cracking under an excessive temperature difference.
As can be seen from fig. 3 to 5, the compressive strength of the commercial boron nitride/epoxy resin composite material (95 BN/EP) prepared in example 14 is only 18MPa, the compressive modulus is 0.47GPa, and is much lower than that of the boron nitride nanosheet/epoxy resin composite material (95 BNNSs/EP) prepared in example 7, on one hand, because the polymer long-chain molecules in the boron nitride nanosheet/epoxy resin composite material can have strong bonding effect with the surface active sites, the surface functional groups and the dangling bonds of the boron nitride nanosheet, when stressed, the local stress is effectively transferred to the boron nitride nanosheet through the close contact with the epoxy matrix, while in the commercial boron nitride/epoxy resin composite material, the epoxy resin is only coated on the surface of the commercial boron nitride; on the other hand, due to the layered structure of commercial boron nitride, the applied mechanical load promotes slippage between the boron nitride layer and the layer, which results in destruction of the internal structure of the composite. Through the infrared thermal imaging photo of fig. 8 and the temperature collection and summary display of the highest temperature point of the upper surface of the sample in the temperature rising and cooling processes, the epoxy resin is uniformly coated on the surface of the highly-filled boron nitride nanosheet in the boron nitride nanosheet/epoxy resin composite material prepared in example 7 in an ultrathin layer manner, and the polymer long-chain molecules in the boron nitride nanosheet/epoxy resin composite material can generate a strong bonding effect with the surface active sites, the surface functional groups and the dangling bonds of the boron nitride nanosheet, so that a "sea-island two-phase system" structure formed by the boron nitride nanosheet filler and the polymer matrix can be obviously reduced, a denser heat conduction particle mutual contact network can be constructed in the polymer body, the interface thermal resistance between the polymer and the filler interface is greatly reduced, a high-density heat flow conduction path can be formed along the heat conduction networks, the rapid conduction of heat flow is promoted, and the heat flow thermal resistance of the composite system can be significantly improved. The composite material prepared by the invention has huge heat management application potential, and can lead out heat in time and quickly during heat management, so that a system works in a proper temperature range to maintain the optimal use state of the system, and the performance and the service life of the system are ensured (a heat conduction performance test method comprises the steps of placing a sample in a constant temperature heating platform with the temperature of 25 ℃ for 24 hours, then placing the sample in a constant temperature heating platform with the temperature of 80 ℃, photographing the upper surface of the sample by using a thermal infrared imager to record the temperature changes of all the samples in 0s, 3s, 6s and 9s respectively, and cooling, wherein the sample is placed in an oven with the temperature of 80 ℃ for heating for 30 minutes, then simultaneously transferring the sample to a polytetrafluoroethylene plate in the room temperature environment, and photographing the upper surface of the sample by using the thermal infrared imager to record the temperature changes of all the samples in 0s, 10s, 20s and 30s respectively).
The core innovation point of the application is as follows: by a mechanical mixing reaction method, in the ball milling and mixing process, a liquid polymer is uniformly coated and reacted to the surface of the hexagonal boron nitride nanosheet in an ultrathin layer mode, and the long-chain molecules of the polymer and the surface active sites, surface functional groups and dangling bonds of the boron nitride nanosheets generate a strong bonding effect. The polymer-coated hexagonal boron nitride nanosheets are subjected to high-density contact and connection of polymer molecules under pressure equipment through further pressure forming, a crosslinking reaction is generated between the ultrathin polymer molecule layers on the surfaces of the hexagonal boron nitride nanosheets in a further curing process, an ultra-strong compact connection structure is formed between the hexagonal boron nitride nanosheets and the polymer matrix, the mechanical property of the material is greatly improved, the transmission path of heat flow between polymers with low heat conductivity property can be greatly shortened, and the heat conductivity is efficiently improved. The initial mixing in a mortar in the first step of the synthesis process is also extremely critical, otherwise non-uniform mixing can occur during the second mechanical mixing step. The rotating speed and the ball milling time of the ball mill and the pressure and the time of the tabletting are critical in the application, the rotating speed is too high, the material in the tank sinks due to overlong time, the mixing is uneven, the pressure of the tabletting is too low, and the inside of the composite material cannot form a compact structure due to too short time, so that the performance of the material is influenced, in the parameter range given by the application, the composite material has good formability, no cracks are formed on the surface, the mechanical property is remarkably improved, the compression modulus is about 0.4-2.0GPa, and the compression strength is about 18-92 MPa.
Nothing in this specification is said to apply to the prior art.
Claims (9)
1. A preparation method of a high-filling-amount hexagonal boron nitride/polymer bulk composite material comprises the following steps:
step 1: adding the hexagonal boron nitride and the polymer matrix into a mortar, and grinding and uniformly mixing to obtain a hexagonal boron nitride-polymer matrix mixture; the mass of the hexagonal boron nitride accounts for more than 65 percent of the total mass of the material, and the polymer matrix is liquid at normal temperature and normal pressure and can be solidified under the condition of changing temperature and/or pressure;
step 2: putting the hexagonal boron nitride-polymer matrix mixture obtained in the step 1 into a ball milling tank, and uniformly mixing in a ball mill to obtain a mixture of further uniformly mixed and reacted hexagonal boron nitride and a polymer matrix;
and step 3: putting the mixture of the hexagonal boron nitride and the polymer matrix in the step 2 into a mould, and performing compression molding in pressure molding equipment to obtain a block molding embryonic form of the polymer composite material;
and 4, step 4: polymerizing and curing the block molding embryonic form of the polymer composite material obtained in the step 3 to obtain a block material of the high-filling-amount hexagonal boron nitride/polymer composite material;
the polymer matrix is a polymer main body composed of liquid monomers, can not be polymerized and molded at normal temperature, can be solidified and polymerized and molded by heating in the presence of auxiliary materials which are added to contribute to solidification, and does not generate small molecular substances in the polymerization process;
when the polymer matrix is a polymer containing auxiliary materials which are beneficial to solidification, grinding, ball-milling and mixing the polymer main body and hexagonal boron nitride, uniformly reacting, adding the auxiliary materials which are beneficial to solidification, then grinding and ball-milling, and finally pressing;
or adding auxiliary materials which are helpful for solidification and the polymer main body together, and reducing the stirring speed and/or the stirring time;
the hexagonal boron nitride is a hexagonal boron nitride nanosheet.
2. The method according to claim 1, wherein the polymer matrix comprises a polymer main body of methyl methacrylate, epoxy resin, unsaturated polyester, melamine formaldehyde resin, polybutadiene resin, furan resin or bismaleimide resin, and auxiliary materials of a curing agent and a catalyst or an initiator.
3. The method according to claim 2, wherein the polymer matrix is composed of bisphenol A epoxy resin, methyl tetrahydrophthalic anhydride and 2,4,6-tris (dimethylaminomethyl) phenol, and is cured by heating at 50-100 ℃ and 100-180 ℃ in sequence in step 4; the heating curing time of each temperature section is 1-12h, and the high-filling-amount boron nitride/epoxy resin blocky composite material is obtained.
4. The preparation method according to claim 2, wherein the polymer matrix is composed of methyl methacrylate and benzoyl peroxide as an initiator, and the high-filling-amount boron nitride nanosheet/polymethyl methacrylate bulk composite material is obtained by respectively heating at 50 ℃ and 100 ℃ for 24h and 1h in step 4 for curing.
5. The preparation method according to claim 1, wherein the mortar in the step 1 is a manual mortar or an electric mortar, and the mortar is made of agate, alumina or zirconia; in the step 2, the ball milling tank is made of polytetrafluoroethylene, agate, alumina, zirconia or steel, and the corresponding ball milling beads are made of polytetrafluoroethylene, agate, alumina, zirconia or steel; in the step 2, the type of the ball mill is a planetary ball mill, a short-barrel ball mill, a long-barrel ball mill, a tube mill or a cone mill; the transmission mode of the ball mill is central transmission or peripheral transmission; the process operation mode of the ball mill is a batch type or a continuous type.
6. The preparation method according to claim 5, wherein in the step 2, the rotation speed of the ball mill is 50-500rpm, and the ball milling time is 5-1800min; in step 3, the cylindrical, rectangular or square stainless steel metal or ceramic die with the diameter of 10, 20, 30 or 50mm is pressed by a pressure forming device under the pressure of 1-120MPa for 3-120min.
7. The production method according to any one of claims 1 to 6, wherein the hexagonal boron nitride is contained in an amount of 65 to 95% by mass based on the total amount of the substance.
8. The preparation method according to claim 7, wherein hexagonal boron nitride nanosheets are exfoliated using commercial hexagonal boron nitride powder; the diameter of the hexagonal boron nitride nanosheet is 10-1000nm.
9. A high loading boron nitride/polymer bulk composite prepared by the method of any one of claims 1-8.
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