CN114075340A - Preparation method of composite hydrogel with three-dimensional heat conduction network - Google Patents
Preparation method of composite hydrogel with three-dimensional heat conduction network Download PDFInfo
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- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
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- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/02—Polyamines
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Abstract
A preparation method of a composite hydrogel with a three-dimensional heat conducting network comprises the following steps: repeatedly and circularly dipping the three-dimensional flexible skeleton in Boron Nitride (BN) and Polyethyleneimine (PEI) solution to obtain primary heat-conducting network three-dimensional BN; utilizing Dopamine (DA) to perform functionalization treatment on Boron Nitride (BN) attached to a network to obtain functionalized three-dimensional BN-PDA; and adding a polyvinyl alcohol (PVA) solution into the heat conducting network by utilizing a vacuum defoaming technology, and repeatedly freezing and thawing to prepare the hydrogel, wherein the PVA is a composite material matrix.
Description
Technical Field
The invention relates to the field of composite material heat conduction, in particular to a preparation technology of heat-conducting composite hydrogel.
Background
In recent years, with the rapid development of electronic technology, the integration level and power density of electronic components are increasing, and the amount of heat generated by the electronic components is increasing, which has an adverse effect on the service life of the electronic components. It is very important to improve the heat dissipation capability of the heat sink. The key point is to increase the thermal conductivity of the thermal conductive material to promote the rapid heat dissipation of the electronic device. Therefore, how to combine the high thermal conductivity of the polymer composite material while maintaining the flexibility of the polymer composite material becomes the key to solve the problem. Generally, the incorporation of highly thermally conductive fillers into the matrix material is a common method of making thermally conductive reinforced composites. Highly thermally conductive fillers, such as metals, ceramics, and carbon-based materials, are used to increase the thermal conductivity of polymer composites, all of which exhibit higher thermal conductivity.
Among the above fillers, Boron Nitride (BN) has received much attention because of its electrical insulation and high thermal conductivity. The hexagonal boron nitride has a honeycomb crystal structure, has good chemical stability, thermal conductivity and electrical conductivity, and has good chemical stability and mechanical strength. The boron atoms and nitrogen atoms are bonded in a cellular structure in sp2, which gives it a graphite-like structure. Boron nitride has been introduced into various polymer composite materials as a heat conductive filler to meet the requirement of high heat conductive performance of the materials.
However, the thermal conductivity of the thermal conductive composite material filled with the thermal conductive particles in a random distribution is improved to a very limited extent, and a high content is required to obtain high thermal conductivity. This is because the thermal conductive filler is randomly dispersed in the polymer matrix, which increases the interface thermal resistance of the material, but is not favorable for improving the thermal conductivity of the composite material. Meanwhile, excessive use of the heat-conducting filler inevitably leads to reduction of mechanical properties of the composite material, increase of cost and increase of processing difficulty. It is well known that in composite materials, the ability to form a continuous heat conduction path is of great significance to the ability of the material to possess excellent heat conduction properties. The construction of three-dimensional filler networks in composite materials is of great interest because it can reduce filler usage and reduce inter-filler thermal resistance. Therefore, there is a need to build three-dimensional networks to make improved thermally conductive polymer composites. The carbon nanotubes are introduced into the epoxy resin through the network by the aid of the flying tigers, so that the thermal management capability of the epoxy resin is effectively improved (Lianxin, flying tigers. the three-dimensional network of the single-walled carbon nanotubes is constructed by the aid of the epoxy nanocomposite of the reduced graphene oxide, and the thermal management capability of the epoxy resin is enhanced under low filler load [ J ]. ACS material interface, 2019 (volume 12)).
Hydrogels are promising crosslinked polymers for various biomedical applications, wound healing and drug delivery. In recent years, the hydrogel developed by researchers can be used for the sensory driving of biomolecular circuits. This increases their importance in biomedical research, as the swelling shape of the hydrogels themselves controls the swelling and shrinking of organisms. In addition, hydrogels are also used for thermal conduction of nanocomposites. The plum is bright, and the agarose gel-based composite material containing different boron nitride fillers is synthesized, so that the heat conductivity coefficient of the hydrogel material is effectively improved. (Liliang. boron nitride/agar hydrogel composite with high thermal conductivity [ J ] rare metals 2020, (stage 39)).
However, there has been little research into the effect of boron nitride fillers on the thermal conductivity of hydrogel-based composites. We decided that the system investigated the effect of the manner in which the boron nitride filler was introduced on the thermal conductivity of the hydrogel.
Disclosure of Invention
The invention provides a preparation method of PVA composite hydrogel with high thermal conductivity, aiming at the characteristic of low thermal conductivity coefficient of polyvinyl alcohol (PVA) hydrogel.
The invention adopts the following technical scheme:
a preparation method of a composite hydrogel with a three-dimensional heat conducting network comprises the following steps: repeatedly and circularly dipping the three-dimensional flexible skeleton in Boron Nitride (BN) and Polyethyleneimine (PEI) solution, and obtaining primary heat-conducting network three-dimensional BN as shown in figure 1; utilizing Dopamine (DA) to perform functionalization treatment on Boron Nitride (BN) attached to a network to obtain functionalized three-dimensional BN-PDA; and adding a polyvinyl alcohol (PVA) solution into the heat conducting network by utilizing a vacuum defoaming technology, and repeatedly freezing and thawing to prepare the hydrogel, wherein the PVA is a composite material matrix.
The invention discloses a preparation method of a composite hydrogel with a three-dimensional heat conduction network, which comprises the following specific steps:
1) sequentially dipping the three-dimensional flexible framework in a Boron Nitride (BN) solution and a Polyethyleneimine (PEI) solution, and circulating for 5-30 times; drying the soaked sponge for 60-120 minutes by using a blast dryer to obtain primary heat-conducting network three-dimensional BN; wherein the concentration of the BN solution is 0.5-2 mg/mL, and the concentration of the PEI is 0.5-2 mg/mL;
2) preparing a buffer solution by using Tris (hydroxymethyl) aminomethane (Tris), and adjusting the pH to 8.5 by using dilute hydrochloric acid; weighing 0.05-0.1% by mass of Dopamine (DA), adding the DA and the primary heat-conducting network three-dimensional BN prepared in the step 1) into a buffer solution under the condition of keeping out of the sun, stirring for 5-30 minutes under the condition of water bath heating, taking out the heat-conducting network, and then placing the heat-conducting network into a blast drier for drying for 60-120 minutes to obtain functionalized three-dimensional BN-PDA; the heating and stirring temperature is 50-70 ℃, and the stirring speed is 60-200 r/min;
3) under the conditions of water bath heating and continuous stirring, slowly adding 5-20% by mass of polyvinyl alcohol (PVA) particles into a beaker filled with distilled water until the particles are completely dissolved, continuously stirring for 60-120 minutes, standing and cooling to normal temperature to obtain a uniform PVA solution; the heating and stirring temperature is 85-95 ℃, and the stirring speed is 60-200 r/min;
4) filling the three-dimensional heat conducting network by adopting a vacuum defoaming technology, completely soaking the functionalized three-dimensional BN-PDA prepared in the step 2) into the PVA solution prepared in the step 3), placing the solution into a vacuum oven for standing and defoaming for 60-120 minutes, and taking out the three-dimensional network after the solution is completely defoamed to obtain the completely soaked three-dimensional heat conducting network;
5) preparing the composite hydrogel by adopting a freezing-thawing mode, freezing the three-dimensional heat conduction network completely filled with the PVA solution for 8-20h at the temperature of-10 to-80 ℃, taking out the three-dimensional heat conduction network, unfreezing the three-dimensional heat conduction network for 4-10h at the temperature of 20-30 ℃, and repeatedly circulating for 5-10 times to obtain the composite hydrogel with the solid-liquid interpenetrating three-dimensional network structure.
The concrete description is as follows:
1) the thermal conductivity of the pure PVA hydrogel was denoted as T1The thermal conductivity coefficient of the modified composite hydrogel with the three-dimensional network structure is recorded as T2. The heat conduction promotion rate of the composite hydrogel is
In this experiment, the main reasons that the thermal conductivity of the composite hydrogel could be improved were: the three-dimensional heat-conducting network framework is filled in the PVA hydrogel matrix in a continuous path mode, and polydopamine is connected in the PVA hydrogel and the three-dimensional heat-conducting network framework, so that the interface thermal resistance between the high polymer material and the three-dimensional heat-conducting network is reduced. When one end of the composite hydrogel is acted by high temperature of the environment, the phonons conducting heat can conduct along the heat conducting paths mutually connected in the matrix, so that the interface thermal resistance between the high polymer material and the high heat conducting filler is reduced, and the accumulation of heat is avoided. Therefore, the problem of low heat conductivity coefficient of the polymer matrix is solved.
The invention has the beneficial effects that: PVA is rich in hydroxyl, has certain biocompatibility and has great potential in biological application convenience. The hydrogel material PVA is cheap and easy to obtain, and is prepared in a physical crosslinking mode, the preparation method is simple, and the requirement on equipment is low. The hydrogel is compounded with the prepared three-dimensional heat conducting network, so that the heat conducting performance of the high polymer material is improved, and the hydrogel has wide application in the aspects of heat dissipation of some electronic devices or organism cooling.
Detailed description of the invention
The following examples of the present invention are given to further illustrate the present invention, but not to limit the scope of the present invention.
Example 1
1) Sequentially dipping the three-dimensional flexible framework in a Boron Nitride (BN) solution and a Polyethyleneimine (PEI) solution, and circulating for 5 times; drying the soaked sponge for 120 minutes by using a blast dryer to obtain primary heat-conducting network three-dimensional BN; wherein the concentration of the BN solution is 0.5mg/mL, and the concentration of the PEI is 0.5 mg/mL;
2) preparing a buffer solution by using Tris (hydroxymethyl) aminomethane (Tris), and adjusting the pH to 8.5 by using dilute hydrochloric acid; weighing 0.06% by mass of Dopamine (DA), adding the DA and the primary heat-conducting network three-dimensional BN prepared in the step 1) into a buffer solution under the condition of keeping out of the sun, stirring for 20 minutes under the condition of water bath heating, taking out the heat-conducting network, and then placing the heat-conducting network in a blast drier for drying for 120 minutes to obtain the functionalized three-dimensional BN-PDA; the heating and stirring temperature is 55 ℃, and the stirring speed is 60r/min
3) Under the conditions of water bath heating and continuous stirring, slowly adding polyvinyl alcohol (PVA) particles with the mass fraction of 10% into a beaker filled with distilled water until the particles are completely dissolved, continuously stirring for 60 minutes, standing and cooling to normal temperature to obtain a uniform PVA solution; the heating and stirring temperature is 90 ℃, and the stirring speed is 60r/min
4) Filling the three-dimensional heat conduction network by adopting a vacuum defoaming technology, completely soaking the functionalized three-dimensional BN-PDA prepared in the step 2) into the PVA solution prepared in the step 3), placing the solution into a vacuum oven for standing and defoaming for 100 minutes, and taking out the three-dimensional network after the solution is completely defoamed to obtain a completely soaked three-dimensional heat conduction network;
5) preparing the composite hydrogel by adopting a freezing-thawing mode, freezing the three-dimensional heat conduction network completely filled with the PVA solution for 15h at the temperature of minus 30 ℃, thawing for 10h at the temperature of 20 ℃ after taking out, and repeatedly cycling for 8 times to obtain the composite hydrogel with the solid-liquid interpenetrating three-dimensional network structure.
Example 2
1) Sequentially dipping the three-dimensional flexible framework in a Boron Nitride (BN) solution and a Polyethyleneimine (PEI) solution, and circulating for 20 times; drying the soaked sponge for 60 minutes by using a blast dryer to obtain primary heat-conducting network three-dimensional BN; wherein the concentration of the BN solution is 2mg/mL, and the concentration of the PEI is 1.5 mg/mL;
2) preparing a buffer solution by using Tris (hydroxymethyl) aminomethane (Tris), and adjusting the pH to 8.5 by using dilute hydrochloric acid; weighing 0.08% by mass of Dopamine (DA), adding the DA and the primary heat-conducting network three-dimensional BN prepared in the step 1) into a buffer solution under the condition of keeping out of the sun, stirring for 30 minutes under the condition of water bath heating, taking out the heat-conducting network, and then placing the heat-conducting network in a forced air drier for drying for 60 minutes to obtain the functionalized three-dimensional BN-PDA; the heating and stirring temperature is 70 ℃, and the stirring speed is 150r/min
3) Under the conditions of water bath heating and continuous stirring, slowly adding 5% by mass of polyvinyl alcohol (PVA) particles into a beaker filled with distilled water until the particles are completely dissolved, continuously stirring for 90 minutes, standing and cooling to normal temperature to obtain a uniform PVA solution; the heating and stirring temperature is 85 ℃, and the stirring speed is 100r/min
4) Filling the three-dimensional heat conduction network by adopting a vacuum defoaming technology, completely soaking the functionalized three-dimensional BN-PDA prepared in the step 2) into the PVA solution prepared in the step 3), placing the solution into a vacuum oven for standing and defoaming for 120 minutes, and taking out the three-dimensional network after the solution is completely defoamed to obtain a completely soaked three-dimensional heat conduction network;
5) preparing the composite hydrogel by adopting a freezing-thawing mode, freezing the three-dimensional heat conduction network completely filled with the PVA solution for 20h at the temperature of minus 40 ℃, taking out the three-dimensional heat conduction network, thawing for 4h at the temperature of 25 ℃, and repeatedly circulating for 10 times to obtain the composite hydrogel with the solid-liquid interpenetrating three-dimensional network structure.
Example 3
1) Sequentially dipping the three-dimensional flexible framework in a Boron Nitride (BN) solution and a Polyethyleneimine (PEI) solution, and circulating for 30 times; drying the soaked sponge for 80 minutes by using a blast dryer to obtain primary heat-conducting network three-dimensional BN; wherein the concentration of the BN solution is 1mg/mL, and the concentration of the PEI is 2 mg/mL;
2) preparing a buffer solution by using Tris (hydroxymethyl) aminomethane (Tris), and adjusting the pH to 8.5 by using dilute hydrochloric acid; weighing 0.1% by mass of Dopamine (DA), adding the dopamine and the primary heat-conducting network three-dimensional BN prepared in the step 1) into a buffer solution under the condition of keeping out of the sun, stirring for 5 minutes under the condition of water bath heating, taking out the heat-conducting network, and then placing the heat-conducting network in a forced air drier for drying for 60 minutes to obtain functionalized three-dimensional BN-PDA; the heating and stirring temperature is 50 ℃, and the stirring speed is 200r/min
3) Under the conditions of water bath heating and continuous stirring, slowly adding 20% by mass of polyvinyl alcohol (PVA) particles into a beaker filled with distilled water until the particles are completely dissolved, continuously stirring for 120 minutes, standing and cooling to normal temperature to obtain a uniform PVA solution; the heating and stirring temperature is 5 ℃, and the stirring speed is 70r/min
4) Filling the three-dimensional heat conduction network by adopting a vacuum defoaming technology, completely soaking the functionalized three-dimensional BN-PDA prepared in the step 2) into the PVA solution prepared in the step 3), placing the solution into a vacuum oven for standing and defoaming for 60 minutes, and taking out the three-dimensional network after the solution is completely defoamed to obtain a completely soaked three-dimensional heat conduction network;
5) preparing the composite hydrogel by adopting a freezing-thawing mode, freezing the three-dimensional heat conduction network completely filled with the PVA solution for 8 hours at the temperature of-10 ℃, taking out the three-dimensional heat conduction network, thawing for 5 hours at the temperature of 30 ℃, and repeatedly circulating for 8 times to obtain the composite hydrogel with the solid-liquid interpenetrating three-dimensional network structure.
Example 4
1) Sequentially dipping the three-dimensional flexible framework in a Boron Nitride (BN) solution and a Polyethyleneimine (PEI) solution, and circulating for 15 times; drying the soaked sponge for 120 minutes by using a blast dryer to obtain primary heat-conducting network three-dimensional BN; wherein the concentration of the BN solution is 0.6mg/mL, and the concentration of the PEI is 1.5 mg/mL;
2) preparing a buffer solution by using Tris (hydroxymethyl) aminomethane (Tris), and adjusting the pH to 8.5 by using dilute hydrochloric acid; weighing 0.05% by mass of Dopamine (DA), adding the DA and the primary heat-conducting network three-dimensional BN prepared in the step 1) into a buffer solution under the condition of keeping out of the sun, stirring for 20 minutes under the condition of water bath heating, taking out the heat-conducting network, and then placing the heat-conducting network in a forced air drier for drying for 70 minutes to obtain functionalized three-dimensional BN-PDA; the heating and stirring temperature is 65 ℃, and the stirring speed is 100r/min
3) Under the conditions of water bath heating and continuous stirring, slowly adding 15% by mass of polyvinyl alcohol (PVA) particles into a beaker filled with distilled water until the particles are completely dissolved, continuously stirring for 90 minutes, standing and cooling to normal temperature to obtain a uniform PVA solution; the heating and stirring temperature is 95 ℃, and the stirring speed is 200r/min
4) Filling the three-dimensional heat conduction network by adopting a vacuum defoaming technology, completely soaking the functionalized three-dimensional BN-PDA prepared in the step 2) into the PVA solution prepared in the step 3), placing the solution into a vacuum oven for standing and defoaming for 60 minutes, and taking out the three-dimensional network after the solution is completely defoamed to obtain a completely soaked three-dimensional heat conduction network;
5) preparing the composite hydrogel by adopting a freezing-thawing mode, freezing the three-dimensional heat conduction network completely filled with the PVA solution for 15h at the temperature of minus 30 ℃, taking out the three-dimensional heat conduction network, thawing for 6h at the temperature of 30 ℃, and repeatedly circulating for 5 times to obtain the composite hydrogel with the solid-liquid interpenetrating three-dimensional network structure.
Example 5
1) Sequentially dipping the three-dimensional flexible framework in a Boron Nitride (BN) solution and a Polyethyleneimine (PEI) solution, and circulating for 25 times; drying the soaked sponge for 90 minutes by using a blast dryer to obtain primary heat-conducting network three-dimensional BN; wherein the concentration of the BN solution is 1.7mg/mL, and the concentration of the PEI is 0.7 mg/mL;
2) preparing a buffer solution by using Tris (hydroxymethyl) aminomethane (Tris), and adjusting the pH to 8.5 by using dilute hydrochloric acid; weighing 0.08% by mass of Dopamine (DA), adding the DA and the primary heat-conducting network three-dimensional BN prepared in the step 1) into a buffer solution under the condition of keeping out of the sun, stirring for 25 minutes under the condition of water bath heating, taking out the heat-conducting network, and then placing the heat-conducting network in a blast drier for drying for 90 minutes to obtain the functionalized three-dimensional BN-PDA; the heating and stirring temperature is 55 ℃, and the stirring speed is 150r/min
3) Under the conditions of water bath heating and continuous stirring, slowly adding polyvinyl alcohol (PVA) particles with the mass fraction of 8% into a beaker filled with distilled water until the particles are completely dissolved, continuously stirring for 90 minutes, standing and cooling to normal temperature to obtain a uniform PVA solution; the heating and stirring temperature is 90 ℃, and the stirring speed is 150r/min
4) Filling the three-dimensional heat conduction network by adopting a vacuum defoaming technology, completely soaking the functionalized three-dimensional BN-PDA prepared in the step 2) into the PVA solution prepared in the step 3), placing the solution into a vacuum oven for standing and defoaming for 100 minutes, and taking out the three-dimensional network after the solution is completely defoamed to obtain a completely soaked three-dimensional heat conduction network;
5) preparing the composite hydrogel by adopting a freezing-thawing mode, freezing the three-dimensional heat conduction network completely filled with the PVA solution for 17h at the temperature of-25 ℃, taking out the three-dimensional heat conduction network, thawing for 7h at the temperature of 26 ℃, and repeatedly circulating for 7 times to obtain the composite hydrogel with the solid-liquid interpenetrating three-dimensional network structure.
Example 6
1) Sequentially dipping the three-dimensional flexible framework in a Boron Nitride (BN) solution and a Polyethyleneimine (PEI) solution, and circulating for 20 times; drying the soaked sponge for 100 minutes by using a blast dryer to obtain primary heat-conducting network three-dimensional BN; wherein the concentration of the BN solution is 0.5mg/mL, and the concentration of the PEI is 0.5 mg/mL;
2) preparing a buffer solution by using Tris (hydroxymethyl) aminomethane (Tris), and adjusting the pH to 8.5 by using dilute hydrochloric acid; weighing 0.08% by mass of Dopamine (DA), adding the DA and the primary heat-conducting network three-dimensional BN prepared in the step 1) into a buffer solution under the condition of keeping out of the sun, stirring for 17 minutes under the condition of water bath heating, taking out the heat-conducting network, and then placing the heat-conducting network in a forced air drier for drying for 70 minutes to obtain functionalized three-dimensional BN-PDA; the heating and stirring temperature is 65 ℃, and the stirring speed is 80r/min
3) Under the conditions of water bath heating and continuous stirring, slowly adding 15% by mass of polyvinyl alcohol (PVA) particles into a beaker filled with distilled water until the particles are completely dissolved, continuously stirring for 80 minutes, standing and cooling to normal temperature to obtain a uniform PVA solution; the heating and stirring temperature is 85 ℃, and the stirring speed is 140r/min
4) Filling the three-dimensional heat conduction network by adopting a vacuum defoaming technology, completely soaking the functionalized three-dimensional BN-PDA prepared in the step 2) into the PVA solution prepared in the step 3), placing the solution into a vacuum oven for standing and defoaming for 100 minutes, and taking out the three-dimensional network after the solution is completely defoamed to obtain a completely soaked three-dimensional heat conduction network;
5) preparing the composite hydrogel by adopting a freezing-thawing mode, freezing the three-dimensional heat conduction network completely filled with the PVA solution for 18h at the temperature of-30 ℃, taking out the three-dimensional heat conduction network, thawing for 6h at the temperature of 25 ℃, and repeatedly circulating for 9 times to obtain the composite hydrogel with the solid-liquid interpenetrating three-dimensional network structure.
Example 7
1) Sequentially dipping the three-dimensional flexible framework in a Boron Nitride (BN) solution and a Polyethyleneimine (PEI) solution, and circulating for 28 times; drying the soaked sponge for 80 minutes by using a blast dryer to obtain primary heat-conducting network three-dimensional BN; wherein the concentration of the BN solution is 1mg/mL, and the concentration of the PEI is 2 mg/mL;
2) preparing a buffer solution by using Tris (hydroxymethyl) aminomethane (Tris), and adjusting the pH to 8.5 by using dilute hydrochloric acid; weighing 0.1% by mass of Dopamine (DA), adding the DA and the primary heat-conducting network three-dimensional BN prepared in the step 1) into a buffer solution under the condition of keeping out of the sun, stirring for 300 minutes under the condition of water bath heating, taking out the heat-conducting network, and then placing the heat-conducting network in a forced air drier for drying for 100 minutes to obtain the functionalized three-dimensional BN-PDA; the heating and stirring temperature is 70 ℃, and the stirring speed is 120r/min
3) Under the conditions of water bath heating and continuous stirring, slowly adding polyvinyl alcohol (PVA) particles with the mass fraction of 10% into a beaker filled with distilled water until the particles are completely dissolved, continuously stirring for 60 minutes, standing and cooling to normal temperature to obtain a uniform PVA solution; the heating and stirring temperature is 90 ℃, and the stirring speed is 180r/min
4) Filling the three-dimensional heat conduction network by adopting a vacuum defoaming technology, completely soaking the functionalized three-dimensional BN-PDA prepared in the step 2) into the PVA solution prepared in the step 3), placing the solution into a vacuum oven for standing and defoaming for 90 minutes, and taking out the three-dimensional network after the solution is completely defoamed to obtain a completely soaked three-dimensional heat conduction network;
5) preparing the composite hydrogel by adopting a freezing-thawing mode, freezing the three-dimensional heat conduction network completely filled with the PVA solution for 18h at the temperature of-15 ℃, taking out the three-dimensional heat conduction network, thawing for 8h at the temperature of 30 ℃, and repeatedly circulating for 10 times to obtain the composite hydrogel with the solid-liquid interpenetrating three-dimensional network structure.
Claims (4)
1. A preparation method of a composite hydrogel with a three-dimensional heat conducting network comprises the following steps: repeatedly and circularly dipping the three-dimensional flexible skeleton in Boron Nitride (BN) and Polyethyleneimine (PEI) solution to obtain primary heat-conducting network three-dimensional BN; utilizing Dopamine (DA) to perform functionalization treatment on Boron Nitride (BN) attached to a network to obtain functionalized three-dimensional BN-PDA; and adding a polyvinyl alcohol (PVA) solution into the heat conducting network by utilizing a vacuum defoaming technology, and repeatedly freezing and thawing to prepare the hydrogel, wherein the PVA is a composite material matrix.
2. A preparation method of composite hydrogel with a three-dimensional heat conduction network comprises the following specific steps:
1) sequentially dipping the three-dimensional flexible framework in a Boron Nitride (BN) solution and a Polyethyleneimine (PEI) solution, and circulating for 5-30 times; drying the soaked sponge for 60 minutes by using a blast dryer to obtain primary heat-conducting network three-dimensional BN; wherein the concentration of the BN solution is 0.5-2 mg/mL, and the concentration of the PEI is 0.5-2 mg/mL;
2) preparing a buffer solution by using Tris (hydroxymethyl) aminomethane (Tris), and adjusting the pH to 8.5 by using dilute hydrochloric acid; weighing 0.05-0.1% by mass of Dopamine (DA), adding the DA and the primary heat-conducting network three-dimensional BN prepared in the step 1) into a buffer solution under the condition of keeping out of the sun, stirring for 5-30 minutes under the condition of water bath heating, taking out the heat-conducting network, and then placing the heat-conducting network into a blast drier for drying for 60 minutes to obtain functionalized three-dimensional BN-PDA; the heating and stirring temperature is 50-70 ℃, and the stirring speed is 60-200 r/min
3) Under the conditions of water bath heating and continuous stirring, slowly adding 5-20% by mass of polyvinyl alcohol (PVA) particles into a beaker filled with distilled water until the particles are completely dissolved, continuously stirring for 60 minutes, standing and cooling to normal temperature to obtain a uniform PVA solution; the heating and stirring temperature is 85-95 ℃, and the stirring speed is 60-200 r/min
4) Filling the three-dimensional heat conduction network by adopting a vacuum defoaming technology, completely soaking the functionalized three-dimensional BN-PDA prepared in the step 2) into the PVA solution prepared in the step 3), placing the solution into a vacuum oven for standing and defoaming for 60 minutes, and taking out the three-dimensional network after the solution is completely defoamed to obtain a completely soaked three-dimensional heat conduction network;
5) preparing the composite hydrogel by adopting a freezing-thawing mode, freezing the three-dimensional heat conduction network completely filled with the PVA solution for 8-20h at the temperature of-10 to-80 ℃, taking out, unfreezing for 4-10h at the temperature of 20-30 ℃, and repeatedly circulating for 5-10 times to obtain the composite hydrogel with the three-dimensional network structure.
3. The method as set forth in claim 2, wherein in the step 1), the three-dimensional flexible skeleton means a porous network having a three-dimensional continuous pore structure, which may be a polyamide network, a polycellulose network, or a polyester network.
4. The composite hydrogel with three-dimensional heat-conducting network according to claim 1, wherein the three-dimensional heat-conducting network is utilized to form a continuous heat-conducting path inside the polymer hydrogel, and polydopamine is used to connect the polymer material and the boron nitride filler with high heat conductivity, so as to reduce the interface thermal resistance between the polymer material and the heat-conducting filler.
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| CN115895269B (en) * | 2022-10-31 | 2023-09-22 | 长沙先进电子材料工业技术研究院有限公司 | Heat-conducting gel and preparation method and application thereof |
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