CN113461988A - High-thermal-conductivity side-chain liquid crystal polymer film and preparation method thereof - Google Patents
High-thermal-conductivity side-chain liquid crystal polymer film and preparation method thereof Download PDFInfo
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- 229920000106 Liquid crystal polymer Polymers 0.000 title claims abstract description 91
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 73
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000011259 mixed solution Substances 0.000 claims abstract description 38
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000000137 annealing Methods 0.000 claims abstract description 8
- 238000005266 casting Methods 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 claims description 60
- 235000012000 cholesterol Nutrition 0.000 claims description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 26
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 26
- 239000000178 monomer Substances 0.000 claims description 19
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 13
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 239000003208 petroleum Substances 0.000 claims description 9
- 239000003480 eluent Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 6
- 230000003098 cholesteric effect Effects 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229910052582 BN Inorganic materials 0.000 claims description 3
- 239000002135 nanosheet Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
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- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000235 small-angle X-ray scattering Methods 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
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- 238000001228 spectrum Methods 0.000 description 2
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 239000004020 conductor Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 229920006254 polymer film Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 1
- 239000005266 side chain polymer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08J2333/04—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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Abstract
The invention discloses a high-thermal-conductivity side chain liquid crystal polymer film and a preparation method thereof, wherein the preparation method of the high-thermal-conductivity side chain liquid crystal polymer film comprises the following steps: dissolving a side chain liquid crystal polymer in an organic solvent to obtain a solution A; sequentially soaking inorganic high-thermal-conductivity particles in a nitric acid solution and a hydrogen peroxide solution, and then adding the inorganic high-thermal-conductivity particles into a tetrahydrofuran solution dissolved with monoamino POSS for ultrasonic dispersion to obtain a solution B; adding the solution B into the solution A and mixing to obtain a mixed solution; and casting the mixed solution on a template with a fixed size, volatilizing the solvent, annealing under the protection of inert gas, and cooling to obtain the high-thermal-conductivity side chain liquid crystal polymer film. The high-thermal-conductivity side chain liquid crystal polymer film prepared by the invention has better thermal conductivity and can meet the requirement of the electronic field on high-thermal-conductivity materials.
Description
Technical Field
The invention relates to the field of liquid crystal polymers, in particular to a high-thermal-conductivity side chain liquid crystal polymer film and a preparation method thereof.
Background
With the development of industrial demands and scientific technologies, higher requirements are put forward on various engineering heat conducting materials, and in order to ensure the reliability of the operation of electronic components at the use environment temperature, high-heat-dissipation interface materials and packaging materials are required to be used for quickly and effectively transferring and releasing heat accumulated by heating components, so that the service life of the electronic components is prolonged. Therefore, the research and development of the polymer-based heat-conducting composite material with high heat conductivity has urgent theoretical significance and practical application value for the design and development of materials in the electronic field.
The chemical structure of the Side Chain Liquid Crystal Polymers (SCLCPs) is composed of four parts, namely a main chain (Polymer backbone), a spacer (flexible spacer), a mesogen unit (mesogen unit) and a tail chain (tail chain).
However, the application of the side chain liquid crystal polymer depends on the phase state structure and the phase behavior of the side chain liquid crystal polymer to a great extent, in the invention, firstly, a cholesteric side chain liquid crystal polymer material is provided, the cholesteric side chain liquid crystal polymer with stable liquid crystal phase is obtained by changing the length of the flexible spacer group and the cholesteric side group structure, and secondly, the side chain liquid crystal polymer film with high heat conductivity is obtained by doping inorganic high heat conductivity particles in the side chain liquid crystal polymer, thereby meeting the requirements of materials in related fields.
Accordingly, there is still a need for advancement and development of the prior art.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention provides a high thermal conductivity side chain liquid crystal polymer film and a method for preparing the same, which aims to improve the thermal conductivity of the side chain liquid crystal polymer film.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of a high-thermal-conductivity side chain liquid crystal polymer film comprises the following steps:
dissolving a side chain liquid crystal polymer in an organic solvent to obtain a solution A;
sequentially soaking inorganic high-thermal-conductivity particles in a nitric acid solution and a hydrogen peroxide solution, and then adding the inorganic high-thermal-conductivity particles into a tetrahydrofuran solution dissolved with monoamino POSS for ultrasonic dispersion to obtain a solution B;
adding the solution B into the solution A and mixing to obtain a mixed solution;
casting the mixed solution on a template with a fixed size, volatilizing the solvent, annealing under the protection of inert gas, and cooling to obtain the high-thermal-conductivity side chain liquid crystal polymer film;
wherein the side chain liquid crystal polymer is a copolymer obtained by reacting acrylic acid cholesterol with methyl acrylate, and the molar ratio of the acrylic acid cholesterol to the methyl acrylate is 6:4 to 8: 2.
The high-thermal-conductivity side chain liquid crystal polymer film is characterized in that the organic solvent is one or more of chloroform, tetrahydrofuran, acetone or toluene.
The high-thermal-conductivity side chain liquid crystal polymer film is characterized in that the inorganic high-thermal-conductivity particles are one or more of boron nitride nanosheets, boron nitride nanotubes or silicon nitride.
The high-thermal-conductivity side chain liquid crystal polymer film is characterized in that the nitric acid solution is 20-30% of nitric acid solution in mass fraction.
The high-thermal-conductivity side chain liquid crystal polymer film is characterized in that the hydrogen peroxide solution is a 30% hydrogen peroxide solution in mass fraction.
The high-thermal-conductivity side chain liquid crystal polymer film is characterized in that the template is a glass template.
The high-thermal-conductivity side chain liquid crystal polymer film is characterized in that the preparation of the side chain liquid crystal polymer comprises the following steps:
and (3) reacting acrylic acid cholesterol monomer, methyl acrylate, a CPDB solution, an AIBN solution and chlorobenzene for 12 hours at the temperature of 75 ℃ to obtain the side chain liquid crystal polymer.
The high-thermal-conductivity side chain liquid crystal polymer film comprises a high-thermal-conductivity side chain liquid crystal polymer film body, wherein the preparation of the acrylic acid cholesterol monomer comprises the following steps:
mixing cholesterol, triethylamine and tetrahydrofuran, and performing reflux reaction on the mixed solution A for 2-3h at the temperature of 70-80 ℃ to obtain an intermediate mixed solution;
dripping tetrahydrofuran solution of acryloyl chloride into the intermediate mixed solution, and performing reflux reaction for 12-15h to obtain mixed solution;
and pouring the mixed solution into an HCl/methanol mixed solution to obtain a light yellow solid, and then removing impurities by using a mixed solution of petroleum ether and dichloromethane as an eluent to obtain a white acrylic acid cholesterol monomer.
The high-thermal-conductivity side chain liquid crystal polymer film is characterized in that the volume ratio of petroleum ether to dichloromethane in the eluent is 1: 2.
Meanwhile, the invention also provides a high-thermal-conductivity side chain liquid crystal polymer film which is prepared by adopting the preparation method of the high-thermal-conductivity side chain liquid crystal polymer film.
Has the advantages that: according to the high-thermal-conductivity side chain liquid crystal polymer film prepared by the invention, the side chain liquid crystal polymers in the high-thermal-conductivity side chain liquid crystal polymer film have a more ordered structure, and the gaps in the side chain liquid crystal polymer structure are filled by adopting the surface-functionalized inorganic high-thermal-conductivity particles as the thermal conductive filler, so that the high-thermal-conductivity side chain liquid crystal polymer film can be endowed with high thermal conductivity on the premise of not damaging the inherent ordered structure of the side chain liquid crystal polymers.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing a high thermal conductivity side chain liquid crystal polymer film according to the present invention;
FIG. 2 is a normal temperature small angle scattering (SAXS) spectrum of the side chain liquid crystalline polymer prepared in examples 1 to 3 of the present invention.
Detailed Description
The invention provides a high-thermal-conductivity side-chain liquid crystal polymer film and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
1. Preparation of acrylic acid cholesterol monomer
Firstly, adding cholesterol, triethylamine and THF (tetrahydrofuran) into a round-bottom flask to obtain an intermediate mixed solution, carrying out reflux reaction for 2-3h at 70-80 ℃, then slowly dropwise adding a tetrahydrofuran solution of acryloyl chloride into the intermediate mixed solution, continuing reflux reaction for 12-15h, cooling the obtained mixed solution to room temperature after the reaction is finished, pouring the cooled mixed solution into a HCL/methanol mixed solution to obtain a light yellow solid, and finally adding petroleum ether: and (3) taking dichloromethane as an eluent, and performing column separation to obtain a white solid, namely the acrylic acid cholesterol monomer. Preferably, when the volume ratio of the petroleum ether to the dichloromethane is 1:2, the purity of the acrylic acid cholesterol monomer obtained by separation is higher.
2. Preparation of side chain liquid crystal polymer
In the present invention, a side chain liquid crystal polymer was obtained by reacting a cholesteric acrylic monomer, methyl acrylate, a CPDB solution, an AIBN solution, and chlorobenzene at 75 ℃ for 12 hours by a RAFT polymerization method.
3. Preparation of high-thermal-conductivity side-chain liquid crystal polymer film
As shown in fig. 1, the preparation of the high thermal conductivity side chain liquid crystal polymer film comprises the following steps:
s10, dissolving the side chain liquid crystal polymer in an organic solvent to obtain a solution A;
s20, sequentially soaking inorganic high-thermal-conductivity particles in a nitric acid solution and a hydrogen peroxide solution, and then adding the inorganic high-thermal-conductivity particles into a tetrahydrofuran solution dissolved with monoamino POSS for ultrasonic dispersion to obtain a solution B;
s30, adding the solution B into the solution A and mixing to obtain a mixed solution;
and S40, casting the mixed solution on a template with a fixed size, volatilizing the solvent, annealing under the protection of inert gas, and cooling to obtain the high-thermal-conductivity side chain liquid crystal polymer film.
According to the invention, inorganic high-thermal-conductivity particles (such as boron nitride nanosheets, boron nitride nanotubes or silicon nitride) are sequentially soaked in a nitric acid solution and a hydrogen peroxide solution, and then added into a tetrahydrofuran solution dissolved with monoamino POSS for ultrasonic dispersion, and the inorganic high-thermal-conductivity particles with functionalized surfaces are obtained after vacuum drying.
And then, mixing the solution A in which the side chain liquid crystal polymer is dispersed and the solution B in which the surface functionalized inorganic high-thermal-conductivity particles are dispersed respectively, ultrasonically dispersing uniformly to obtain a mixed solution, casting the mixed solution on a template with a fixed size, treating the solvent, and then annealing under the protection of inert gas to obtain the high-thermal-conductivity side chain liquid crystal polymer film.
The following is a further explanation of the preparation method of the high thermal conductivity side chain liquid crystal polymer film of the present invention by specific examples:
example 1
Synthesis of acrylic acid cholesterol monomer: sequentially adding cholesterol, triethylamine and THF (tetrahydrofuran) into a round-bottom flask to obtain a mixed solution A, carrying out reflux reaction for 2 hours at the temperature of 75 ℃, slowly dropwise adding a tetrahydrofuran solution of acryloyl chloride into the solution A, continuously refluxing for 12 hours, cooling to room temperature after the reaction is finished, pouring the mixed solution into an HCl/methanol mixed solution to obtain a light yellow solid, and adding petroleum ether: and (3) taking dichloromethane as an eluent, and separating by using a column to obtain white acrylic acid cholesterol monomer.
Synthesizing a side chain liquid crystal polymer: adding acrylic cholesterol monomer, methyl acrylate, CPDB solution, AIBN solution and chlorobenzene into a polymerization tube, and reacting for 12 hours at 75 ℃ to obtain the side chain liquid crystal polymer, wherein the molar ratio of acrylic cholesterol to methyl acrylate is 8: 2.
Synthesizing a high-thermal-conductivity side chain liquid crystal polymer: dissolving a side chain liquid crystal polymer in tetrahydrofuran to obtain a solution A, simultaneously sequentially soaking silicon nitride powder in a nitric acid solution and a hydrogen peroxide solution, then adding the solution into the tetrahydrofuran solution dissolved with monoamino POSS for ultrasonic dispersion to obtain a solution B, mixing the solution A and the solution B, casting the mixture on a template with a fixed size, volatilizing the tetrahydrofuran, then annealing the mixture in a tubular furnace under the protection of inert gas, and cooling to obtain the high-thermal-conductivity side chain liquid crystal polymer film.
Example 2
Synthesis of acrylic acid cholesterol monomer: sequentially adding cholesterol, triethylamine and THF (tetrahydrofuran) into a round-bottom flask to obtain a mixed solution A, carrying out reflux reaction for 2 hours at the temperature of 75 ℃, slowly dropwise adding a tetrahydrofuran solution of acryloyl chloride into the solution A, continuously refluxing for 12 hours, cooling to room temperature after the reaction is finished, pouring the mixed solution into an HCl/methanol mixed solution to obtain a light yellow solid, and adding petroleum ether: and (3) taking dichloromethane as an eluent, and separating by using a column to obtain white acrylic acid cholesterol monomer.
Synthesizing a side chain liquid crystal polymer: adding acrylic cholesterol monomer, methyl acrylate, CPDB solution, AIBN solution and chlorobenzene into a polymerization tube, and reacting for 12 hours at 75 ℃ to obtain the side chain liquid crystal polymer, wherein the molar ratio of the acrylic cholesterol to the methyl acrylate is 7: 3.
Synthesizing a high-thermal-conductivity side chain liquid crystal polymer: dissolving a side chain liquid crystal polymer in tetrahydrofuran to obtain a solution A, simultaneously sequentially soaking silicon nitride powder in a nitric acid solution and a hydrogen peroxide solution, then adding the solution into the tetrahydrofuran solution dissolved with monoamino POSS for ultrasonic dispersion to obtain a solution B, mixing the solution A and the solution B, casting the mixture on a template with a fixed size, volatilizing the tetrahydrofuran, then annealing the mixture in a tubular furnace under the protection of inert gas, and cooling to obtain the high-thermal-conductivity side chain liquid crystal polymer film.
Example 3
Synthesis of acrylic acid cholesterol monomer: sequentially adding cholesterol, triethylamine and THF (tetrahydrofuran) into a round-bottom flask to obtain a mixed solution A, carrying out reflux reaction for 2 hours at the temperature of 75 ℃, slowly dropwise adding a tetrahydrofuran solution of acryloyl chloride into the solution A, continuously refluxing for 12 hours, cooling to room temperature after the reaction is finished, pouring the mixed solution into an HCl/methanol mixed solution to obtain a light yellow solid, and adding petroleum ether: and (3) taking dichloromethane as an eluent, and separating by using a column to obtain white acrylic acid cholesterol monomer.
Synthesizing a side chain liquid crystal polymer: adding acrylic cholesterol monomer, methyl acrylate, CPDB solution, AIBN solution and chlorobenzene into a polymerization tube, and reacting for 12 hours at 75 ℃ to obtain the side chain liquid crystal polymer, wherein the molar ratio of the acrylic cholesterol to the methyl acrylate is 6: 4.
Synthesizing a high-thermal-conductivity side chain liquid crystal polymer: dissolving a side chain liquid crystal polymer in tetrahydrofuran to obtain a solution A, simultaneously sequentially soaking silicon nitride powder in a nitric acid solution and a hydrogen peroxide solution, then adding the solution into the tetrahydrofuran solution dissolved with monoamino POSS for ultrasonic dispersion to obtain a solution B, mixing the solution A and the solution B, casting the mixture on a template with a fixed size, volatilizing the tetrahydrofuran, then annealing the mixture in a tubular furnace under the protection of inert gas, and cooling to obtain the high-thermal-conductivity side chain liquid crystal polymer film.
Further, in the present invention, the properties of the side chain liquid crystal polymer and the high thermal conductivity side chain liquid crystal polymer film prepared in examples 1 to 3 were tested, wherein the following table shows the molecular characteristics and the basic properties of the side chain liquid crystal polymer.
| Sample (I) | Mn(×104)a | MW(×104)a | PDIa | Td(℃)b | Tg(℃)c | Ti(℃)c |
| Example 1 | 1.13 | 1.31 | 1.17 | 360 | 123 | 201 |
| Example 2 | 1.09 | 1.26 | 1.15 | 355 | 121 | 187 |
| Example 3 | 1.04 | 1.21 | 1.13 | 350 | 116 | 190 |
As can be seen from the data in the table, the present invention successfully produced the liquid crystal polymer having a large molecular weight for measurement.
Further, as shown in fig. 2, fig. 2 is a normal temperature small angle scattering (SAXS) spectrum of the side chain liquid crystal polymers prepared in examples 1 to 3 of the present invention, wherein the side chain liquid crystal polymers prepared in examples 1 to 3 have two distinct diffraction peaks in a small angle region, which indicates that the polymers prepared in examples 1 to 3 all form a smectic a phase, and the corresponding SAXS parameters are as follows:
| sample (I) | q1(nm-1)a | d1(nm) | L(nm)b | 2L(nm) | Phasec |
| Example 1 | 1.84 | 3.35 | 1.94 | 3.91 | SmA2 |
| Example 2 | 1.81 | 3.42 | 1.94 | 3.91 | SmA2 |
| Example 3 | 1.80 | 3.43 | 1.94 | 3.91 | SmA2 |
Further, in the present invention, the thermal conductivity of the high thermal conductivity side chain liquid crystal polymer films prepared in examples 1 to 3 was also tested, and it should be noted that the thermal conductivity was tested based on the high thermal conductivity side chain liquid crystal polymer film with a thickness of 100um, and the results are shown in the following table:
| sample (I) | Temperature/. degree.C | Thickness/um | Thermal diffusivity/mm2/s | Thermal conductivity/W/mK |
| Example 1 | 27.3 | 100 | 0.6324 | 0.6529 |
| Example 2 | 24.6 | 100 | 0.5823 | 0.5981 |
| Example 3 | 27.1 | 100 | 0.6127 | 0.6458 |
As can be seen from the data in the table above, the high thermal conductivity side chain polymer film prepared by the invention has excellent thermal conductivity.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a high-thermal-conductivity side chain liquid crystal polymer film is characterized by comprising the following steps:
dissolving a side chain liquid crystal polymer in an organic solvent to obtain a solution A;
sequentially soaking inorganic high-thermal-conductivity particles in a nitric acid solution and a hydrogen peroxide solution, and then adding the inorganic high-thermal-conductivity particles into a tetrahydrofuran solution dissolved with monoamino POSS for ultrasonic dispersion to obtain a solution B;
adding the solution B into the solution A and mixing to obtain a mixed solution;
casting the mixed solution on a template with a fixed size, volatilizing the solvent, annealing under the protection of inert gas, and cooling to obtain the high-thermal-conductivity side chain liquid crystal polymer film;
wherein the side chain liquid crystal polymer is a copolymer obtained by reacting acrylic acid cholesterol with methyl acrylate, and the molar ratio of the acrylic acid cholesterol to the methyl acrylate is 6:4 to 8: 2.
2. The high thermal conductivity side chain liquid crystal polymer film according to claim 1, wherein the organic solvent is one or more of chloroform, tetrahydrofuran, acetone or toluene.
3. The high thermal conductivity side chain liquid crystal polymer film according to claim 1, wherein the inorganic high thermal conductivity particles are one or more of boron nitride nanosheets, boron nitride nanotubes or silicon nitride.
4. The high thermal conductivity side chain liquid crystal polymer film according to claim 1, wherein the nitric acid solution is 20-30% by mass.
5. The high thermal conductivity side chain liquid crystal polymer film according to claim 1, wherein the hydrogen peroxide solution is a 30% by mass hydrogen peroxide solution.
6. The high thermal conductivity side chain liquid crystal polymer film according to claim 1, wherein the template is a glass template.
7. The high thermal conductivity side chain liquid crystal polymer film according to claim 1, wherein the preparation of the side chain liquid crystal polymer comprises the steps of:
and (3) reacting acrylic acid cholesterol monomer, methyl acrylate, a CPDB solution, an AIBN solution and chlorobenzene for 12 hours at the temperature of 75 ℃ to obtain the side chain liquid crystal polymer.
8. The high thermal conductive side chain liquid crystal polymer film according to claim 7, wherein the preparation of the acrylic cholesteric monomer comprises the steps of:
mixing cholesterol, triethylamine and tetrahydrofuran, and performing reflux reaction on the mixed solution A for 2-3h at the temperature of 70-80 ℃ to obtain an intermediate mixed solution;
dripping tetrahydrofuran solution of acryloyl chloride into the intermediate mixed solution, and performing reflux reaction for 12-15h to obtain mixed solution;
and pouring the mixed solution into an HCl/methanol mixed solution to obtain a light yellow solid, and then removing impurities by using a mixed solution of petroleum ether and dichloromethane as an eluent to obtain a white acrylic acid cholesterol monomer.
9. The high thermal conductivity side chain liquid crystal polymer film according to claim 8, wherein the volume ratio of petroleum ether to dichloromethane in the eluent is 1: 2.
10. A high thermal conductivity side chain liquid crystal polymer film, characterized in that, it is prepared by the method of any one of claims 1-9.
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| JP2011001452A (en) * | 2009-06-18 | 2011-01-06 | Jsr Corp | Heat-conductive resin composition and heat-conductive film |
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| JP2011001452A (en) * | 2009-06-18 | 2011-01-06 | Jsr Corp | Heat-conductive resin composition and heat-conductive film |
| CN109180979A (en) * | 2018-10-31 | 2019-01-11 | 西安科技大学 | A kind of preparation method of high thermal conductivity side chain type liquid crystal macromolecule member material |
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