CN109180979B - Preparation method of high-thermal-conductivity side chain type liquid crystal polymer film material - Google Patents
Preparation method of high-thermal-conductivity side chain type liquid crystal polymer film material Download PDFInfo
- Publication number
- CN109180979B CN109180979B CN201811289062.3A CN201811289062A CN109180979B CN 109180979 B CN109180979 B CN 109180979B CN 201811289062 A CN201811289062 A CN 201811289062A CN 109180979 B CN109180979 B CN 109180979B
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- side chain
- film material
- conductivity
- polymer film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
- C08J2383/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
- C08J2383/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
Abstract
The invention discloses a preparation method of a high-thermal-conductivity side chain type liquid crystal polymer film material, which comprises the following steps: preparing a side chain liquid crystal polysiloxane solution; pretreating inorganic high-heat-conductivity particles; modified inorganic high thermal conductive particles; dispersing the inorganic high-thermal-conductivity particles with surface functionalization modification into an organic solvent, performing ultrasonic treatment, and then adding the inorganic high-thermal-conductivity particles into a polysiloxane side chain liquid crystal solution for dispersion; casting the mixed solution on a glass template, heating and volatilizing to form a film, and obtaining a film material with a certain thickness and a certain pattern; and annealing under the protection of inert gas to obtain the high-heat-conductivity side chain type liquid crystal polymer film material. The method can realize the high thermal conductivity and the high mechanical strength of the high thermal conductivity side chain type liquid crystal polymer film material under the condition of lower filling amount of the thermal conductive filler.
Description
Technical Field
The invention relates to an electronic packaging heat conduction material, in particular to a preparation method of a high heat conduction side chain type liquid crystal polymer film material.
Background
With the development of industrial demands and scientific technology, the requirements on various engineering heat conducting materials are updated and higher. In order to ensure the reliability of the operation of the electronic components at the use environment temperature, a high-heat-dissipation interface material and a packaging material are required to be used, so that heat accumulated by the heating components is quickly and effectively transferred and released, and the service life of the electronic components is prolonged. Therefore, research and development of the polymer-based heat-conducting composite material with high heat conductivity and excellent mechanical property have urgent theoretical significance and practical application value on design and expansion of materials in the fields of microelectronics, electronic information and electronic shielding. The method is far more effective than the method of improving the heat conductivity of heat conducting particles by improving the heat conductivity of the polymer continuous phase matrix, and is a core method for solving the problems that the mechanical properties such as toughness of the polymer are deteriorated, the heat conductivity is poor and the service life of an electronic component is influenced.
Based on phonon heat conduction theory analysis, the premise of obtaining the high-heat-conductivity polymer is to form a heat-conducting particle path or network which is beneficial to phonon transmission in a polymer matrix. Unlike electron hopping and tunneling, CNTs and graphene, which are small numbers of thermally conductive particles, can rapidly increase the electrical conductivity of the polymer, but cannot improve the thermal conductivity, and usually needs to be used in an amount of 30-40 wt% to significantly improve the thermal conductivity of the system, which is attributed to the fact that the thermal transfer is strongly dependent on phonon free path. The amount of the filler is usually required to be more than or equal to 65 wt% for constructing the insulating and heat-conducting particle network, but the electrical insulation and mechanical properties of the polymer are obviously reduced at the moment, the processing performance is poor, and the engineering application of the polymer is seriously influenced.
Therefore, how to consider the high thermal conductivity and excellent mechanical properties of the polymer-based composite material and synchronously realize the highest possible thermal conductivity and mechanical properties of the polymer-based composite material under the condition of lower filling amount of the thermal conductive filler is a problem to be solved urgently.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a preparation method of a high-thermal-conductivity side-chain type liquid crystal polymer film material. The high-thermal-conductivity side chain type liquid crystal polymer film material with high thermal conductivity and excellent mechanical property is obtained under the condition of low filling amount of the thermal conductive filler.
The invention is realized by the following technical scheme.
The preparation method of the high-thermal-conductivity side chain type liquid crystal polymer film material provided by the embodiment of the invention comprises the following steps:
1) preparation of a solution of a side-chain liquid-crystalline polysiloxane
According to the mass ratio of (0.5-1.5): (2-18) dissolving the side chain liquid crystal polysiloxane in an organic solvent, heating and soaking;
2) pretreatment of inorganic high thermal conductivity particles
Soaking inorganic high-heat-conductivity particles in 20-30% nitric acid solution by mass; taking out, centrifugally separating, and soaking in hydrogen peroxide solution at normal temperature;
3) modification of inorganic high thermal conductivity particles
Then, the sample prepared in the step 2) is prepared according to the mass ratio of (1-10): (5-50) adding the mixture into a tetrahydrofuran solution dissolved with monoamino POSS for ultrasonic dispersion; then taking out for centrifugal separation, collecting the lower-layer precipitate, and then carrying out vacuum drying to obtain inorganic high-thermal-conductivity particles with surface functionalized modification;
4) according to the mass ratio (0.5-1.5): (5-25) dispersing the inorganic high thermal conductive particles with the surface functionalized and modified into the same organic solvent as the organic solvent in the step 1) and carrying out ultrasonic treatment;
5) then according to the mass ratio (0.2-1): (4-10) adding the inorganic high-thermal-conductivity particles with surface functionalized modification into the side chain liquid crystal polysiloxane solution according to the proportion, and uniformly dispersing;
6) casting the mixed solution on a glass template with a fixed size, and heating and volatilizing the mixed solution to form a film according to the selected solvent to obtain a film material with a certain thickness and a certain pattern;
7) annealing treatment in a precisely controlled tube furnace at the temperature of more than or equal to 260 ℃ under the protection of inert gas, and cooling to normal temperature to obtain the high-heat-conductivity side chain type liquid crystal polymer film material.
Preferably, in the step 1), the side chain liquid crystal polysiloxane is obtained by polymerizing polysiloxane with trans-4-vinyl-trans-4 '-propylbicyclohexyl, trans-4-propenyl-trans-4' -propylbicyclohexyl, 4-allyloxybenzoic acid-4 '-hydroxybenzenecyano ester and 4-allyloxybenzoic acid-4' -hydroxybenzenemethoxy ester respectively.
Preferably, in the step 1), the organic solvent is one or more of chloroform, tetrahydrofuran, acetone, toluene, 1, 4-dioxane, dimethylformamide and dimethylpyrrolidone.
Preferably, in the step 1), the heating temperature is 25-80 ℃, and the soaking time is 10-12 h.
Preferably, in the step 2), the nitric acid with the concentration of 20-30% by mass is soaked for 4-6h at the temperature of 80-90 ℃; the hydrogen peroxide concentration is 30 percent by mass, and the soaking time is 0.5-1 h;
the centrifugal rotation speed in the step 2) and the step 3) is 6000-.
Preferably, in the step 3), the mass fraction ratio of the tetrahydrofuran solution of the monoamino POSS is tetrahydrofuran: 1:2 monoamino POSS; the ultrasonic dispersion power is 4-6 W.ml-1The temperature is 45-60 ℃, and the reaction time is 1-2 h.
Preferably, the inorganic high thermal conductive particles are boron nitride nanosheets, boron nitride nanotubes or silicon nitride.
Preferably, in the step 6), the solvent is heated to volatilize at a temperature of 25-60 ℃.
Preferably, in the step 6), the thickness of the film material is 100-200 μm.
Preferably, the thermal conductivity of the high thermal conductivity side chain type liquid crystal polymer film material is not less than 0.6004W/mK, the tensile strength is not less than 1.03MPa, and the elongation at break is not less than 106.26%.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
the invention adopts a new method combining an intrinsic type preparation process and a filling type preparation process, and prepares the high-heat-conductivity side chain type liquid crystal polymer film material from a multi-scale structure design; the synthesized side chain liquid crystal polysiloxane (LCEs) provides a complete molecular chain network for phonon transfer, and endows the LCEs with high order degree and excellent thermal stability (T)mNot less than 260 ℃. Preparing intrinsic high-thermal-conductivity LCEs through molecular design and actual accurate control; the inorganic high-thermal-conductivity particles with surface functionalization modification are adopted as the thermal conductive filler to carry out doping modification on the thermal conductive filler, the synergistic promotion effect with the thermal conductive filler of 'bridging-penetrating' is realized based on the ordered regulation and control of LCEs, and the high thermal conductivity and excellent mechanical property of the high-thermal-conductivity side-chain liquid crystal polymer film material are synchronously realized under the lower filling amount of the thermal conductive filler.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention:
FIG. 1 is a flow chart of the preparation of a high thermal conductivity side chain type liquid crystal polymer film material;
FIG. 2 is a schematic diagram of a process for preparing a high thermal conductivity side chain type liquid crystal polymer film material.
Detailed Description
The present invention will now be described in detail with reference to the drawings and specific embodiments, wherein the exemplary embodiments and descriptions of the present invention are provided to explain the present invention without limiting the invention thereto.
As shown in fig. 1, the preparation method of the high thermal conductivity side chain type liquid crystal polymer film material of the present invention comprises the following steps:
1) preparation of a solution of a side-chain liquid-crystalline polysiloxane
According to the mass ratio of (0.5-1.5): (2-18) dissolving the side chain liquid crystal polysiloxane in an organic solvent, heating at the temperature of 25-80 ℃, and soaking for 10-12 h;
wherein the side chain liquid crystal polysiloxane is obtained by graft polymerization of polysiloxane and liquid crystal monomer, and the side chain liquid crystal polysiloxane obtained by polymerization of polysiloxane and trans-4-vinyl-trans-4' -propylbicyclohexane is P1The side chain liquid crystal polysiloxane obtained by polymerizing the polysiloxane and trans-4-propenyl-trans-4' -propylbicyclohexane is P2The side chain liquid crystal polysiloxane obtained by polymerizing the polysiloxane and 4-allyloxybenzoic acid-4' -hydroxybenzonitrile ester is P3Polysiloxane and 4-allyloxybenzoic acid-4The side chain liquid crystal polysiloxane obtained by polymerizing' -hydroxyl benzyloxy ester is P4. The structure is shown in table 1.
TABLE 1 molecular structural formulas of different side chain liquid crystalline polysiloxanes
The synthesis method of the side chain liquid crystal polysiloxane is shown in (P)1：Ying Li,Guangcheng Zhang，Ying Jiang，Zhenzhong Hou，Longgui Peng，Synthesis and Characterization of Side-Chain Liquid-Crystalline Polysiloxanes exhibiting Spherulite Texture of Polymeric Smectic A Phase，Journal of Chemical Research,2011,35(35)：715-719.P2: synthesis and performance of Li Ying, cholesteric phase small plate texture polysiloxane side chain liquid crystal, 2016,29(01):80-84.P3: li Ying, Zhang Guang Cheng, Hulingpeak, Smith, synthesis and characterization of smectic polysiloxane side chain liquid crystal, journal of functional polymer 2011,24(02):211-216.P4: jianying, Li Ying, Yangjian, Zhanliang, Chenjing, the synthesis and characterization of novel anisole group-containing nematic polysiloxane side chain liquid crystal, synthetic chemistry, 2013,21(4): 420-423).
The organic solvent is one or more of chloroform, tetrahydrofuran, acetone, toluene, 1, 4-dioxane, dimethylformamide and dimethyl pyrrolidone.
2) Pretreatment of inorganic high thermal conductivity particles
Soaking inorganic high-thermal-conductivity particles (boron nitride nanosheets, boron nitride nanotubes or silicon nitride) in a nitric acid solution with the mass fraction of 20-30%, wherein the temperature is 80-90 ℃, and the soaking time is 4-6 h; taking out for centrifugal separation, centrifuging at a rotating speed of 6000-;
3) modification of inorganic high-heat-conductivity particles
Then, the sample prepared in the step 2) is prepared according to the mass ratio of (1-10): (5-50) adding the mixture into a tetrahydrofuran solution (THF: monoamino POSS ═ 1:2) dissolved with monoamino POSS to perform ultrasonic dispersion (the power is 4-6 W.ml)-1) The reaction time is 1-2h at the set temperature of 45-60 ℃; taking out for centrifugal separation, centrifuging at the rotating speed of 6000-.
4) According to the mass ratio (0.5-1.5): (5-25) dispersing the inorganic high thermal conductive particles with the surface functionalized and modified into the same organic solvent as the organic solvent in the step 1) and carrying out ultrasonic treatment;
5) then according to the mass ratio (0.2-1): (4-10) adding the inorganic high-thermal-conductivity particles with surface functionalized modification into the side chain liquid crystal polysiloxane solution according to the proportion, and uniformly dispersing;
6) the mixed solution is cast on a glass template with a fixed size, and a film material with a given thickness of 100-200 mu m and a pattern is obtained by volatilizing the solvent at the temperature of 25-60 ℃ according to the selected solvent;
7) annealing treatment in a precisely controlled tube furnace at high temperature (not less than 260 ℃) under the protection of inert gas, and cooling to normal temperature to obtain the high-heat-conduction side chain type liquid crystal polymer film material.
The following different specific examples are given to further illustrate the invention.
Example 1
1) Preparation of a solution of a side-chain liquid-crystalline polysiloxane
According to the mass ratio of 1 g: 10ml of the side chain liquid crystalline polysiloxane (P)1) Dissolving in acetone, heating at 25 deg.C, and soaking for 12 hr;
2) pretreatment of inorganic high-thermal-conductivity particle boron nitride nanosheet
Soaking the boron nitride nanosheets in a nitric acid solution with the mass fraction of 20%, wherein the temperature is 90 ℃, and the soaking time is 4 hours; taking out, centrifuging at 7000r/min for 0.5 hr, and soaking in hydrogen peroxide solution at room temperature with concentration of 30% for 1 hr;
3) modification of inorganic high-thermal-conductivity particle boron nitride nanosheet
Then, mixing the sample prepared in the step 2) according to a mass ratio of 1: 5 was added to a tetrahydrofuran solution (THF: monoamino POSS ═ 1:2) containing an appropriate amount of monoamino POSS, and ultrasonic dispersion was carried out (power: 4W. multidot.ml)-1) The reaction time is 2h at the set temperature of 45 ℃; taking out, performing centrifugal separation, centrifuging at the rotating speed of 6000r/min for 1h, collecting the lower-layer precipitate, and performing vacuum drying to obtain the surface functionalized modified boron nitride nanosheet;
4) dispersing the surface functionalized modified boron nitride nanosheet into the same organic solvent as the organic solvent in the step 1) and performing ultrasonic treatment, wherein the ratio of the boron nitride nanosheet to the organic solvent is 1 g: 15 ml;
5) then, mixing the components in a mass ratio of 1: 6, adding the inorganic high-thermal-conductivity particle solution into the side-chain liquid crystal polysiloxane solution, and uniformly dispersing;
6) and casting the mixed solution on a glass template with a fixed size, and volatilizing the solvent at the temperature of 40 ℃ to form a film according to the selected solvent to obtain the film material with the given thickness of 100-200 mu m and the pattern. As shown in fig. 2.
7) Annealing treatment in a precisely controlled tube furnace at high temperature (not less than 260 ℃) under the protection of inert gas, and cooling to normal temperature to obtain the high-heat-conduction side chain type liquid crystal polymer film material.
Example 2
1) Preparation of a solution of a side-chain liquid-crystalline polysiloxane
According to the mass ratio of 0.5 g: 4ml of the side-chain liquid crystalline polysiloxane (P)2) Dissolving in dimethylformamide, heating at 60 deg.C, and soaking for 10 hr;
2) pretreatment of inorganic high-heat-conductivity particle boron nitride nanotube
Soaking the boron nitride nanotube in a nitric acid solution with the mass fraction of 25%, wherein the temperature is 90 ℃, and the soaking time is 5 hours; taking out, centrifuging at 6000r/min for 1h, and soaking in hydrogen peroxide solution at room temperature, wherein the concentration of the hydrogen peroxide solution is 30% and the soaking time is 0.5 h;
3) modification of inorganic high heat-conducting particle boron nitride nanotube
Then, mixing the sample prepared in the step 2) according to a mass ratio of 3: 10, adding the mixture into a tetrahydrofuran solution (THF: monoamino POSS ═ 1:2) dissolved with a proper amount of monoamino POSS, and performing ultrasonic dispersion (the power is 4-6 W.ml)-1) The reaction time is 1h at the set temperature of 60 ℃; taking out, performing centrifugal separation, centrifuging at the rotating speed of 7000r/min for 0.5h, collecting the lower-layer precipitate, and performing vacuum drying to obtain the surface functionalized modified boron nitride nanotube;
4) dispersing the surface functionalized modified boron nitride nanotubes into the same organic solvent as the step 1) and carrying out ultrasonic treatment, wherein the ratio is 0.5 g: 6 ml;
5) then, according to the mass ratio of 0.2: 4, adding the boron nitride nanotube solution with the surface functionalized and modified into the side chain liquid crystal polysiloxane solution, and uniformly dispersing;
6) and casting the mixed solution on a glass template with a fixed size, and volatilizing the solvent at the temperature of 25 ℃ to form a film according to the selected solvent to obtain the film material with the given thickness of 100-200 mu m and the pattern.
7) Annealing treatment in a precisely controlled tube furnace at high temperature (not less than 260 ℃) under the protection of inert gas, and cooling to normal temperature to obtain the high-heat-conduction side chain type liquid crystal polymer film material.
Example 3
1) Preparation of a solution of a side-chain liquid-crystalline polysiloxane
According to the mass ratio of 1.5 g: 18ml of side chain liquid crystalline polysiloxane (P)3) Dissolving in mixed solution of chloroform and tetrahydrofuran, heating at 80 deg.C, and soaking for 10 hr;
dimethylformamide, and one or more of the mixtures.
2) Pretreatment of inorganic high-heat-conductivity particle silicon nitride
Soaking silicon nitride in a nitric acid solution with the mass fraction of 30%, wherein the temperature is 80 ℃, and the soaking time is 6 hours; taking out, centrifuging at 6000r/min for 1h, and soaking in hydrogen peroxide solution at room temperature, wherein the concentration of the hydrogen peroxide solution is 30% and the soaking time is 1 h;
3) modification of inorganic high heat-conducting particle silicon nitride
Then step 2) The prepared sample is 10: 42, adding the mixture into a tetrahydrofuran solution (THF: monoamino POSS ═ 1:2) dissolved with a proper amount of monoamino POSS, and performing ultrasonic dispersion (the power is 4-6 W.ml)-1) The reaction time is 2 hours at the set temperature of 50 ℃; taking out, centrifuging at 8000r/min for 0.5h, collecting lower precipitate, and vacuum drying to obtain surface functionalized modified silicon nitride;
4) dispersing the surface functionalized modified silicon nitride into the same organic solvent as the step 1) and carrying out ultrasonic treatment, wherein the ratio is 1.5 g: 25 ml;
5) then, mixing the components in a mass ratio of 1: 8, adding the inorganic high-thermal-conductivity particle solution into the side-chain liquid crystal polysiloxane solution, and uniformly dispersing;
6) and casting the mixed solution on a glass template with a fixed size, and volatilizing the solvent at the temperature of 60 ℃ to form a film according to the selected solvent to obtain the film material with the given thickness of 100-200 mu m and the pattern.
7) Annealing treatment in a precisely controlled tube furnace at high temperature (not less than 260 ℃) under the protection of inert gas, and cooling to normal temperature to obtain the high-heat-conduction side chain type liquid crystal polymer film material.
Example 4
1) Preparation of a solution of a side-chain liquid-crystalline polysiloxane
According to the mass ratio of 0.5 g: 2ml of side chain liquid crystalline polysiloxane (P)4) Dissolving in dimethyl pyrrolidone, heating at 50 deg.C, and soaking for 10 hr;
2) pretreatment of inorganic high-thermal-conductivity particle boron nitride nanosheet
Soaking the inorganic high-thermal-conductivity particle boron nitride nanosheets in a nitric acid solution with the mass fraction of 20% -30%, wherein the temperature is 80-90 ℃, and the soaking time is 4-6 h; taking out for centrifugal separation, centrifuging at a rotating speed of 6000-;
3) modification of inorganic high-thermal-conductivity particle boron nitride nanosheet
Then, mixing the sample prepared in the step 2) according to a mass ratio of 9: 50 to a solution of appropriate amount of monoamino POSS dissolved in tetrahydrofuran (THF:performing ultrasonic dispersion (power is 4-6 W.ml) in monoamino POSS (1: 2)-1) The reaction time is 1-2h at the set temperature of 45-60 ℃; taking out for centrifugal separation, centrifuging at the rotating speed of 6000-.
4) Dispersing the surface functionalized modified boron nitride nanosheet into the same organic solvent as the step 1) and performing ultrasonic treatment, wherein the proportion is 0.8 g: 20ml of the solution;
5) then, mixing the components in a mass ratio of 1: 4, adding the inorganic high-thermal-conductivity particle solution into the side-chain liquid crystal polysiloxane solution, and uniformly dispersing;
6) and casting the mixed solution on a glass template with a fixed size, and volatilizing the solvent at the temperature of 60 ℃ to form a film according to the selected solvent to obtain the film material with the given thickness of 100-200 mu m and the pattern.
7) Annealing treatment in a precisely controlled tube furnace at high temperature (not less than 260 ℃) under the protection of inert gas, and cooling to normal temperature to obtain the high-heat-conduction side chain type liquid crystal polymer film material.
Testing and discussing the Performance of the membranes
The invention puts 100-200 mu m thin film in Hot Disk thermal conductivity meter, measures thermal diffusivity and thermal conductivity of sample, characterizes and analyzes thermal conductivity of sample. The thermal conductivity of four polymer samples synthesized according to the invention was tested in the test and is shown in table 2.
TABLE 2 Performance testing of the samples
As can be seen from Table 2, the high-thermal-conductivity side chain type liquid crystal polymer film material prepared by the invention has excellent thermal conductivity, the thermal conductivity of the high-thermal-conductivity side chain type liquid crystal polymer film material reaches 0.6696W/mK, and the thermal conductivity of the high-thermal-conductivity side chain type liquid crystal polymer film material is not less than 0.6004W/mK and is far higher than that of a common polymer material (about 0.2W/mK), the tensile strength of the high-thermal-conductivity side chain type liquid crystal polymer film material reaches 1.86 MPa; the elongation at break reaches 138.57%, and the elongation at break is not less than 106.26%. Therefore, the high-thermal-conductivity side chain type liquid crystal polymer film material prepared by the method is a liquid crystal film with good thermal conductivity and mechanical properties.
The present invention is not limited to the above-mentioned embodiments, and based on the technical solutions disclosed in the present invention, those skilled in the art can make some substitutions and modifications to some technical features without creative efforts according to the disclosed technical contents, and these substitutions and modifications are all within the protection scope of the present invention.
Claims (10)
1. A preparation method of a high-thermal-conductivity side chain type liquid crystal polymer film material is characterized by comprising the following steps:
1) preparation of a solution of a side-chain liquid-crystalline polysiloxane
According to the mass ratio of (0.5-1.5): (2-18) dissolving the side chain liquid crystal polysiloxane in an organic solvent, heating and soaking;
2) pretreatment of inorganic high thermal conductivity particles
Soaking inorganic high-heat-conductivity particles in 20-30% nitric acid solution by mass; taking out, centrifugally separating, and soaking in hydrogen peroxide solution at normal temperature;
3) modification of inorganic high thermal conductivity particles
Then, the sample prepared in the step 2) is prepared according to the mass ratio of (1-10): (5-50) adding the mixture into a tetrahydrofuran solution dissolved with monoamino POSS for ultrasonic dispersion; then taking out for centrifugal separation, collecting the lower-layer precipitate, and then carrying out vacuum drying to obtain inorganic high-thermal-conductivity particles with surface functionalized modification;
4) according to the mass ratio (0.5-1.5): (5-25) dispersing the inorganic high thermal conductive particles with the surface functionalized and modified into the same organic solvent as the organic solvent in the step 1) and carrying out ultrasonic treatment;
5) then according to the mass ratio (0.2-1): (4-10) adding the inorganic high-thermal-conductivity particles with surface functionalized modification into the side chain liquid crystal polysiloxane solution according to the proportion, and uniformly dispersing;
6) casting the mixed solution on a glass template with a fixed size, and heating and volatilizing the mixed solution to form a film according to the selected solvent to obtain a film material with a certain thickness and a certain pattern;
7) annealing treatment in a precisely controlled tube furnace at the temperature of more than or equal to 260 ℃ under the protection of inert gas, and cooling to normal temperature to obtain the high-heat-conductivity side chain type liquid crystal polymer film material.
2. The method for preparing a high thermal conductivity side chain type liquid crystal polymer film material according to claim 1, wherein in the step 1), the side chain liquid crystalline polysiloxane is obtained by polymerizing polysiloxane with trans-4-vinyl-trans-4 '-propylbicyclohexane, trans-4-propenyl-trans-4' -propylbicyclohexane, 4-allyloxybenzoic acid-4 '-hydroxybenzenecyanoester and 4-allyloxybenzoic acid-4' -hydroxybenzenemethoxy ester, respectively.
3. The method for preparing a high thermal conductivity side chain type liquid crystal polymer film material according to claim 1, wherein in the step 1), the organic solvent is one or more of chloroform, tetrahydrofuran, acetone, toluene, 1, 4-dioxane, dimethylformamide or dimethylpyrrolidone.
4. The preparation method of the high thermal conductivity side chain type liquid crystal polymer film material according to claim 1, wherein in the step 1), the heating temperature is 25-80 ℃ and the soaking time is 10-12 h.
5. The preparation method of the high-thermal-conductivity side-chain type liquid crystal polymer film material according to claim 1, wherein in the step 2), the nitric acid is soaked for 4-6h at 80-90 ℃ with the mass fraction of 20% -30%; the mass fraction of the hydrogen peroxide is 30 percent, and the soaking time is 0.5-1 h;
the centrifugal rotation speed in the step 2) and the step 3) is 6000-.
6. The preparation method of the high-thermal-conductivity side-chain type liquid crystal polymer film material as claimed in claim 1, wherein in the step 3), the mass fraction ratio of the tetrahydrofuran solution of the monoamino POSS is tetrahydrofuran: 1:2 monoamino POSS; the ultrasonic dispersion power is 4-6 W.ml-1The temperature is 45-60 DEG CThe reaction time is 1-2 h.
7. The preparation method of the high-thermal-conductivity side-chain type liquid crystal polymer film material as claimed in claim 1, wherein the inorganic high-thermal-conductivity particles are boron nitride nanosheets, boron nitride nanotubes or silicon nitride.
8. The method for preparing the high thermal conductivity side chain type liquid crystal polymer film material according to claim 1, wherein in the step 6), the solvent heating volatilization temperature is 25-60 ℃.
9. The method for preparing a high thermal conductivity side chain type liquid crystal polymer film material as claimed in claim 1, wherein in the step 6), the film material thickness is 100-200 μm.
10. The method for preparing the high thermal conductivity side chain type liquid crystal polymer film material of claim 1, wherein the thermal conductivity of the high thermal conductivity side chain type liquid crystal polymer film material is not less than 0.6004W/mK, the tensile strength is not less than 1.03Mpa, and the elongation at break is not less than 106.26%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811289062.3A CN109180979B (en) | 2018-10-31 | 2018-10-31 | Preparation method of high-thermal-conductivity side chain type liquid crystal polymer film material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811289062.3A CN109180979B (en) | 2018-10-31 | 2018-10-31 | Preparation method of high-thermal-conductivity side chain type liquid crystal polymer film material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109180979A CN109180979A (en) | 2019-01-11 |
| CN109180979B true CN109180979B (en) | 2020-11-24 |
Family
ID=64941110
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811289062.3A Active CN109180979B (en) | 2018-10-31 | 2018-10-31 | Preparation method of high-thermal-conductivity side chain type liquid crystal polymer film material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109180979B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110760310B (en) * | 2019-09-27 | 2021-08-10 | 深圳市信维通信股份有限公司 | Method for improving mechanical property of liquid crystal polymer product |
| TWI740515B (en) | 2019-12-23 | 2021-09-21 | 長春人造樹脂廠股份有限公司 | Liquid crystal polymer film and laminate comprising the same |
| CN113461988A (en) * | 2021-08-05 | 2021-10-01 | 宁夏清研高分子新材料有限公司 | High-thermal-conductivity side-chain liquid crystal polymer film and preparation method thereof |
| CN115572486B (en) * | 2022-10-18 | 2024-03-29 | 中科院广州化学有限公司 | Heat-conducting insulating polymer material composite film based on boron nitride filler and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6592997B2 (en) * | 2001-06-25 | 2003-07-15 | General Electric Company | Curable silicone compositions, methods and articles made thereby |
| JP4290083B2 (en) * | 2004-07-05 | 2009-07-01 | キヤノン株式会社 | Heat fixing member |
| CN102757645A (en) * | 2012-08-18 | 2012-10-31 | 邵成芬 | Thermal-conductive silicone grease with high thermal conductivity and high temperature resistance and preparation method thereof |
| CN103013058A (en) * | 2012-12-04 | 2013-04-03 | 合肥杰事杰新材料股份有限公司 | Liquid crystal polymer/cubic boron nitride master batch and preparation method for same |
| CN103936994A (en) * | 2014-04-21 | 2014-07-23 | 苏州大学 | Active-amino-terminated hyperbranched polysiloxane liquid crystalline and preparation method thereof |
-
2018
- 2018-10-31 CN CN201811289062.3A patent/CN109180979B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6592997B2 (en) * | 2001-06-25 | 2003-07-15 | General Electric Company | Curable silicone compositions, methods and articles made thereby |
| JP4290083B2 (en) * | 2004-07-05 | 2009-07-01 | キヤノン株式会社 | Heat fixing member |
| CN102757645A (en) * | 2012-08-18 | 2012-10-31 | 邵成芬 | Thermal-conductive silicone grease with high thermal conductivity and high temperature resistance and preparation method thereof |
| CN103013058A (en) * | 2012-12-04 | 2013-04-03 | 合肥杰事杰新材料股份有限公司 | Liquid crystal polymer/cubic boron nitride master batch and preparation method for same |
| CN103936994A (en) * | 2014-04-21 | 2014-07-23 | 苏州大学 | Active-amino-terminated hyperbranched polysiloxane liquid crystalline and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 低介电常数双马来酰亚胺导热复合材料的制备及机理研究;党婧;《中国博士学位论文全文数据库》;20170831;第二章 * |
| 聚硅氧烷/石墨烯导热散热涂层的制备及表征;梁天元;《涂料工业》;20171031;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109180979A (en) | 2019-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109180979B (en) | Preparation method of high-thermal-conductivity side chain type liquid crystal polymer film material | |
| Shen et al. | Structure and electrical properties of grafted polypropylene/graphite nanocomposites prepared by solution intercalation | |
| CN104861910B (en) | A kind of graphene coated inorganic filler epoxy resin compound adhesive and preparation method thereof | |
| CN102925100B (en) | High-thermal conductivity conductive silver adhesive and preparation method thereof | |
| Wang et al. | The effect of two‐dimensional d‐Ti3C2 on the mechanical and thermal conductivity properties of thermoplastic polyurethane composites | |
| Wu et al. | Improved dielectric and thermal properties of core-shell structured SiO2/polyolefin polymer composites for high-frequency copper clad laminates | |
| CN105621960A (en) | Heat conducting gap filling material and preparing method thereof | |
| Aradhana et al. | High performance electrically conductive epoxy/reduced graphene oxide adhesives for electronics packaging applications | |
| Xie et al. | Investigation of covalently grafted polyacrylate chains onto graphene oxide for epoxy composites with reinforced mechanical performance | |
| Tong et al. | Effect of nanosilica on the thermal, mechanical, and dielectric properties of polyarylene ether nitriles terminated with phthalonitrile | |
| Ma et al. | Unveiling the role of filler surface energy in enhancing thermal conductivity and mechanical properties of thermal interface materials | |
| Zhang et al. | Positive temperature coefficient effect and mechanism of compatible LLDPE/HDPE composites doping conductive graphite powders | |
| Gao et al. | Enhanced thermal conductivity for traditional epoxy packaging composites by constructing hybrid conductive network | |
| Zhong et al. | Silica sol nanoparticles hybridized allyl phenolic resins for improving mechanical and thermal performance | |
| Yuan et al. | Poly (dimethyl-diphenyl-imide) siloxane/phenolic-based double network hybrid resin coatings for ablation thermal protection | |
| Yang et al. | The relationship between processing and performances of polyarylene ether nitriles terminated with phthalonitrile/trifunctional phthalonitrile composites | |
| CN113969040A (en) | Modified boron nitride/epoxy resin heat-conducting composite material and preparation method thereof | |
| CN113667309A (en) | Organic-inorganic hybrid crosslinked heat-conducting silica gel and preparation method thereof | |
| Jiang et al. | Simultaneously enhancing the thermal conductivity and dielectric constant of BN/CF hybrid filled polypropylene/polystyrene composites via in situ reactive processing | |
| Zhao et al. | Hybridization of polyhedral oligomeric silsesquioxane and boron nitride for epoxy composites with improved dielectric, thermal and tensile properties | |
| Niu et al. | Mechanical properties of epoxy resin composites modified by epoxy styrene‐butadiene latex | |
| CN109722899B (en) | Polyetherimide resin-based carbon fiber suspension sizing agent and preparation method thereof | |
| Zhu et al. | Enhanced thermal conductivity of polyarylene ether nitrile composites blending hexagonal boron nitride | |
| Zheng et al. | Improved thermal conductivity and excellent electrical insulation properties of polysiloxane nanocomposite-incorporated functional boron nitride sheets via in situ polymerization | |
| Cao et al. | Improving properties of ceramic silicone rubber composites using high vinyl silicone oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210601 Address after: 226500 No.5 factory building, No.1, Huajiang Avenue, Changjiang Town, Rugao City, Nantong City, Jiangsu Province Patentee after: Liuxing new material technology (Jiangsu) Co.,Ltd. Address before: Room 3003-1, building 1, Gaode land center, Jianggan District, Hangzhou City, Zhejiang Province Patentee before: Zhejiang Zhiduo Network Technology Co.,Ltd. Effective date of registration: 20210601 Address after: Room 3003-1, building 1, Gaode land center, Jianggan District, Hangzhou City, Zhejiang Province Patentee after: Zhejiang Zhiduo Network Technology Co.,Ltd. Address before: 710054 No. 58, Yanta Road, Shaanxi, Xi'an Patentee before: XI'AN University OF SCIENCE AND TECHNOLOGY |