CN114058155A - High-thermal-conductivity liquid crystal polymer material and preparation method thereof - Google Patents
High-thermal-conductivity liquid crystal polymer material and preparation method thereof Download PDFInfo
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- 229920000106 Liquid crystal polymer Polymers 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 47
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 36
- 229920000767 polyaniline Polymers 0.000 claims abstract description 36
- 239000002135 nanosheet Substances 0.000 claims abstract description 33
- 239000011256 inorganic filler Substances 0.000 claims abstract description 24
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 24
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 24
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 20
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 20
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003063 flame retardant Substances 0.000 claims abstract description 17
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 16
- 229910000077 silane Inorganic materials 0.000 claims abstract description 15
- -1 silane modified boron nitride Chemical class 0.000 claims abstract description 14
- 239000003822 epoxy resin Substances 0.000 claims abstract description 12
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 12
- 239000004952 Polyamide Substances 0.000 claims abstract description 10
- 229920002647 polyamide Polymers 0.000 claims abstract description 10
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 26
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 24
- 229910052582 BN Inorganic materials 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- 239000002861 polymer material Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000006084 composite stabilizer Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004974 Thermotropic liquid crystal Substances 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 claims description 3
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 3
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- SHLNMHIRQGRGOL-UHFFFAOYSA-N barium zinc Chemical compound [Zn].[Ba] SHLNMHIRQGRGOL-UHFFFAOYSA-N 0.000 claims description 3
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 230000017525 heat dissipation Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 17
- 239000002131 composite material Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 5
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
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- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229920006039 crystalline polyamide Polymers 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
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- 230000009257 reactivity Effects 0.000 description 1
- 239000011208 reinforced composite material Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a high-thermal-conductivity liquid crystal polymer material and a preparation method thereof, wherein the high-thermal-conductivity liquid crystal polymer material comprises the following components in parts by weight: 80-100 parts of liquid crystal polyamide or liquid crystal epoxy resin, 10-15 parts of graphene modified polyaniline derivative, 10-20 parts of silane modified boron nitride nanosheet, 5-10 parts of inorganic filler, 0.1-0.2 part of antioxidant, 0.1-0.2 part of heat stabilizer and 0.1-0.2 part of flame retardant. The liquid crystal polymer material with high heat conductivity prepared by the invention has certain electrical conductivity, can have good antistatic effect, and can be widely applied to electronic shells and products with high heat dissipation requirements.
Description
Technical Field
The invention relates to the technical field of liquid crystal polymer composite materials, in particular to a high-thermal-conductivity liquid crystal polymer material and a preparation method thereof.
Background
The Liquid Crystal Polymer (LCP) material is a polymer with excellent performance developed at present, the molecules of the LCP material have spontaneous orientation, and the LCP material has the characteristics of light weight, chemical corrosion resistance, easy processing, excellent electrical insulation performance and the like, and is mainly used for preparing special fiber materials and special engineering plastics. However, most high molecular materials have extremely low thermal conductivity and are thermal insulators. The prior art generally improves the thermal conductivity by improving the polymer material, thereby expanding the application range of the polymer material. Along with the development of electrical equipment towards the direction of large capacity, high power density and small-size lightweight, the heat that its produced in unit volume is showing to increase in operation working process, if the heat can not in time, high-efficient the transmission goes out, and the ageing inefficacy of macromolecular material can be accelerated to the heat of constantly accumulating and the temperature rise that produces from this, reduces work efficiency and reliability, shortens life. Therefore, the demand for liquid crystal polymer materials is becoming wider and higher, and the demand for the properties thereof is also becoming higher.
Although the prior art has a plurality of methods and technologies for improving the thermal conductivity of the polymer, the thermal conductivity of the polymer has a plurality of influencing factors, including chemical composition, bond energy, structure type, side groups, molecular weight and distribution thereof, structural defects, molecular chain distribution, processing technology, temperature, crystallinity and the like. That is, in a specific system, the method capable of increasing the thermal conductivity may not be suitable for other systems, and even the opposite effect may occur, so how to select a suitable way to improve the liquid crystal polymer material is still a need in the industry.
Disclosure of Invention
In view of the disadvantages and drawbacks of the prior art, an object of the present invention is to provide a liquid crystal polymer material with high thermal conductivity, which has a certain electrical conductivity and excellent thermal conductivity, and can effectively prolong the service life of the liquid crystal polymer material. Another object of the present invention is to provide a method for preparing a liquid crystal polymer material with high thermal conductivity, which is simple and convenient, does not require a complex processing process, can ensure the performance of a composite material, and can be industrially produced in batch, thereby reducing the production cost.
The purpose of the invention is realized by the following technical scheme:
a high-thermal-conductivity liquid crystal polymer material comprises the following components in parts by weight:
80-100 parts of liquid crystal polyamide or liquid crystal epoxy resin;
10-15 parts of graphene modified polyaniline derivative;
10-20 parts of silane modified boron nitride nanosheets;
5-10 parts of inorganic filler;
0.1-0.2 part of antioxidant;
0.1-0.2 part of heat stabilizer;
0.1-0.2 part of flame retardant.
Further, the liquid crystal polymer material with high thermal conductivity comprises the following components in parts by weight:
85-95 parts of liquid crystal polyamide or liquid crystal epoxy resin;
12-13 parts of graphene modified polyaniline derivative;
13-17 parts of silane modified boron nitride nanosheets;
7-8 parts of inorganic filler;
0.1-0.2 part of antioxidant;
0.1-0.2 part of heat stabilizer;
0.1-0.2 part of flame retardant.
Further, the structural formula of the graphene modified polyaniline derivative is as follows:
Further, the preparation method of the graphene modified polyaniline derivative comprises the following steps: (1) at room temperature, adding 0.2-0.3mol of aniline monomer into 1mol/L HCl solution, stirring for 20-30min, then adding 0.2-0.3mol of graphene powder, and continuing stirring for 30-60 min; (2) after temperature balance is achieved in an ice bath at 0-3 ℃, 0.1-0.2mol of ammonium sulfate is dissolved in 150-200mL of 1mol/L HCl solution and is slowly added into the mixed solution of aniline monomer and graphene; (3) continuously stirring and reacting for 60-90min at the temperature of 90-100 ℃; and filtering, washing and drying the reaction solution to obtain the graphene modified polyaniline derivative.
Further, the structural formula of the aniline monomer is as follows:
wherein R is hydrogen, methyl or ethyl.
Polyaniline is a widely used high molecular polymer, has special electro-optic property, can have conductivity after being doped, and is a good electrode material, an anti-static and electromagnetic shielding material, a conductive fiber, an anti-corrosion material and the like. According to the application, the polyaniline is subjected to graphene modification, so that the polyaniline has certain electrical conductivity and is matched with a liquid crystal polymer material, and finally, the liquid crystal polymer material with high thermal conductivity and electrical conductivity is realized. On the other hand, graphene has thermal conductivity and is usually added to a polymer matrix composite material as an independent component, and the graphene reacts with polyaniline to form a chemical bond between the graphene and the polyaniline, so that the polyaniline is conductive, and the thermal conductivity of the high polymer material can be improved to a certain extent.
Further, the size of the boron nitride nanosheet is (400-600nm) × (300-400nm) × (10-25 nm).
Further, the preparation method of the silane modified boron nitride nanosheet comprises the following steps: adding 2.0-5.0g of boron nitride nanosheet and 50-60g of silane coupling agent into 200-500g of anhydrous xylene, uniformly stirring, refluxing the mixed solution at 50-70 ℃, then adding 20-30g of water into the mixed solution, and heating to 70-80 ℃ for reaction for 3-5 h. After the reaction is finished, centrifugal separation is carried out, and then absolute ethyl alcohol and deionized water are used for cleaning, and finally drying is carried out at 50-70 ℃.
Further, the silane coupling agent is selected from one or more of gamma-aminopropyltriethoxysilane and gamma-mercaptopropyltrimethoxysilane.
The boron nitride nanosheets have good chemical stability, are not easy to form chemical bonds, have excellent heat-conducting property, are easy to agglomerate together, and influence the exertion of the excellent properties of the boron nitride nanosheets, so that the improvement of the properties of the boron nitride nanosheet reinforced composite material is influenced. The applicant adopts a coupling agent to carry out functional modification on the boron nitride nanosheets, so that excellent performance of the boron nitride nanosheets can be ensured, and conditions are provided for dispersion of the boron nitride nanosheets and intercalation polymerization in a melt extrusion process through the reactivity of a modification group; in addition, the migration of inorganic filler can be prevented, and the stability of the polymer composite material is improved.
Therefore, the applicant has sought to improve the dispersibility and affinity of the powder by modifying the boron nitride nanosheets, and to improve the thermal conductivity of the polymer material by modifying the boron nitride.
Further, the particle size of the inorganic filler is 10-20 μm, and further, the inorganic filler is selected from one or more of alumina and titanium dioxide.
Further, the antioxidant is a hindered phenol antioxidant;
further, the heat stabilizer is selected from one or more of calcium-zinc composite stabilizer and barium-zinc composite stabilizer.
Further, the flame retardant is selected from one or more of decabromodiphenyl ethane, decabromodiphenyl ether and ammonium polyphosphate.
According to the invention, the influence of heat on the performance of the composite material can be prevented or delayed by using a proper heat stabilizer, the thermal stability of the composite material is improved, and the service life is prolonged; the antioxidant is added to further improve the oxidation resistance of the composite material, so that the chemical weather resistance of the composite material is improved; the flame retardant is added to improve the flame retardant property of the composite material.
A preparation method of a high-thermal-conductivity liquid crystal polymer material comprises the following steps:
(1) weighing thermotropic liquid crystal polymer material, thermosetting resin, inorganic filler and other auxiliary agents according to the weight parts, and uniformly mixing to obtain a mixture S1;
(2) heating liquid crystal polyamide or liquid crystal epoxy resin to a molten state, adding the graphene modified polyaniline derivative, and uniformly stirring; cooling and mechanically crushing into particles;
(3) uniformly mixing the particles, the inorganic filler, the antioxidant, the heat stabilizer and the flame retardant to obtain a mixture S1;
(4) and adding the mixture S1 into an extruder from a main feeding port, adding the silane modified boron nitride nanosheets into the extruder from a side feeding port, and performing melt extrusion granulation to obtain the high-thermal-conductivity liquid crystal polymer material.
Further, the temperatures of the first zone to the tenth zone of the extruder are 305-.
The invention is equivalent to the prior art, and has the beneficial effects that:
1. according to the invention, the liquid crystal polyamide or liquid crystal epoxy resin and the graphene modified polyaniline derivative are used as main components, the electrical property of the liquid crystal polymer material is changed by adding the graphene modified polyaniline derivative, so that the liquid crystal polymer material has certain conductivity, and the graphene is also beneficial to improving the heat conductivity of the liquid crystal polymer material.
2. By performing silane modification on the boron nitride nanosheets, on one hand, the dispersibility and the affinity of the powder are improved, and the corrosion resistance and other properties of the composite material are effectively improved; the boron nitride nanosheet also has excellent heat-conducting property, and the heat-conducting property of the liquid crystal polymer material can be obviously improved finally through the cooperation of various substances.
3. The liquid crystal polymer material prepared by the invention has good mechanical property, low preparation cost, simple and easy preparation process and is convenient for industrial production.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A high-thermal-conductivity liquid crystal polymer material comprises the following components in parts by weight:
90 parts of liquid crystal epoxy resin;
12 parts of graphene modified polyaniline derivative;
15 parts of silane modified boron nitride nanosheets;
7 parts of an inorganic filler;
0.1 part of antioxidant;
0.1 part of heat stabilizer;
0.1 part of flame retardant.
The structural formula of the graphene modified polyaniline derivative is as follows:
The preparation method of the graphene modified polyaniline derivative comprises the following steps: (1) at room temperature, adding 0.2mol of aniline monomer into 1mol/L HCl solution, stirring for 20min, then adding 0.2mol of graphene powder, and continuing to stir for 50 min; (2) after temperature balance is achieved in an ice bath at 0 ℃, 0.1mol of ammonium sulfate is dissolved in 150mL of 1mol/L HCl solution and is slowly added into a mixed solution of aniline monomers and graphene; (3) continuously stirring and reacting for 70min at the temperature of 90 ℃; and filtering, washing and drying the reaction solution to obtain the graphene modified polyaniline derivative.
Wherein the structural formula of the aniline monomer is as follows:
wherein R is hydrogen.
Wherein the size of the boron nitride nanosheet is 500nm × 300 × 20 nm.
Wherein the preparation steps of the silane modified boron nitride nanosheet comprise: adding 5.0g of boron nitride nanosheet and 60g of silane coupling agent into 400g of anhydrous xylene, uniformly stirring, refluxing the mixed solution at 60 ℃, then adding 25g of water into the mixed solution, and heating to 80 ℃ for reaction for 4 hours. After the reaction is finished, centrifugal separation is carried out, and then absolute ethyl alcohol and deionized water are used for cleaning, and finally drying is carried out at 60 ℃.
Wherein the silane coupling agent is selected from gamma-aminopropyl triethoxysilane.
Wherein the particle size of the inorganic filler is 20 μm, and the inorganic filler is selected from alumina.
Wherein the antioxidant is a hindered phenol antioxidant;
wherein the heat stabilizer is selected from calcium-zinc composite stabilizers.
Wherein the flame retardant is selected from decabromodiphenylethane.
The preparation method of the high-thermal-conductivity liquid crystal polymer material comprises the following steps:
(1) weighing thermotropic liquid crystal polymer material, thermosetting resin, inorganic filler and other auxiliary agents according to the weight parts, and uniformly mixing to obtain a mixture S1;
(2) heating liquid crystal polyamide or liquid crystal epoxy resin to a molten state, adding the graphene modified polyaniline derivative, and uniformly stirring; cooling and mechanically crushing into particles;
(3) uniformly mixing the particles, the inorganic filler, the antioxidant, the heat stabilizer and the flame retardant to obtain a mixture S1;
(4) and adding the mixture S1 into an extruder from a main feeding port, adding the silane modified boron nitride nanosheets into the extruder from a side feeding port, and performing melt extrusion granulation to obtain the high-thermal-conductivity liquid crystal polymer material.
Wherein the temperatures of the first zone to the tenth zone of the extruder are 305 ℃, 315 ℃, 325 ℃, 345 ℃, 355 ℃, 345 ℃, 335 ℃, 325 ℃, 305 ℃ and 295 ℃ in sequence.
Comparative example 1
Comparative example 1 is identical to example 1 in composition and preparation method, and the only difference is that comparative example 1 only adds a polyaniline derivative without using a graphene-modified polyaniline derivative.
Comparative example 2
Comparative example 2 is identical to example 1 in composition and preparation method, the only difference being that comparative example 2 adds silane-modified boron nitride nanopowder, wherein the boron nitride nanopowder has a particle size of 500 nm.
Example 2
A high-thermal-conductivity liquid crystal polymer material comprises the following components in parts by weight:
liquid crystalline polyamide resin 95;
12 parts of graphene modified polyaniline derivative;
silane-modified boron nitride nanosheets 17;
an inorganic filler 8;
0.2 parts of antioxidant;
0.2 of heat stabilizer;
and 0.2 of flame retardant.
The structural formula of the graphene modified polyaniline derivative is as follows:
The preparation method of the graphene modified polyaniline derivative comprises the following steps: (1) at room temperature, adding 0.3mol of aniline monomer into 1mol/L HCl solution, stirring for 30min, then adding 0.3mol of graphene powder, and continuing to stir for 30-60 min; (2) after temperature balance is achieved in an ice bath at 3 ℃, 0.2mol of ammonium sulfate is dissolved in 200mL of 1mol/L HCl solution and is slowly added into a mixed solution of aniline monomers and graphene; (3) continuously stirring and reacting for 90min at the temperature of 100 ℃; and filtering, washing and drying the reaction solution to obtain the graphene modified polyaniline derivative.
Wherein the structural formula of the aniline monomer is as follows:
wherein R is hydrogen.
Wherein the size of the boron nitride nanosheet is 40nm × 40 × 10 nm.
Wherein the preparation steps of the silane modified boron nitride nanosheet comprise: adding 2.0g of boron nitride nanosheet and 50g of silane coupling agent into 200g of anhydrous xylene, uniformly stirring, refluxing the mixed solution at 70 ℃, then adding 20g of water into the mixed solution, and heating to 75 ℃ for reaction for 3 hours. After the reaction is finished, centrifugal separation is carried out, and then absolute ethyl alcohol and deionized water are used for cleaning, and finally drying is carried out at 70 ℃.
Wherein the silane coupling agent is selected from gamma-mercaptopropyltrimethoxysilane.
Wherein the particle size of the inorganic filler is 10 μm, and the inorganic filler is selected from titanium dioxide.
Wherein the antioxidant is a hindered phenol antioxidant;
wherein the heat stabilizer is selected from barium-zinc composite stabilizers.
Wherein the flame retardant is selected from decabromodiphenyl ether.
The preparation method of the high-thermal-conductivity liquid crystal polymer material comprises the following steps:
(1) weighing thermotropic liquid crystal polymer material, thermosetting resin, inorganic filler and other auxiliary agents according to the weight parts, and uniformly mixing to obtain a mixture S1;
(2) heating liquid crystal polyamide or liquid crystal epoxy resin to a molten state, adding the graphene modified polyaniline derivative, and uniformly stirring; cooling and mechanically crushing into particles;
(3) uniformly mixing the particles, the inorganic filler, the antioxidant, the heat stabilizer and the flame retardant to obtain a mixture S1;
(4) and adding the mixture S1 into an extruder from a main feeding port, adding the silane modified boron nitride nanosheets into the extruder from a side feeding port, and performing melt extrusion granulation to obtain the high-thermal-conductivity liquid crystal polymer material.
Wherein the temperatures of the first zone to the tenth zone of the extruder are 325 ℃, 335 ℃, 345 ℃, 365 ℃, 375 ℃, 365 ℃, 355 ℃, 345 ℃, 315 ℃ and 305 ℃ in sequence.
Comparative example 3
Comparative example 3 is identical to example 2 in composition and preparation method, the only difference being that comparative example 1 only adds a polyaniline derivative without using a graphene-modified polyaniline derivative.
Comparative example 4
Comparative example 4 is identical to example 2 in composition and preparation method, the only difference being that comparative example 1 adds silane-modified boron nitride nanopowder, wherein the boron nitride nanopowder has a particle size of 400 nm.
The liquid crystal polymer materials of examples 1 to 2 and comparative examples 1 to 4 were tested for thermal conductivity and electrical conductivity; wherein the thermal conductivity is measured using a thermal conductivity meter; the conductivity is measured by adopting a three-electrode system, a tested sample is made into a circular sheet with the diameter of 10cm and the thickness of 5mm, and the volume conductivity is calculated.
TABLE 1
| Thermal conductivity (W/(m.K)) | Volume conductivity (S/m) | |
| Example 1 | 2.45 | 5.7×10-7 |
| Comparative example 1 | 1.87 | 1.7×10-10 |
| Comparative example 2 | 2.11 | 3.9×10-7 |
| Example 2 | 1.73 | 8.2×10-8 |
| Comparative example 3 | 1.27 | 7.4×10-12 |
| Comparative example 4 | 1.51 | 7.4×10-11 |
As can be seen from the thermal conductivity and volume conductivity data of the examples 1, 1-2, 2 and 3-4, the liquid crystal polymer material prepared by the invention has high thermal conductivity and certain electrical conductivity, and the thermal conductivity is remarkably improved compared with that of pure epoxy resin and polyamide resin. Compared with the liquid crystal high polymer material prepared without adopting the graphene modified polyaniline derivative, the volume conductivity of the prepared liquid crystal high polymer material is obviously lower than 3-4 orders of magnitude; and the corresponding thermal conductivity is also reduced.
In addition, the shape of the boron nitride also has an influence on the thermal conductivity, and the thermal conductivity is reduced by 10-20% under the condition of adopting the silane modified boron nitride nano powder, so that the boron nitride nano sheet can effectively improve the thermal conductivity of the liquid crystal polymer material.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (10)
1. A liquid crystal high polymer material with high heat conductivity is characterized by comprising the following components:
80-100 parts of liquid crystal polyamide or liquid crystal epoxy resin;
10-15 parts of graphene modified polyaniline derivative;
10-20 parts of silane modified boron nitride nanosheets;
5-10 parts of inorganic filler;
0.1-0.2 part of antioxidant;
0.1-0.2 part of heat stabilizer;
0.1-0.2 part of flame retardant.
2. The liquid crystal polymer material with high thermal conductivity according to claim 1, comprising the following components:
85-95 parts of liquid crystal polyamide or liquid crystal epoxy resin;
12-13 parts of graphene modified polyaniline derivative;
13-17 parts of silane modified boron nitride nanosheets;
7-8 parts of inorganic filler;
0.1-0.2 part of antioxidant;
0.1-0.2 part of heat stabilizer;
0.1-0.2 part of flame retardant.
3. The liquid crystal polymer material with high thermal conductivity according to any one of claims 1 to 2, wherein the structural formula of the graphene-modified polyaniline derivative is as follows:
4. The liquid crystal polymer material with high thermal conductivity according to any one of claims 1 to 2, wherein the preparation method of the graphene-modified polyaniline derivative comprises the following steps: (1) at room temperature, adding 0.2-0.3mol of aniline monomer into 1mol/L HCl solution, stirring for 20-30min, then adding 0.2-0.3mol of graphene powder, and continuing stirring for 30-60 min; (2) after temperature equilibrium is achieved in an ice bath at 0-3 ℃, 0.1-0.2mol of ammonium sulfate is dissolved in 150-200mL of 1mol/L HCl solution and is slowly added into aniline monomer and grapheneIn the mixed solution of (1); (3) continuously stirring and reacting for 60-90min at the temperature of 90-100 ℃; filtering, washing and drying the reaction solution to obtain the graphene modified polyaniline derivative; the structural formula of the aniline monomer is as follows:
wherein R is hydrogen, methyl or ethyl.
5. The liquid crystal polymer material with high thermal conductivity as claimed in any one of claims 1-2, wherein the size of the boron nitride nanosheet is (400-600nm) x (300-400nm) x (10-25 nm).
6. The liquid crystal polymer material with high thermal conductivity according to any one of claims 1-2, wherein the preparation step of the silane-modified boron nitride nanosheet comprises: adding 2.0-5.0g of boron nitride nanosheet and 50-60g of silane coupling agent into 200-500g of anhydrous xylene, uniformly stirring, refluxing the mixed solution at 50-70 ℃, then adding 20-30g of water into the mixed solution, and heating to 70-80 ℃ for reaction for 3-5 h. After the reaction is finished, carrying out centrifugal separation, cleaning with absolute ethyl alcohol and deionized water, and finally drying at 50-70 ℃;
the silane coupling agent is selected from one or more of gamma-aminopropyltriethoxysilane and gamma-mercaptopropyltrimethoxysilane.
7. The liquid crystal polymer material with high thermal conductivity according to any one of claims 1-2, wherein the particle size of the inorganic filler is 10-20 μm, and further, the inorganic filler is selected from one or more of alumina and titanium dioxide.
8. The liquid crystalline polymer material with high thermal conductivity according to any one of claims 1 to 2, wherein the antioxidant is a hindered phenol antioxidant; the heat stabilizer is selected from one or more of calcium-zinc composite stabilizer and barium-zinc composite stabilizer; the flame retardant is selected from one or more of decabromodiphenyl ethane, decabromodiphenyl ether and ammonium polyphosphate.
9. A method for preparing the liquid crystal polymer material with high thermal conductivity according to any one of claims 1 to 8, comprising the following steps:
(1) weighing thermotropic liquid crystal polymer material, thermosetting resin, inorganic filler and other auxiliary agents according to the weight parts, and uniformly mixing to obtain a mixture S1;
(2) heating liquid crystal polyamide or liquid crystal epoxy resin to a molten state, adding the graphene modified polyaniline derivative, and uniformly stirring; cooling and mechanically crushing into particles;
(3) uniformly mixing the particles, the inorganic filler, the antioxidant, the heat stabilizer and the flame retardant to obtain a mixture S1;
(4) and adding the mixture S1 into an extruder from a main feeding port, adding the silane modified boron nitride nanosheets into the extruder from a side feeding port, and performing melt extrusion granulation to obtain the high-thermal-conductivity liquid crystal polymer material.
10. The method as claimed in claim 9, wherein the temperatures of the first zone to the ten zones of the extruder are 305-.
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