CN115368734B - Preparation method of high-heat-conductivity polyimide composite film material - Google Patents
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- CN115368734B CN115368734B CN202211038777.8A CN202211038777A CN115368734B CN 115368734 B CN115368734 B CN 115368734B CN 202211038777 A CN202211038777 A CN 202211038777A CN 115368734 B CN115368734 B CN 115368734B
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- 239000002131 composite material Substances 0.000 title claims abstract description 83
- 229920001721 polyimide Polymers 0.000 title claims abstract description 66
- 239000004642 Polyimide Substances 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910052582 BN Inorganic materials 0.000 claims abstract description 109
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 109
- 239000002135 nanosheet Substances 0.000 claims abstract description 53
- 239000000243 solution Substances 0.000 claims abstract description 47
- 239000003292 glue Substances 0.000 claims abstract description 44
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 239000003607 modifier Substances 0.000 claims abstract description 5
- 239000007822 coupling agent Substances 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 150000004985 diamines Chemical class 0.000 claims description 10
- 239000004952 Polyamide Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 229920002647 polyamide Polymers 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- 239000002313 adhesive film Substances 0.000 claims description 7
- 150000008064 anhydrides Chemical class 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 238000006068 polycondensation reaction Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000012024 dehydrating agents Substances 0.000 claims description 4
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000003880 polar aprotic solvent Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 claims description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 claims description 2
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 claims description 2
- OKDQKPLMQBXTNH-UHFFFAOYSA-N n,n-dimethyl-2h-pyridin-1-amine Chemical compound CN(C)N1CC=CC=C1 OKDQKPLMQBXTNH-UHFFFAOYSA-N 0.000 claims description 2
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000002055 nanoplate Substances 0.000 abstract description 3
- 239000000945 filler Substances 0.000 description 14
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 6
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 5
- 230000017525 heat dissipation Effects 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000002064 nanoplatelet Substances 0.000 description 3
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 150000002466 imines Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- 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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- 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
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Abstract
The invention discloses a preparation method of a high heat conduction polyimide composite film material, which comprises the steps of respectively soaking and modifying a two-dimensional boron nitride nano sheet and a three-dimensional boron nitride empty shell in an alcohol aqueous solution containing a surface modifier, filtering and drying to obtain the surface modified two-dimensional boron nitride nano sheet and the three-dimensional boron nitride empty shell; the polyimide composite film with high out-of-plane thermal conductivity is prepared by adding the surface modified two-dimensional boron nitride nano-plate and the three-dimensional boron nitride blank into polyimide precursor-polyamic acid glue solution according to a certain proportion, and performing the procedures of fully and uniformly mixing, filtering, vacuum defoaming, coating film forming, high-temperature imidization and the like. The composite addition of the two-dimensional boron nitride nanosheets and the three-dimensional boron nitride empty shells can construct a three-dimensional heat conduction path in the polyimide composite film material, and effectively improve the out-of-plane heat conductivity of the composite material while improving the in-plane heat conductivity of the polyimide film.
Description
Technical Field
The invention relates to the technical field of polyimide composite film preparation, in particular to a preparation method of a high-heat-conductivity polyimide composite film material.
Background
The integration level, the working frequency and the power density of electronic products are continuously improved, and effective thermal management of the electronic products is urgent. The main strategy for thermal management is to transfer excess energy from the electronic product to the outside through a thermally conductive material. Flexible thermally conductive films with high thermal conductivity as an emerging candidate material show great potential in thermal management applications for next generation devices, compared to traditional thermal management materials. Compared with isotropic heat conducting materials, low thickness, high mechanical strength and excellent flexibility of the heat conducting film show great potential in flexible heat sink, wearable technology, personal thermal management and other thermal management applications.
Polyimide (PI) is a polymer compound containing an imide group in a molecular structure, and an imine ring contained in a molecular main chain is formed by polycondensing a compound containing diamine and dianhydride in an aprotic polar solvent. Polyimide material has excellent heat stability and good electric insulation property, is called as "energy hand for solving the problem", has developed various application forms such as film, composite material, special engineering plastic, fiber, photoresist and the like, and has wide application in the fields such as aerospace, electronic and electric, bioengineering and the like. Polyimide film is a potential application field of heat dissipation materials due to the advantages of excellent mechanical property, light weight, chemical stability, easiness in preparation and the like. But because of the low inherent thermal conductivity of polyimide films (about 0.2 W.m -1 ·K -1 ) Cannot be directly used as a heat dissipation material. Currently, to satisfy the heat pipeApplications in the field require that inorganic materials are typically added to polyimide substrates to increase their thermal conductivity. Among the numerous inorganic fillers, the two-dimensional boron nitride nanosheets (300 to 2000 W.m due to their excellent thermal conductivity -1 ·K -1 ) And insulating property (5.0-6.0 eV band gap) to become ideal filler, so that the filler has wide application prospect in the field of polyimide composite film materials.
However, the out-of-plane thermal conductivity of the two-dimensional boron nitride nanoplatelet filled polyimide composite film material is difficult to increase relative to the in-plane thermal conductivity of the sample. Referring to the related literature, in order to improve the out-of-plane thermal conductivity of the polyimide composite film material filled with the two-dimensional boron nitride nano-sheets, the heat dissipation requirements of special electronic components are better met, inorganic heat conduction particle bridging (by depositing 0D, 1D heat conduction particles on the surface of BN through chemical reduction/in-situ growth and other means, so as to form dot-plane, line-plane and other bridged heterostructures) and three-dimensional network skeleton structure construction (such as a template method, a foaming method, gel network construction, isolation structure construction and the like) are mainly adopted. Most of the above methods have the disadvantages of complex process and very limited improvement of thermal conductivity.
Disclosure of Invention
The invention aims to solve the problems that the polyimide film in the prior art has low out-of-plane heat conductivity and is difficult to meet the heat dissipation requirement of special electronic components, and the like, and provides a preparation method of a polyimide composite film material with high heat conductivity. The method is to add the two-dimensional boron nitride nano-sheet and the three-dimensional boron nitride blank into polyimide precursor-polyamic acid glue solution according to a certain proportion, and prepare the polyimide composite film with high out-of-plane thermal conductivity through the procedures of fully and uniformly mixing, filtering, vacuum defoamation, coating film formation, high-temperature imidization and the like.
The invention is realized by the following technical scheme.
The preparation method of the polyimide composite film with high heat conductivity comprises the following steps:
(1) And respectively soaking and modifying the two-dimensional boron nitride nano-sheet and the three-dimensional boron nitride empty shell in an alcohol-water solution containing a surface modifier, filtering and drying to obtain the surface modified two-dimensional boron nitride nano-sheet and the three-dimensional boron nitride empty shell.
(2) The polyimide precursor-polyamic acid glue solution is synthesized by solution polycondensation in polar aprotic solvent by taking dicarboxylic anhydride and diamine monomer as raw materials.
(3) The surface modified two-dimensional boron nitride nano-sheet and the three-dimensional boron nitride empty shell obtained in the step (1) are mixed according to the mass ratio of (95-0): and (5) adding the polyamide acid glue solution obtained in the step (2) in a proportion of (5-100), stirring, dispersing, filtering and vacuum defoaming to obtain the stable high-quality polyamide acid composite glue solution, and storing at a low temperature for later use.
(4) And (3) coating the polyamic acid composite glue solution obtained in the step (3) into a film to obtain the polyamic acid composite glue film containing the two-dimensional boron nitride nano-sheets and the three-dimensional boron nitride empty shells. And then imidizing the polyamic acid composite adhesive film at high temperature to obtain the polyimide composite film material with high heat conductivity.
Among the above steps, steps (1) and (2) are raw material preparation steps, and the two steps are not distinguished in sequence.
In the preparation method, the two-dimensional boron nitride nano-sheet in the step (1) is a nano-sheet with the thickness of 5-100 nm and the plane size of 0.5-5 mu m.
In the preparation method, the three-dimensional boron nitride empty shell in the step (1) is a hollow shell with the wall thickness of 5-100 nm and the size of 0.5-5 mu m.
In the preparation method, the three-dimensional boron nitride empty shell in the step (1) is any one or combination of a hollow sphere and a hollow cube shell prepared by a template method.
In the preparation method, the surface modifier in the step (1) is any one or a combination of a titanate coupling agent and a vinyl silane coupling agent. Preferably, the coupling agent is used in an amount of 0.5-2% of the mass of the two-dimensional boron nitride nano-sheet and the three-dimensional boron nitride empty shell.
Further, in the preparation method, the alcohol aqueous solution in the step (1) is a mixture of water and low molecular alcohol. The mass ratio of water to low molecular alcohol is (0.5-2): (9.5 to 8). The low molecular alcohol is any one or combination of methanol, ethanol and isopropanol.
Further, in the preparation method, the dibasic acid anhydride in the step (2) is any one or a composition of the following structures:
further, in the preparation method, the diamine in the step (2) is any one or a composition of the following structures:
further, in the preparation method, the polar aprotic solvent in the step (2) is any one or a combination of solvents of N, N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP) and Dimethylsulfoxide (DMSO).
Further, in the preparation method, the mass ratio of the surface modified two-dimensional boron nitride nano-sheet and the surface modified three-dimensional boron nitride empty shell in the step (3) is preferably (90-50): (10-50).
Further, in the preparation method, the mass ratio of the sum of the mass of the surface-modified two-dimensional boron nitride nano sheet and the mass of the surface-modified three-dimensional boron nitride empty shell in the step (3) to the mass ratio of the polyamic acid glue solution is (5-50): 100.
in the preparation method, the solid content of the polyamic acid composite glue solution in the step (3) is 10-25%.
Further, in the preparation method, the high-temperature imidization in the step (4) is one of thermal imidization and chemical imidization. When a chemical imidization process is adopted, adding a dehydrating agent and a catalyst into the polyamic acid composite glue solution in the step (3) according to a conventional process, wherein the dehydrating agent is any one or a combination of acetic anhydride, propionic anhydride, butyric anhydride and benzoic anhydride; the catalyst is any one or a combination of pyridine and derivatives thereof, picoline and derivatives thereof, lutidine, N-dimethylaminopyridine, quinoline, isoquinoline and triethylamine.
The invention is based on a great deal of systematic experimental research on the preparation of polyimide composite film materials with high heat conductivity by the inventor. Because the polyimide film has low inherent thermal conductivity (about 0.2 W.m -1 ·K -1 ) Cannot be directly used as a heat dissipation material. Currently, to meet the application requirements in the field of thermal management, inorganic materials are often added to polyimide substrates to increase their thermal conductivity. Among the numerous inorganic fillers, two-dimensional boron nitride nanoplatelets are ideal fillers for their excellent thermal conductivity and insulation properties. According to the invention, the two-dimensional boron nitride nanosheets and the three-dimensional boron nitride empty shells are added into polyimide precursor-polyamic acid glue solution according to a certain proportion, and the polyimide composite film with high out-of-plane thermal conductivity is prepared through the procedures of fully and uniformly mixing, filtering, vacuum defoaming, coating film forming, high-temperature imidization and the like, so that the purpose of improving the in-plane thermal conductivity of the polyimide composite film material and simultaneously effectively improving the out-of-plane thermal conductivity of the composite material is achieved.
The beneficial effects of the invention are as follows:
(1) The composite addition of the two-dimensional boron nitride nanosheets and the three-dimensional boron nitride empty shells can construct a three-dimensional heat conduction path in the polyimide composite film material, and effectively improve the out-of-plane heat conductivity of the composite material while improving the in-plane heat conductivity of the polyimide film.
(2) The high-heat-conductivity boron nitride is used as the homogeneous heat-conducting filler, and the bridging of points, lines and surfaces is realized by using the two-dimensional and three-dimensional heat-conducting filler, so that an efficient three-dimensional heat-conducting passage is constructed.
(3) The invention has simple process and is easy for large-scale industrialized implementation.
Drawings
Fig. 1 is an SEM surface morphology diagram of the high thermal conductivity polyimide composite film material of example 1 of the present invention.
Fig. 2 is an SEM cross-sectional morphology diagram of the high thermal conductivity polyimide composite film material of example 1 of the present invention.
Fig. 3 is an SEM morphology of a three-dimensional boron nitride shell of example 1 of the present invention.
FIG. 4 is a cross-sectional morphology of the polyimide composite film material of comparative example 1 of the present invention.
Detailed Description
The invention is further illustrated below in conjunction with specific embodiments. It should be noted that: the following examples are only for illustrating the invention and are not intended to limit the technical solutions described in the invention. Thus, although the present invention has been described in detail with reference to the following examples, it will be understood by those skilled in the art that the present invention may be modified or equivalents; all technical solutions and modifications thereof that do not depart from the spirit and scope of the present invention are intended to be included in the scope of the appended claims.
Example 1.
Three-dimensional boron nitride hollow cube shells with average size of 3 mu m and average wall thickness of 50nm and two-dimensional boron nitride nano-sheets with average size of 5 mu m are selected as high heat conduction fillers. And respectively soaking and modifying the two-dimensional boron nitride nano-sheets and the three-dimensional boron nitride hollow cube shell in an alcohol-water solution (the mass ratio of water to alcohol is 2:8) containing a titanate coupling agent, filtering and drying to obtain the surface modified two-dimensional boron nitride nano-sheets and the three-dimensional boron nitride hollow cube shell. The coupling agent content is 1% of the mass of the two-dimensional boron nitride nano-sheet and the three-dimensional boron nitride hollow cube shell. Pyromellitic dianhydride (PMDA) and 4,4' -diaminodiphenyl ether (ODA) are respectively used as binary anhydride and diamine monomers, and N, N-Dimethylformamide (DMF) is used as an organic solvent, and a polyimide precursor-polyamide acid glue solution is synthesized through polycondensation reaction. The coupling agent surface modified two-dimensional boron nitride nano-sheet and the three-dimensional boron nitride hollow cube shell are subjected to the following mass percent 95:5 (the mass ratio of the heat conducting filler to the polyamic acid glue solution is 30:100) and obtaining the stable and high-quality polyamic acid composite glue solution through fully stirring, dispersing, filtering and vacuum defoaming. And (3) coating the polyamic acid composite glue solution with the solid content of 10% into a film to prepare the polyamic acid composite glue film containing the two-dimensional boron nitride nano-sheets and the three-dimensional boron nitride hollow cube shell. And imidizing the polyamic acid composite adhesive film to obtain the polyimide composite film material with high heat conductivity. Fig. 1 is an SEM surface morphology diagram of a high thermal conductivity polyimide composite film material. FIG. 2 is a high thermal conductivitySEM cross-sectional morphology of polyimide composite film material. Fig. 3 is an SEM topography of a three-dimensional boron nitride shell. The out-of-plane thermal conductivity of the polyimide composite film was 1.13 W.m -1 ·K -1 。
Example 2.
Three-dimensional boron nitride hollow spheres with average size of 2.5 mu m and average wall thickness of 30nm and two-dimensional boron nitride nano-sheets with average size of 2 mu m are selected as high heat conduction filler. And respectively soaking and modifying the two-dimensional boron nitride nano-sheets and the three-dimensional boron nitride hollow spheres in an alcohol aqueous solution (the mass ratio of water to ethanol is 2:8) containing a vinyl silane coupling agent, filtering and drying to obtain the surface modified two-dimensional boron nitride nano-sheets and the three-dimensional boron nitride hollow spheres. The content of the coupling agent is 0.5 percent of the mass of the two-dimensional boron nitride nano-sheet and the three-dimensional boron nitride hollow sphere. The polyimide precursor-polyamic acid glue solution is synthesized by polycondensation reaction with biphenyl tetracarboxylic dianhydride (BPDA) and 4,4' -diaminodiphenyl ether (ODA) as binary anhydride and diamine monomer and N, N-dimethylacetamide (DMAc) as organic solvent. The coupling agent surface modified two-dimensional boron nitride nano-sheet and the three-dimensional boron nitride hollow sphere are subjected to the following mass percent of 85:15 (the mass ratio of the heat conducting filler to the polyamic acid glue solution is 40:100), and the stable and high-quality polyamic acid composite glue solution is obtained through fully stirring, dispersing, filtering and vacuum defoaming. And (3) coating the polyamic acid composite glue solution with the solid content of 15% into a film to prepare the polyamic acid composite glue film containing the two-dimensional boron nitride nano-sheets and the three-dimensional boron nitride hollow spheres. And imidizing the polyamic acid composite adhesive film to obtain the polyimide composite film material with high heat conductivity. The out-of-plane thermal conductivity of the polyimide composite film was 1.42 W.m -1 ·K -1 。
Example 3.
Three-dimensional boron nitride hollow cube shells with average size of 3 mu m and average wall thickness of 50nm and two-dimensional boron nitride nano-sheets with average size of 2 mu m are selected as high heat conduction fillers. Respectively soaking and modifying the two-dimensional boron nitride nanosheets and the three-dimensional boron nitride hollow cube shells in an alcohol aqueous solution (the mass ratio of water to ethanol is 1:9) containing a vinyl silane coupling agent, filtering and drying to obtain the three-dimensional boron nitride hollow cube shellsSurface modified two-dimensional boron nitride nanoplatelets and three-dimensional boron nitride hollow cube shells. The coupling agent content is 1% of the mass of the two-dimensional boron nitride nano-sheet and the three-dimensional boron nitride hollow cube shell. The polyimide precursor-polyamic acid glue solution is synthesized by polycondensation reaction with biphenyl tetracarboxylic dianhydride (BPDA) and 4,4' -diaminodiphenyl ether (ODA) as binary anhydride and diamine monomer and N, N-dimethylacetamide (DMAc) as organic solvent. The coupling agent surface modified two-dimensional boron nitride nano-sheet and the three-dimensional boron nitride hollow cube shell are subjected to the following mass percent 95:5 (the mass ratio of the heat conducting filler to the polyamic acid glue solution is 30:100) and obtaining the stable and high-quality polyamic acid composite glue solution through fully stirring, dispersing, filtering and vacuum defoaming. And (3) coating the polyamic acid composite glue solution with the solid content of 15% into a film to prepare the polyamic acid composite glue film containing the two-dimensional boron nitride nano-sheets and the three-dimensional boron nitride hollow cube shell. And imidizing the polyamic acid composite adhesive film to obtain the polyimide composite film material with high heat conductivity. The out-of-plane thermal conductivity of the polyimide composite film was 1.25 W.m -1 ·K -1 。
Example 4.
Three-dimensional boron nitride hollow spheres with average size of 2.5 mu m and average wall thickness of 30nm and two-dimensional boron nitride nano-sheets with average thickness of 50nm and average size of 5 mu m are selected as high heat conduction filler. And respectively soaking and modifying the two-dimensional boron nitride nano-sheets and the three-dimensional boron nitride hollow spheres in an alcohol-water solution (the mass ratio of water to ethanol is 1:9) containing a titanate coupling agent, filtering and drying to obtain the surface modified two-dimensional boron nitride nano-sheets and the three-dimensional boron nitride hollow spheres. The content of the coupling agent is 2 percent of the mass of the two-dimensional boron nitride nano-sheet and the three-dimensional boron nitride hollow sphere. Pyromellitic dianhydride (PMDA) and 4,4' -diaminodiphenyl ether (ODA) are respectively used as binary anhydride and diamine monomers, and N, N-Dimethylformamide (DMF) is used as an organic solvent, and a polyimide precursor-polyamide acid glue solution is synthesized through polycondensation reaction. The coupling agent surface modified two-dimensional boron nitride nano-sheet and the three-dimensional boron nitride hollow sphere are subjected to the following mass percent 90:10 (the mass ratio of the heat conducting filler to the polyamic acid solution is 35:100), and then fully stirring and separatingDispersing, filtering and vacuum defoaming to obtain the stable high-quality polyamide acid composite glue solution. And (3) coating the polyamic acid composite glue solution with the solid content of 10% into a film to prepare the polyamic acid composite glue film containing the two-dimensional boron nitride nano-sheets and the three-dimensional boron nitride hollow spheres. And imidizing the polyamic acid composite adhesive film to obtain the polyimide composite film material with high heat conductivity. The out-of-plane thermal conductivity of the polyimide composite film was 1.27 W.multidot.m -1 ·K -1 。
Comparative example 1.
And selecting a two-dimensional boron nitride nano sheet with an average size of 5 mu m and an average thickness of 50nm as a high heat conduction filler. And (3) soaking and modifying the two-dimensional boron nitride nano-sheet in an alcohol-water solution (the mass ratio of water to ethanol is 2:8) containing a titanate coupling agent, filtering and drying to obtain the surface modified two-dimensional boron nitride nano-sheet. The content of the coupling agent is 1 percent of the mass of the two-dimensional boron nitride nano-sheet. Pyromellitic dianhydride (PMDA) and 4,4' -diaminodiphenyl ether (ODA) are respectively used as binary anhydride and diamine monomers, and N, N-Dimethylformamide (DMF) is used as an organic solvent, and a polyimide precursor-polyamide acid glue solution is synthesized through polycondensation reaction. And adding the two-dimensional boron nitride nano-plate subjected to surface modification by the coupling agent into the polyamic acid glue solution (the mass ratio of the two-dimensional boron nitride nano-plate to the polyamic acid glue solution is 30:100), and fully stirring, dispersing, filtering and vacuum defoaming to obtain the stable high-quality polyamic acid composite glue solution. And (3) coating the polyamic acid composite glue solution with the solid content of 10% into a film to prepare the polyamic acid composite glue film containing the two-dimensional boron nitride nano-sheets. And imidizing the polyamic acid composite adhesive film to obtain the polyimide composite film material. FIG. 4 is a cross-sectional morphology of a polyimide composite film material. The out-of-plane thermal conductivity of the polyimide composite film was 0.59 W.m -1 ·K -1 。
Claims (10)
1. The preparation method of the high-heat-conductivity polyimide composite film is characterized by comprising the following steps of:
step 1, respectively soaking and modifying a two-dimensional boron nitride nano sheet and a three-dimensional boron nitride empty shell in an alcohol water solution containing a surface modifier, filtering and drying to obtain a surface modified two-dimensional boron nitride nano sheet and a three-dimensional boron nitride empty shell;
step 2, taking dicarboxylic anhydride and diamine monomer as raw materials, and synthesizing polyimide precursor-polyamic acid glue solution in a polar aprotic solvent through solution polycondensation;
step 3, the surface modified two-dimensional boron nitride nano-sheet and the three-dimensional boron nitride empty shell obtained in the step 1 are mixed according to the mass ratio (95-0): adding the polyamide acid glue solution obtained in the step 2 according to the proportion of (5-100), stirring, dispersing, filtering and vacuum defoaming to obtain stable high-quality polyamide acid composite glue solution, and storing at a low temperature for later use;
step 4, coating the polyamic acid composite glue solution obtained in the step 3 into a film to obtain a polyamic acid composite glue film containing two-dimensional boron nitride nano sheets and three-dimensional boron nitride empty shells; then, imidizing the polyamic acid composite adhesive film at high temperature to obtain a polyimide composite film material with high heat conductivity;
among the above steps, step 1 and step 2 are raw material preparation steps, and the two steps are not distinguished in sequence.
2. The preparation method of the high-heat-conductivity polyimide composite film according to claim 1, wherein the two-dimensional boron nitride nano-sheet in the step 1 is a nano-sheet with the thickness of 5-100 nm and the plane size of 0.5-5 μm; the three-dimensional boron nitride empty shell in the step 1 is a hollow shell with the wall thickness of 5-100 nm and the size of 0.5-5 mu m.
3. The method for preparing the high-heat-conductivity polyimide composite film according to claim 1, wherein the three-dimensional boron nitride empty shell prepared in the step 1 is any one or combination of a hollow sphere and a hollow cube shell prepared by a template method.
4. The method for preparing the high-heat-conductivity polyimide composite film according to claim 1, wherein the surface modifier in the step 1 is any one or a combination of a titanate coupling agent and a vinyl silane coupling agent; the alcohol aqueous solution in the step 1 is a mixture of water and low molecular alcohol; the mass ratio of water to low molecular alcohol is (0.5-2): (9.5-8); the low molecular alcohol is any one or combination of methanol, ethanol and isopropanol.
5. The method for preparing the high-heat-conductivity polyimide composite film according to claim 1, wherein the dibasic acid anhydride in the step 2 is any one or a combination of the following structures:
6. the method for preparing the high-heat-conductivity polyimide composite film according to claim 1, wherein diamine in the step 2 is any one or a combination of the following structures:
7. the method for preparing the high-heat-conductivity polyimide composite film according to claim 1, wherein the polar aprotic solvent in the step 2 is any one or a combination of solvents selected from the group consisting of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone and dimethylsulfoxide.
8. The preparation method of the high-heat-conductivity polyimide composite film according to claim 1, wherein the mass ratio of the surface-modified two-dimensional boron nitride nanosheets to the surface-modified three-dimensional boron nitride empty shells in the step 3 is (90-50): (10-50); the mass ratio of the sum of the mass of the surface modified two-dimensional boron nitride nano sheet and the surface modified three-dimensional boron nitride blank to the mass of the polyamic acid glue solution in the step 3 is (5-50): 100.
9. the method for preparing the high-heat-conductivity polyimide composite film according to claim 1, wherein the solid content of the polyamic acid composite glue solution in the step 3 is 10-25%.
10. The method for preparing a high thermal conductivity polyimide composite film according to claim 1, wherein the high temperature imidization in step 4 is one of thermal imidization and chemical imidization; when a chemical imidization process is adopted, adding a dehydrating agent and a catalyst into the polyamic acid composite glue solution in the step 3 according to a conventional process, wherein the dehydrating agent is any one or a combination of acetic anhydride, propionic anhydride, butyric anhydride and benzoic anhydride; the catalyst is any one or a combination of pyridine and derivatives thereof, picoline and derivatives thereof, lutidine, N-dimethylaminopyridine, quinoline, isoquinoline and triethylamine.
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