CN116061525A - Polydopamine modified boron nitride nano-sheet/polyimide composite fiber heat conduction film and preparation method and application thereof - Google Patents
Polydopamine modified boron nitride nano-sheet/polyimide composite fiber heat conduction film and preparation method and application thereof Download PDFInfo
- Publication number
- CN116061525A CN116061525A CN202211718146.0A CN202211718146A CN116061525A CN 116061525 A CN116061525 A CN 116061525A CN 202211718146 A CN202211718146 A CN 202211718146A CN 116061525 A CN116061525 A CN 116061525A
- Authority
- CN
- China
- Prior art keywords
- boron nitride
- sheet
- nitride nano
- composite fiber
- modified boron
- 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.)
- Pending
Links
- 229920001690 polydopamine Polymers 0.000 title claims abstract description 243
- 239000002135 nanosheet Substances 0.000 title claims abstract description 175
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical class N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 171
- 239000002131 composite material Substances 0.000 title claims abstract description 144
- 239000000835 fiber Substances 0.000 title claims abstract description 134
- 229920001721 polyimide Polymers 0.000 title claims abstract description 122
- 239000004642 Polyimide Substances 0.000 title claims abstract description 117
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000748 compression moulding Methods 0.000 claims abstract description 60
- 239000000243 solution Substances 0.000 claims abstract description 59
- 238000003756 stirring Methods 0.000 claims abstract description 58
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 54
- 239000004952 Polyamide Substances 0.000 claims abstract description 38
- 239000002253 acid Substances 0.000 claims abstract description 38
- 229920002647 polyamide Polymers 0.000 claims abstract description 38
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 37
- 239000011259 mixed solution Substances 0.000 claims abstract description 36
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 35
- 239000000178 monomer Substances 0.000 claims description 34
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 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 claims description 24
- 239000005457 ice water Substances 0.000 claims description 16
- 150000004985 diamines Chemical class 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000009489 vacuum treatment Methods 0.000 claims description 10
- 239000003880 polar aprotic solvent Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 8
- ZHDTXTDHBRADLM-UHFFFAOYSA-N hydron;2,3,4,5-tetrahydropyridin-6-amine;chloride Chemical compound Cl.NC1=NCCCC1 ZHDTXTDHBRADLM-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 238000004100 electronic packaging Methods 0.000 claims description 4
- 238000006068 polycondensation reaction Methods 0.000 abstract description 11
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 38
- 238000002347 injection Methods 0.000 description 28
- 239000007924 injection Substances 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- 239000000843 powder Substances 0.000 description 26
- 229910052582 BN Inorganic materials 0.000 description 24
- 229960003638 dopamine Drugs 0.000 description 19
- 239000002184 metal Substances 0.000 description 18
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 16
- 239000007983 Tris buffer Substances 0.000 description 15
- 238000005520 cutting process Methods 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 238000001035 drying Methods 0.000 description 13
- 238000002156 mixing Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 239000006228 supernatant Substances 0.000 description 13
- 238000001132 ultrasonic dispersion Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000001816 cooling Methods 0.000 description 12
- 238000011049 filling Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000010907 mechanical stirring Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- PDVGPRKWYIVXGR-UHFFFAOYSA-N 4-phenylcyclohexa-2,4-diene-1,1-diamine Chemical group C1=CC(N)(N)CC=C1C1=CC=CC=C1 PDVGPRKWYIVXGR-UHFFFAOYSA-N 0.000 description 4
- 238000001523 electrospinning Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/022—Non-woven fabric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
- B32B5/265—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary characterised by one fibrous or filamentary layer being a non-woven fabric layer
- B32B5/266—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary characterised by one fibrous or filamentary layer being a non-woven fabric layer next to one or more non-woven fabric layers
-
- 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/76—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres otherwise than in a plane, e.g. in a tubular way
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/302—Conductive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Fluid Mechanics (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a polydopamine modified boron nitride nano-sheet/polyimide composite fiber heat conduction film, a preparation method and application thereof, wherein polydopamine modified boron nitride nano-sheet is added into polyamic acid solution, and after stirring, polydopamine modified boron nitride nano-sheet/polyamic acid mixed solution is prepared; preparing a composite fiber felt by using a polydopamine modified boron nitride nano sheet/polyamide acid mixed solution through an electrostatic spinning method, and performing thermal imidization treatment on the composite fiber felt to prepare the polydopamine modified boron nitride nano sheet/polyimide composite fiber felt; and carrying out compression molding on a plurality of layers of polydopamine modified boron nitride nano-sheet/polyimide composite fiber felt to obtain the polydopamine modified boron nitride nano-sheet/polyimide composite fiber heat conducting film. The method combines low-temperature polycondensation, electrostatic spinning and compression molding, realizes zigzag directional arrangement of PI fibers, and obviously improves the mechanical property and the heat conducting property of the PI fiber film.
Description
Technical Field
The invention belongs to the technical field of preparation of polymer films, and relates to a polydopamine modified boron nitride nanosheet/polyimide composite fiber heat-conducting film, and a preparation method and application thereof.
Background
Polyimide (PI) is a high polymer material with excellent comprehensive performance, has the advantages of excellent high and low temperature resistance, good chemical corrosion resistance, outstanding electrical insulation, high dimensional stability and the like, and has been widely applied to the fields of aviation, aerospace, microelectronics and the like, however, the low thermal conductivity limits the application of the polyimide to the field of thermal management. The boron nitride nano-sheet (BNNS) has the advantages of high heat conductivity coefficient (lambda), low dielectric constant (epsilon), dielectric loss tangent value (tan delta), excellent oxidation resistance, corrosion resistance and the like, so that the boron nitride nano-sheet (BNNS) becomes an ideal filler for preparing the PI heat-conducting insulating composite material. Therefore, an effective combination of polyimide and highly thermally conductive filler (BNNS) is considered to be an ideal solution.
Currently, methods for preparing polyimide films include an electrospinning method, a doctor blade coating method, and a casting method. Among them, electrospinning under a high electric field is a simple and effective method for preparing polymer fibers by solution. Advantages of the prepared fibers mainly include small diameter, high length-diameter ratio and large specific surface area, which makes it possible to prepare oriented high-thermal-conductivity nanocomposite fibers. In addition, the multifunctional and simple electrospinning technique provides an effective way to improve uniform dispersion of the filler while also achieving effective alignment of the inorganic filler in the polymer matrix. However, the boron nitride nano-sheets in the prior art have higher usage amount, the heat conduction performance is improved, but the high filler usage amount leads to poor processing capability of the composite fiber and obviously reduced mechanical property, and meanwhile, the boron nitride nano-sheets have poor dispersibility in polyimide films, so that the potential application fields of the boron nitride nano-sheets are limited.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a polyimide composite fiber heat conduction film, and a preparation method and application thereof, thereby solving the technical problems that the mechanical property is poor and the dispersibility of the boron nitride nano-sheet is poor while the heat conduction property of the polyimide composite fiber film is improved by utilizing the boron nitride nano-sheet in the prior art.
The invention is realized by the following technical scheme:
the preparation method of the polydopamine modified boron nitride nano sheet/polyimide composite fiber heat conduction film is characterized by comprising the following steps of:
s1: adding the polydopamine modified boron nitride nano-sheet into a polyamic acid solution, and stirring to obtain a polydopamine modified boron nitride nano-sheet/polyamic acid mixed solution;
s2: preparing a polydopamine modified boron nitride nano sheet/polyamide acid composite fiber felt by using the polydopamine modified boron nitride nano sheet/polyamide acid mixed solution through an electrostatic spinning method; the collecting mode in the electrostatic spinning process is Z-shaped;
s3: carrying out thermal imidization treatment on the polydopamine modified boron nitride nano-sheet/polyamide acid composite fiber felt to obtain polydopamine modified boron nitride nano-sheet/polyimide composite fiber felt;
S4: and carrying out compression molding on a plurality of layers of the polydopamine modified boron nitride nano-sheet/polyimide composite fiber felt to obtain the polydopamine modified boron nitride nano-sheet/polyimide composite fiber heat conducting film.
Preferably, the preparation process of the polyamic acid solution comprises the following steps: under the ice water bath condition, adding diamine monomer into polar aprotic solvent, stirring to dissolve diamine monomer completely, adding dianhydride monomer, and continuously stirring until polymerization reaction is complete to obtain polyamic acid solution.
Preferably, the diamine monomer is one or a mixture of more of 4, 4-diaminodiphenyl ether, 4-diaminobiphenyl and p-phenylenediamine in any proportion; the dianhydride monomer is one or a mixture of more of pyromellitic anhydride, hexafluorodianhydride and 3,3', 4' -benzophenone tetracarboxylic dianhydride in any proportion.
Preferably, the polar aprotic solvent is one or a mixture of more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide in any proportion.
Preferably, the dianhydride monomer is added in several batches, after each dianhydride monomer is added, the dianhydride monomer is stirred to be dissolved and reacted completely, and then the dianhydride monomer of the next batch is added.
Preferably, in the electrospinning method, the voltage is 15kV to 25kV.
Preferably, before the polydopamine modified boron nitride nano-sheet/polyamide acid composite fiber felt is subjected to thermal imidization treatment, the polydopamine modified boron nitride nano-sheet/polyamide acid composite fiber felt is subjected to vacuum treatment; the conditions of the vacuum treatment are as follows: vacuum degree is 0.08-0.1 MPa, temperature is 60-80 ℃ and time is 4-6 h.
Preferably, the temperature of the compression molding is 290-320 ℃, the pressure is 5-10 MPa, and the time is 10-15 min.
The polydopamine modified boron nitride nano sheet/polyimide composite fiber heat conducting film is prepared by the method; the tensile strength coefficient of the polydopamine modified boron nitride nano sheet/polyimide composite fiber heat conduction film is 7.1-36.8 Mpa, and the heat conductivity is 0.21-0.64W/(m.K).
The polydopamine modified boron nitride nano sheet/polyimide composite fiber heat conduction film prepared by the method is applied to the field of electronic packaging.
Compared with the prior art, the invention has the following beneficial technical effects:
the preparation method of the polydopamine modified boron nitride nano sheet/polyimide composite fiber heat conduction film comprises the steps that a polydopamine modified structure constructed on the boron nitride nano sheet can be effectively bonded with polyimide, so that the dispersibility of the boron nitride nano sheet in the polyimide film is effectively improved.
Further, the preparation process of the polyamic acid solution comprises the following steps: under the ice water bath condition, adding diamine monomer into polar aprotic solvent, stirring to dissolve diamine monomer completely, adding dianhydride monomer, continuously stirring until polymerization reaction is complete, and obtaining polyamic acid solution.
Further, the polar aprotic solvent is one or a mixture of more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide in any proportion, and the selected polar aprotic solvent has high boiling point, low solidifying point and good chemical and thermal stability.
Further, the dianhydride monomer is added in a plurality of batches, after each dianhydride monomer is added, the dianhydride monomer is stirred to be dissolved and react completely, and then the dianhydride monomer of the next batch is added, so that the dianhydride and the diamine can react fully.
Furthermore, the voltage in the electrostatic spinning method is 15 kV-25 kV, so that the fiber is uniformly and stably produced, and the yield is high.
Further, before the polydopamine modified boron nitride nano sheet/polyamide acid composite fiber felt is subjected to thermal imidization treatment, the polydopamine modified boron nitride nano sheet/polyamide acid composite fiber felt is treated under vacuum, so that the release of an organic solvent in a room can be effectively reduced, and further, the vacuum treatment conditions are as follows: vacuum degree is 0.08-0.1 MPa, temperature is 60-80 ℃ and time is 4-6 h, so that DMF solvent can be effectively volatilized
Further, the temperature of compression molding is 290-320 ℃, the pressure is 5-10 MPa, and the time is 10-15 min, so that the multi-layer fluffy film can be molded into a single-layer compact film.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of a preparation method of a polydopamine modified boron nitride nano-sheet/polyimide composite fiber heat conducting film;
FIG. 2 is a schematic diagram of a method for preparing a polydopamine modified boron nitride nanosheet/polyimide composite fiber heat-conducting film by adopting different collecting modes in an electrostatic spinning method;
FIG. 3 shows the tensile strength test results of the composite fiber films prepared in examples 1 to 8 of the present invention;
FIG. 4 shows the results of thermal conductivity test of the composite fiber films prepared in examples 1 to 8 of the present invention.
Detailed Description
So that those skilled in the art can appreciate the features and effects of the present invention, a general description and definition of the terms and expressions set forth in the specification and claims follows. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and in the event of a conflict, the present specification shall control.
The theory or mechanism described and disclosed herein, whether right or wrong, is not meant to limit the scope of the invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features such as values, amounts, and concentrations that are defined herein in the numerical or percent ranges are for brevity and convenience only. Accordingly, the description of a numerical range or percentage range should be considered to cover and specifically disclose all possible sub-ranges and individual values (including integers and fractions) within the range.
Herein, unless otherwise indicated, "comprising," "including," "having," or similar terms encompass the meanings of "consisting of … …" and "consisting essentially of … …," e.g., "a includes a" encompasses the meanings of "a includes a and the other and" a includes a only.
In this context, not all possible combinations of the individual technical features in the individual embodiments or examples are described in order to simplify the description. Accordingly, as long as there is no contradiction between the combinations of these technical features, any combination of the technical features in the respective embodiments or examples is possible, and all possible combinations should be considered as being within the scope of the present specification.
The invention provides a preparation method of a polydopamine modified boron nitride nano sheet/polyimide composite fiber heat-conducting film, which takes polyamide acid (PAA) formed by polycondensation of 4,4' -diaminodiphenyl ether (ODA) and pyromellitic anhydride (PMDA) as a matrix, adopts an electrostatic spinning method to prepare a polyamide acid (PAA) fiber felt, and then prepares the Polyimide (PI) composite film with high strength and heat conduction through thermal imidization and compression molding processes. As shown in fig. 1, the specific process of the preparation method is as follows:
s1: adding the polydopamine modified boron nitride nano-sheet into a polyamic acid solution, and stirring to obtain a polydopamine modified boron nitride nano-sheet/polyamic acid mixed solution;
the preparation process of the polyamic acid solution comprises the steps of adding diamine monomer into polar aprotic solvent under ice water bath condition, stirring to completely dissolve the diamine monomer, adding dianhydride monomer, and continuously stirring until polymerization reaction is complete to obtain the polyamic acid solution. The diamine monomer is one or more of 4, 4-diaminodiphenyl ether, 4-diaminodiphenyl and p-phenylenediamine, the dianhydride monomer is one or more of pyromellitic anhydride, hexafluorodianhydride and 3,3', 4' -benzophenone tetracarboxylic dianhydride, the polar aprotic solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide. Further preferably, the dianhydride monomer is added in several batches, and after each dianhydride monomer is added, the dianhydride monomer is stirred to be dissolved and reacted completely, and then the next dianhydride monomer is added. Wherein the diameter of the polydopamine modified boron nitride nanosheets is 80-200 nm, and the thickness is 10-20 nm.
The preparation process of the polydopamine modified boron nitride nanosheets comprises the steps of adding Tris (Tris (hydroxymethyl) aminomethane) solid powder into a mixed solution of deionized water and ethanol, and uniformly mixing; adding boron nitride nano-sheets (BNNS), performing ultrasonic dispersion, stirring to uniformly disperse the boron nitride nano-sheets, adding dopamine powder, and stirring at room temperature until the solution is grey black; standing at room temperature, removing supernatant, and drying to obtain polydopamine modified boron nitride nano-sheet (BNNS@PDA). Tris provides alkaline environment for dopamine polymerization, and the mass ratio of the boron nitride nano-sheet to the dopamine in the reaction is (1.5-2.5) (0.6-1); in addition, the mass fraction of the polydopamine modified boron nitride nano-sheet in the polydopamine modified boron nitride nano-sheet/polyamic acid mixed solution is 5-30%.
S2: preparing a polydopamine modified boron nitride nano sheet/polyamide acid composite fiber felt by using a polydopamine modified boron nitride nano sheet/polyamide acid mixed solution through an electrostatic spinning method under the voltage of 15 kV-25 kV; wherein the collecting mode of the electrostatic spinning method is Z-shaped;
the electrostatic spinning process comprises the following steps: the polyamide acid (PAA) solution is filled into an injection needle tube provided with a metal needle, then the injection needle tube is horizontally fixed on an injection device, a positive electrode of a high-voltage power supply of an electrostatic spinning instrument is connected with the metal needle tube, tin foil collecting paper is coated on a roller-shaped negative electrode, the injection needle tube is aligned with the center of a roller, a working chamber of the electrostatic spinning instrument is kept in a sealed state, the temperature of the working chamber is 18-25 ℃ in the electrostatic spinning process, the relative humidity of the environment is 50-60%, the voltage of the high-voltage power supply is 15-25 kV, the distance from the needle tube to the center of the roller is 15-20 cm, the rotating speed of the roller is 40-120 m/min, and the arrangement mode in the invention comprises random, directional, vertical and Z-shaped arrangement modes according to the difference of the roller collecting mode and the lamination arrangement mode as shown in figure 2.
S3: carrying out thermal imidization treatment on the polydopamine modified boron nitride nano-sheet/polyamide acid composite fiber felt to obtain polydopamine modified boron nitride nano-sheet/polyimide composite fiber felt;
before the polydopamine modified boron nitride nano-sheet/polyamide acid composite fiber felt is subjected to thermal imidization treatment, the polydopamine modified boron nitride nano-sheet/polyamide acid composite fiber felt is treated under vacuum; the conditions of the vacuum treatment are as follows: vacuum degree is 0.08-0.1 MPa, temperature is 60-80 ℃ and time is 4-6 h.
S4: and carrying out compression molding on a plurality of layers of the polydopamine modified boron nitride nano-sheet/polyimide composite fiber felt to obtain the polydopamine modified boron nitride nano-sheet/polyimide composite fiber heat conducting film. In the prepared polydopamine modified boron nitride nanosheet/polyimide composite fiber heat-conducting film, BNNS@PDA accounts for 5% -10% of the mass of PAA, namely the BNNS addition proportion is preferably 5% -10%, the higher the addition amount of BNNS is, the lower the mechanical property is, the addition amount is too low, and the heat-conducting property of the material is limited to improve.
The specific process of compression molding comprises the following steps: weighing 2g of polydopamine modified boron nitride nanosheet/polyimide composite fiber mat, cutting into samples with the size of 20mm multiplied by 20mm, stacking the samples into a mould according to the arrangement modes of vertical, Z-shaped and the like, and performing compression molding on a small flat vulcanizing machine at the temperature of 290-320 ℃, the pressure of 5-10 MPa and the time of 10-15 min.
The invention adopts a method of combining low-temperature polycondensation, electrostatic spinning and compression molding to realize the effective arrangement of polyimide fibers, so that the mechanical property and the heat conducting property of the polyimide fiber film are obviously improved, and the tensile strength coefficient of the polydopamine modified boron nitride nano sheet/polyimide composite fiber heat conducting film obtained by the method is 7.1-36.8 Mpa, and the heat conductivity is 0.21-0.64W/(m.K). The obtained polydopamine modified boron nitride nano sheet/polyimide composite fiber heat conduction film can be applied to the field of electronic packaging.
According to the preparation method of the polydopamine modified boron nitride nanosheets/polyimide composite fiber heat conducting film, a polydopamine modified structure constructed on the boron nitride nanosheets can be effectively bonded with polyimide, so that the dispersibility of the boron nitride nanosheets in the polyimide film is effectively improved.
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
The following examples use instrumentation conventional in the art. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. The following examples used various starting materials, unless otherwise indicated, were conventional commercial products, the specifications of which are conventional in the art. In the description of the present invention and the following examples, "%" means weight percent, and "parts" means parts by weight, and ratios means weight ratio, unless otherwise specified.
Example 1
Adding 1.2g of Tris (Tris (hydroxymethyl aminomethane) solid powder into a mixed solution of 300mL of deionized water and 100mL of ethanol, and uniformly mixing; adding 2.0g of boron nitride nano-sheets (BNNS), performing ultrasonic dispersion for 10min, stirring to uniformly disperse the boron nitride nano-sheets, adding 0.8g of dopamine powder, and stirring at room temperature for 6h until the solution is gray black; standing at room temperature for 24 hours, removing supernatant, and drying at 60 ℃ for 12 hours to obtain the polydopamine modified boron nitride nano-sheet (BNNS@PDA), wherein the polydopamine modified boron nitride nano-sheet has the diameter of 80nm and the thickness of 10nm.
1.08g of 4,4' -diaminodiphenyl ether (ODA) is added into a three-neck flask, 19g of N, N-Dimethylformamide (DMF) is added under the ice water bath condition, 1.244g of pyromellitic anhydride (PMDA) is added in batches after the ODA is completely dissolved, 0.15g of PMDA is added in batches, after the PMDA is completely added and dissolved, 0.19g of BNNS@PDA is added after mechanical stirring for 30min, stirring is continued for 30min, and the poly dopamine modified boron nitride nano sheet/polyamide acid (BNNS@PDA/PAA) mixed solution is obtained through polycondensation.
BNNS@PDA/PAA solution is filled into a 6mL injection needle tube provided with a metal needle, and then the injection needle tube is horizontally fixed on an injection device, and a random arrangement mode is adopted: connecting a positive electrode joint of a high-voltage power supply of an electrostatic spinning instrument with a metal needle, coating tin foil collecting paper on a flat plate-shaped negative electrode, aligning an injection needle tube with the center of the flat plate, keeping a working chamber of the electrostatic spinning instrument in a sealed state, keeping the temperature of the working chamber at 18 ℃, keeping the electrostatic positive voltage at 15kV, keeping the working distance at 15cm, keeping the relative humidity of the environment at 50%, keeping the rotating speed of a receiving shaft at 40m/min, carrying out electrostatic spinning to obtain a BNNS@PDA/PAA heat-conducting composite fiber felt, carrying out thermal imidization in a vacuum oven according to the procedures of 120 ℃/1h,200 ℃/1h and 250 ℃/1h and with the heating rate of 5 ℃/min, and taking out after cooling to room temperature to obtain the polydopamine modified boron nitride nanosheet/polyimide (BNNS@PDA/PI) composite fiber felt;
Cutting 2g of BNNS@PDA/PI heat conduction composite fiber felt into a sample with the length of 20mm multiplied by 20mm, filling the sample into a mould, and carrying out compression molding on a small flat vulcanizing machine to prepare the BNNS@PDA/PI composite material, wherein the compression molding temperature is 290 ℃, the compression molding pressure is 5MPa, and the compression molding time is 10min, so as to prepare the polydopamine modified boron nitride nano sheet/polyimide (BNNS@PDA/PI) composite fiber heat conduction film, wherein the BNNS@PDA accounts for 5% of the PAA by mass.
Example 2
Adding 1.2g of Tris solid powder into a mixed solution of 300mL of deionized water and 100mL of ethanol, and uniformly mixing; adding 2.0g of BNNS, performing ultrasonic dispersion for 10min to uniformly disperse, adding 0.8g of dopamine powder, and stirring at room temperature for 6h until the solution is grey black; standing at room temperature for 24h, removing supernatant, and drying at 60 ℃ for 12h to obtain polydopamine modified boron nitride nanosheets with the diameter of 81nm and the thickness of 10.5nm.
1.08g of ODA is added into a three-neck flask, 19g of DMF is added under the condition of ice water bath, 1.244g of PMDA is added in batches after the ODA is completely dissolved, 0.15g of PMDA is added in batches, after the PMDA is completely added and dissolved, 0.19g of BNNS@PDA is added after mechanical stirring for 30min, stirring is continued for 30min, and the BNNS@PDA/PAA solution is obtained through polycondensation.
BNNS@PDA/PAA solution is filled into a 6mL injection needle tube provided with a metal needle, and then the injection needle tube is horizontally fixed on an injection device, and a directional arrangement mode is adopted: connecting a positive electrode joint of a high-voltage power supply of an electrostatic spinning instrument with a metal needle, coating tin foil collecting paper on a roller-shaped negative electrode, aligning an injection needle tube with the center of a roller, keeping a working chamber of the electrostatic spinning instrument in a sealed state, keeping the temperature of the working chamber at 18 ℃, keeping the electrostatic positive voltage at 20kV, keeping the working distance at 15cm, keeping the relative humidity at 50%, keeping the rotating speed of a receiving shaft at 120m/min, and carrying out electrostatic spinning to obtain BNNS@PDA/PAA heat conduction composite fiber felt, carrying out thermal imidization according to a program of 120 ℃/1h+200 ℃/1h+250 ℃/1h and a heating rate of 5 ℃/min in a vacuum oven, and cooling to room temperature and then taking out to obtain the BNNS@PDA/PI heat conduction composite fiber felt; cutting 2g of BNNS@PDA/PI heat conduction composite fiber mat into a sample with the length of 20mm multiplied by 20mm, filling the sample into a mould, and carrying out compression molding on a small flat vulcanizing machine to prepare the BNNS@PDA/PI heat conduction insulation composite material, wherein the compression molding temperature is 320 ℃, the compression molding pressure is 10MPa, and the compression molding time is 10min, thereby preparing the BNNS@PDA/PI composite film, wherein the BNNS@PDA accounts for 5% of the PAA mass.
Example 3
Adding 1.2g of Tris solid powder into a mixed solution of 300mL of deionized water and 100mL of ethanol, and uniformly mixing; adding 2.0g of BNNS, performing ultrasonic dispersion for 10min, stirring to uniformly disperse, adding 0.8g of dopamine powder, and stirring at room temperature for 6h until the solution is grey black; standing at room temperature for 24h, removing supernatant, and drying at 60 ℃ for 12h to obtain BNNS@PDA, wherein the polydopamine modified boron nitride nanosheets have a diameter of 80nm and a thickness of 12nm.
1.08g of ODA is added into a three-neck flask, 19g of DMF is added under the condition of ice water bath, 1.244g of PMDA is added in batches after the ODA is completely dissolved, 0.15g of PMDA is added in batches, after the PMDA is completely added and dissolved, 0.19g of BNNS@PDA is added after mechanical stirring for 30min, stirring is continued for 30min, and the BNNS@PDA/PAA solution is obtained through polycondensation.
BNNS@PDA/PAA solution was loaded into a 6mL syringe equipped with a metal needle, and then the syringe was horizontally fixed to the injection device in a vertical arrangement: connecting a positive electrode joint of a high-voltage power supply of an electrostatic spinning instrument with a metal needle, coating tin foil collecting paper on a flat plate-shaped negative electrode, aligning an injection needle tube with the center of the flat plate, keeping a working chamber of the electrostatic spinning instrument in a sealing state, keeping the temperature of the working chamber at 18 ℃, keeping the electrostatic positive voltage at 15kV, keeping the working distance at 15cm, keeping the relative humidity at 50%, keeping the rotating speed of a receiving shaft at 40m/min, and carrying out electrostatic spinning to obtain BNNS@PDA/PAA heat-conducting composite fiber felt, carrying out thermal imidization according to a program of 120 ℃/1h+200 ℃/1h+250 ℃/1h and a heating rate of 5 ℃/min in a vacuum oven, and cooling to room temperature and then taking out to obtain the BNNS@PDA/PI heat-conducting composite fiber felt;
Cutting 2g BNNS@PDA/PI heat conduction composite fiber mat into four layers with 20mm multiplied by 20mm samples which are arranged vertically in a crossing way, filling the four layers into a mould, and carrying out compression molding on a small flat vulcanizing machine to prepare the BNNS@PDA/PI composite material, wherein the compression molding temperature is 290 ℃, the compression molding pressure is 5MPa, and the compression molding time is 10min, so as to prepare the BNNS@PDA/PI composite film, and the BNNS@PDA accounts for 5% of the mass of PAA.
Example 4
Adding 1.2g of Tris solid powder into a mixed solution of 300mL of deionized water and 100mL of ethanol, and uniformly mixing; adding 2.0g of BNNS, performing ultrasonic dispersion for 10min to uniformly disperse, adding 0.8g of dopamine powder, and stirring at room temperature for 6h until the solution is grey black; standing at room temperature for 24h, removing supernatant, and drying at 60 ℃ for 12h to obtain polydopamine modified boron nitride nanosheets with the diameter of 83nm and the thickness of 13nm.
1.08g of ODA is added into a three-neck flask, 19g of DMF is added under the condition of ice water bath, 1.244g of PMDA is added in batches after the ODA is completely dissolved, 0.15g of PMDA is added in batches, after the PMDA is completely added and dissolved, 0.19g of BNNS@PDA is added after mechanical stirring for 30min, stirring is continued for 30min, and the BNNS@PDA/PAA solution is obtained through polycondensation.
BNNS@PDA/PAA solution was loaded into a 6mL syringe equipped with a metal needle, and then the syringe was horizontally fixed to the injection device in a zigzag arrangement: connecting a positive electrode joint of a high-voltage power supply of an electrostatic spinning instrument with a metal needle, coating tin foil collecting paper on a roller-shaped negative electrode, horizontally moving an injection needle tube at the center of a roller at a constant speed, keeping the working chamber of the electrostatic spinning instrument in a sealed state, keeping the temperature of the working chamber at 18 ℃, keeping the electrostatic positive voltage at 20kV, keeping the working distance at 15cm, keeping the relative humidity at 50%, keeping the rotating speed of a receiving shaft at 120m/min, carrying out electrostatic spinning to obtain BNNS@PDA/PAA heat-conducting composite fiber felt, carrying out thermal imidization according to a program of 120 ℃/1h+200 ℃/1h+250 ℃/1h and a heating rate of 5 ℃/min in a vacuum oven, and taking out after cooling to room temperature to obtain the BNNS@PDA/PI heat-conducting composite fiber felt; cutting 2g of BNNS@PDA/PI heat conduction composite fiber mat into a sample with the length of 20mm multiplied by 20mm, filling the sample into a mould, and carrying out compression molding on a small flat vulcanizing machine to prepare the BNNS@PDA/PI heat conduction insulation composite material, wherein the compression molding temperature is 320 ℃, the compression molding pressure is 10MPa, and the compression molding time is 10min, thereby preparing the BNNS@PDA/PI composite film, wherein the BNNS@PDA accounts for 5% of the PAA mass.
Example 5
Adding 1.2g of Tris solid powder into a mixed solution of 300mL of deionized water and 100mL of ethanol, and uniformly mixing; adding 2.0g of BNNS, performing ultrasonic dispersion for 10min, stirring to uniformly disperse, adding 0.8g of dopamine powder, and stirring at room temperature for 6h until the solution is grey black; standing at room temperature for 24h, removing supernatant, and drying at 60 ℃ for 12h to obtain BNNS@PDA, wherein the polydopamine modified boron nitride nanosheets have a diameter of 81nm and a thickness of 10nm.
1.08g of ODA is added into a three-neck flask, 19g of DMF is added under the condition of ice water bath, 1.244g of PMDA is added in batches after the ODA is completely dissolved, 0.15g of PMDA is added in batches, after the PMDA is completely added and dissolved, 0.38g of BNNS@PDA is added after mechanical stirring for 30min, stirring is continued for 30min, and the BNNS@PDA/PAA solution is obtained through polycondensation.
BNNS@PDA/PAA solution is filled into a 6mL injection needle tube provided with a metal needle, and then the injection needle tube is horizontally fixed on an injection device, and a random arrangement mode is adopted: connecting a positive electrode joint of a high-voltage power supply of an electrostatic spinning instrument with a metal needle, coating tin foil collecting paper on a flat plate-shaped negative electrode, aligning an injection needle tube with the center of the flat plate, keeping a working chamber of the electrostatic spinning instrument in a sealing state, keeping the temperature of the working chamber at 18 ℃, keeping the electrostatic positive voltage at 15kV, keeping the working distance at 15cm, keeping the relative humidity at 50%, keeping the rotating speed of a receiving shaft at 40m/min, and carrying out electrostatic spinning to obtain BNNS@PDA/PAA heat-conducting composite fiber felt, carrying out thermal imidization according to a program of 120 ℃/1h+200 ℃/1h+250 ℃/1h and a heating rate of 5 ℃/min in a vacuum oven, and cooling to room temperature and then taking out to obtain the BNNS@PDA/PI heat-conducting composite fiber felt;
Cutting 2g of BNNS@PDA/PI heat conduction composite fiber mat into a sample with the length of 20mm multiplied by 20mm, filling the sample into a mould, and carrying out compression molding on a small flat vulcanizing machine to prepare the BNNS@PDA/PI composite material, wherein the compression molding temperature is 290 ℃, the compression molding pressure is 5MPa, and the compression molding time is 10 minutes, so as to prepare the BNNS@PDA/PI composite film, and the BNNS@PDA accounts for 10% of the mass of PAA.
Example 6
Adding 1.2g of Tris solid powder into a mixed solution of 300mL of deionized water and 100mL of ethanol, and uniformly mixing; adding 2.0g of BNNS, performing ultrasonic dispersion for 10min to uniformly disperse, adding 0.8g of dopamine powder, and stirring at room temperature for 6h until the solution is grey black; standing at room temperature for 24h, removing supernatant, and drying at 60 ℃ for 12h to obtain polydopamine modified boron nitride nanosheets with the diameter of 80nm and the thickness of 12nm.
1.08g of ODA is added into a three-neck flask, 19g of DMF is added under the condition of ice water bath, 1.244g of PMDA is added in batches after the ODA is completely dissolved, 0.15g of PMDA is added in batches, after the PMDA is completely added and dissolved, 0.38g of BNNS@PDA is added after mechanical stirring for 30min, stirring is continued for 30min, and the BNNS@PDA/PAA solution is obtained through polycondensation.
BNNS@PDA/PAA solution is filled into a 6mL injection needle tube provided with a metal needle, and then the injection needle tube is horizontally fixed on an injection device, and a directional arrangement mode is adopted: connecting a positive electrode joint of a high-voltage power supply of an electrostatic spinning instrument with a metal needle, coating tin foil collecting paper on a roller-shaped negative electrode, aligning an injection needle tube with the center of a roller, keeping a working chamber of the electrostatic spinning instrument in a sealed state, keeping the temperature of the working chamber at 18 ℃, keeping the electrostatic positive voltage at 20kV, keeping the working distance at 15cm, keeping the relative humidity at 50%, keeping the rotating speed of a receiving shaft at 120m/min, and carrying out electrostatic spinning to obtain BNNS@PDA/PAA heat conduction composite fiber felt, carrying out thermal imidization according to a program of 120 ℃/1h+200 ℃/1h+250 ℃/1h and a heating rate of 5 ℃/min in a vacuum oven, and cooling to room temperature and then taking out to obtain the BNNS@PDA/PI heat conduction composite fiber felt; cutting 2g of BNNS@PDA/PI heat conduction composite fiber mat into a sample with the length of 20mm multiplied by 20mm, filling the sample into a mould, and carrying out compression molding on a small flat vulcanizing machine to prepare the BNNS@PDA/PI heat conduction insulation composite material, wherein the compression molding temperature is 320 ℃, the compression molding pressure is 10MPa, and the compression molding time is 10min, thereby preparing the BNNS@PDA/PI composite film, wherein the BNNS@PDA accounts for 10% of the PAA mass.
Example 7
Adding 1.2g of Tris solid powder into a mixed solution of 300mL of deionized water and 100mL of ethanol, and uniformly mixing; adding 2.0g of BNNS, performing ultrasonic dispersion for 10min, stirring to uniformly disperse, adding 0.8g of dopamine powder, and stirring at room temperature for 6h until the solution is grey black; standing at room temperature for 24h, removing supernatant, and drying at 60 ℃ for 12h to obtain BNNS@PDA, wherein the polydopamine modified boron nitride nanosheets have a diameter of 80nm and a thickness of 11nm.
1.08g of ODA is added into a three-neck flask, 19g of DMF is added under the condition of ice water bath, 1.244g of PMDA is added in batches after the ODA is completely dissolved, 0.15g of PMDA is added in batches, after the PMDA is completely added and dissolved, 0.38g of BNNS@PDA is added after mechanical stirring for 30min, stirring is continued for 30min, and the BNNS@PDA/PAA solution is obtained through polycondensation.
BNNS@PDA/PAA solution was loaded into a 6mL syringe equipped with a metal needle, and then the syringe was horizontally fixed to the injection device in a vertical arrangement: connecting a positive electrode joint of a high-voltage power supply of an electrostatic spinning instrument with a metal needle, coating tin foil collecting paper on a flat plate-shaped negative electrode, aligning an injection needle tube with the center of the flat plate, keeping a working chamber of the electrostatic spinning instrument in a sealing state, keeping the temperature of the working chamber at 18 ℃, keeping the electrostatic positive voltage at 15kV, keeping the working distance at 15cm, keeping the relative humidity at 50%, keeping the rotating speed of a receiving shaft at 40m/min, and carrying out electrostatic spinning to obtain BNNS@PDA/PAA heat-conducting composite fiber felt, carrying out thermal imidization according to a program of 120 ℃/1h+200 ℃/1h+250 ℃/1h and a heating rate of 5 ℃/min in a vacuum oven, and cooling to room temperature and then taking out to obtain the BNNS@PDA/PI heat-conducting composite fiber felt;
Cutting 2g BNNS@PDA/PI heat conduction composite fiber mat into four layers with 20mm multiplied by 20mm samples which are arranged vertically in a crossing way, filling the four layers into a mould, and carrying out compression molding on a small flat vulcanizing machine to prepare the BNNS@PDA/PI composite material, wherein the compression molding temperature is 290 ℃, the compression molding pressure is 5MPa, and the compression molding time is 10min, so as to prepare the BNNS@PDA/PI composite film, and the BNNS@PDA accounts for 10% of the mass of PAA.
Example 8
Adding 1.2g of Tris solid powder into a mixed solution of 300mL of deionized water and 100mL of ethanol, and uniformly mixing; adding 2.0g of BNNS, performing ultrasonic dispersion for 10min to uniformly disperse, adding 0.8g of dopamine powder, and stirring at room temperature for 6h until the solution is grey black; standing at room temperature for 24h, removing supernatant, and drying at 60 ℃ for 12h to obtain polydopamine modified boron nitride nanosheets with the diameter of 84nm and the thickness of 10nm.
1.08g of ODA is added into a three-neck flask, 19g of DMF is added under the condition of ice water bath, 1.244g of PMDA is added in batches after the ODA is completely dissolved, 0.15g of PMDA is added in batches, after the PMDA is completely added and dissolved, 0.38g of BNNS@PDA is added after mechanical stirring for 30min, stirring is continued for 30min, and the BNNS@PDA/PAA solution is obtained through polycondensation.
BNNS@PDA/PAA solution was loaded into a 6mL syringe equipped with a metal needle, and then the syringe was horizontally fixed to the injection device in a zigzag arrangement: connecting a positive electrode joint of a high-voltage power supply of an electrostatic spinning instrument with a metal needle, coating tin foil collecting paper on a roller-shaped negative electrode, horizontally moving an injection needle tube at the center of a roller at a constant speed, keeping the working chamber of the electrostatic spinning instrument in a sealed state, keeping the temperature of the working chamber at 18 ℃, keeping the electrostatic positive voltage at 20kV, keeping the working distance at 15cm, keeping the relative humidity at 50%, keeping the rotating speed of a receiving shaft at 120m/min, carrying out electrostatic spinning to obtain BNNS@PDA/PAA heat-conducting composite fiber felt, carrying out thermal imidization according to a program of 120 ℃/1h+200 ℃/1h+250 ℃/1h and a heating rate of 5 ℃/min in a vacuum oven, and taking out after cooling to room temperature to obtain the BNNS@PDA/PI heat-conducting composite fiber felt; cutting 2g of BNNS@PDA/PI heat conduction composite fiber mat into a sample with the length of 20mm multiplied by 20mm, filling the sample into a mould, and carrying out compression molding on a small flat vulcanizing machine to prepare the BNNS@PDA/PI heat conduction insulation composite material, wherein the compression molding temperature is 320 ℃, the compression molding pressure is 10MPa, and the compression molding time is 10min, thereby preparing the BNNS@PDA/PI composite film, wherein the BNNS@PDA accounts for 10% of the PAA mass.
The tensile strength test results of the composite fiber films prepared in examples 1 to 8 of the present invention are shown in FIG. 3;
the thermal conductivity test results of the composite fiber films prepared in examples 1 to 8 of the present invention are shown in FIG. 4;
as can be seen from fig. 3 and 4, the heat conduction and mechanical properties of the PI film can be effectively improved by adopting four arrangement modes of random, directional, vertical and zigzag, wherein the optimal arrangement mode is the zigzag arrangement mode, and the heat conduction and mechanical properties of the bnns@pda/PI composite film in the zigzag (i.e. zigzag) arrangement mode are obviously improved.
As can be seen from FIG. 3, the mechanical strength of the films varies with the arrangement of the fibers. When the fibers are arranged in a zigzag manner, the mechanical strength of the film is 36.8MPa, and compared with the random arranged fiber film (7.1 MPa), the mechanical strength of the film is increased by 418.31 percent, so that the zigzag arrangement mode in the electrostatic spinning process is beneficial to improving the mechanical strength of the composite film.
As can be seen from fig. 4, the fibers have different thermal conductivity in different arrangements. When the fibers are arranged in a zigzag manner, the thermal conductivity is 0.64W/(m.K), and compared with the randomly arranged fiber film (0.21W/(m.K)), the mechanical strength is increased by 204.76%, so that the zigzag arrangement manner in the electrostatic spinning process is beneficial to improving the thermal conductivity of the composite film.
Example 9
The preparation method of the polydopamine modified boron nitride nano sheet/polyimide composite fiber heat conduction film comprises the following steps:
s1: preparing a polyamic acid solution, adding 4, 4-diaminodiphenyl ether into N, N-dimethylformamide under the ice water bath condition, stirring to completely dissolve the 4, 4-diaminodiphenyl ether, adding pyromellitic anhydride for a plurality of times, stirring to completely dissolve and react after each time of pyromellitic anhydride is added, adding the next batch of pyromellitic anhydride, adding 0.2g of pyromellitic anhydride in each batch, and continuously stirring until the polymerization reaction is complete after all the pyromellitic anhydride is added, thus obtaining the polyamic acid solution.
S2: preparing polydopamine modified boron nitride nanosheets, adding Tris solid powder into a mixed solution of deionized water and ethanol, and uniformly mixing; adding Boron Nitride Nanosheets (BNNS), performing ultrasonic dispersion, stirring to uniformly disperse the nanosheets, adding dopamine powder, and stirring at room temperature until the solution is grey black; standing at room temperature, removing supernatant, precipitating, and drying to obtain polydopamine modified boron nitride nano-sheet (BNNS@PDA), wherein the mass ratio of the boron nitride nano-sheet to the dopamine is 1.5:0.6, and the diameter of the polydopamine modified boron nitride nano-sheet is 95nm and the thickness is 15nm.
S3: adding the polydopamine modified boron nitride nano-sheet into a polyamic acid solution, and stirring to obtain a polydopamine modified boron nitride nano-sheet/polyamic acid mixed solution, wherein the mass fraction of the polydopamine modified boron nitride nano-sheet in the polydopamine modified boron nitride nano-sheet/polyamic acid mixed solution is 5%.
S4: preparing a polydopamine modified boron nitride nano sheet/polyamide acid composite fiber felt by using a polydopamine modified boron nitride nano sheet/polyamide acid mixed solution through an electrostatic spinning method; wherein the temperature of a working chamber in the electrostatic spinning process is 18 ℃, the relative humidity of the environment is 50%, the voltage of a high-voltage power supply is 15kV, the distance from a needle to the center of a roller is 15cm, the rotating speed of the roller is 40m/min, and the collecting mode of an electrostatic spinning method is Z-shaped;
s3: vacuum-treating the polydopamine modified boron nitride nano sheet/polyamide acid composite fiber felt for 4 hours under the conditions of vacuum degree of 0.08MPa and temperature of 60 ℃, and then carrying out thermal imidization treatment on the polydopamine modified boron nitride nano sheet/polyamide acid composite fiber felt subjected to vacuum treatment under the conditions of 120 ℃/1 hour, 200 ℃/1 hour and 250 ℃/1 hour, wherein the heating rate is 5 ℃/min, and taking out the polydopamine modified boron nitride nano sheet/polyimide (BNNS@PDA/PI) composite fiber felt after cooling to room temperature;
S4: cutting a polydopamine modified boron nitride nano sheet/polyimide composite fiber felt into samples with the length of 20mm multiplied by 20mm, taking three samples, filling the three samples into a die, and carrying out compression molding on a small flat vulcanizing machine to prepare the BNNS@PDA/PI composite material, wherein the compression molding temperature is 290 ℃, the compression molding pressure is 5MPa, and the compression molding time is 10min, so that the polydopamine modified boron nitride nano sheet/polyimide composite fiber heat conducting film is prepared, wherein BNNS@PDA accounts for 8.9% of the mass of PAA.
The tensile strength coefficient of the polydopamine modified boron nitride nano sheet/polyimide composite fiber heat conduction film prepared in the embodiment is 7.1Mpa, and the heat conductivity is 0.21W/(m.K).
Example 10
The preparation method of the polydopamine modified boron nitride nano sheet/polyimide composite fiber heat conduction film comprises the following steps:
s1: preparing a polyamic acid solution, adding 4, 4-diaminobiphenyl into N, N-dimethylacetamide under the ice water bath condition, stirring to completely dissolve the 4, 4-diaminobiphenyl, adding hexafluorodianhydride for a plurality of times, stirring to completely dissolve and react after each addition of the hexafluorodianhydride, adding 0.15g of the hexafluorodianhydride in the next batch after each addition of the hexafluorodianhydride, and continuously stirring until the polymerization reaction is complete after all the hexafluorodianhydride is added to obtain a polyamic acid solution.
S2: preparing polydopamine modified boron nitride nanosheets, adding Tris solid powder into a mixed solution of deionized water and ethanol, and uniformly mixing; adding Boron Nitride Nanosheets (BNNS), performing ultrasonic dispersion, stirring to uniformly disperse the nanosheets, adding dopamine powder, and stirring at room temperature until the solution is grey black; standing at room temperature, removing supernatant, precipitating, and drying to obtain polydopamine modified boron nitride nano-sheet (BNNS@PDA), wherein the mass ratio of the boron nitride nano-sheet to the dopamine is 2:0.8, and the polydopamine modified boron nitride nano-sheet has the diameter of 105nm and the thickness of 15nm.
S3: adding the polydopamine modified boron nitride nano-sheet into a polyamic acid solution, and stirring to obtain a polydopamine modified boron nitride nano-sheet/polyamic acid mixed solution, wherein the mass fraction of the polydopamine modified boron nitride nano-sheet in the polydopamine modified boron nitride nano-sheet/polyamic acid mixed solution is 15%;
s4: preparing a polydopamine modified boron nitride nano sheet/polyamide acid composite fiber felt by using a polydopamine modified boron nitride nano sheet/polyamide acid mixed solution through an electrostatic spinning method; wherein the temperature of a working chamber in the electrostatic spinning process is 20 ℃, the relative humidity of the environment is 55%, the voltage of a high-voltage power supply is 18kV, the distance from a needle to the center of a roller is 17cm, the rotating speed of the roller is 60m/min, and the collecting mode of an electrostatic spinning method is Z-shaped;
S3: vacuum-treating the polydopamine modified boron nitride nano sheet/polyamide acid composite fiber felt for 5 hours under the conditions that the vacuum degree is 0.09MPa and the temperature is 70 ℃, and then performing thermal imidization treatment on the polydopamine modified boron nitride nano sheet/polyamide acid composite fiber felt subjected to vacuum treatment under the conditions of 120 ℃/1 hour, 200 ℃/1 hour and 250 ℃/1 hour, wherein the heating rate is 5 ℃/min, and taking out the polydopamine modified boron nitride nano sheet/polyimide (BNNS@PDA/PI) composite fiber felt after cooling to room temperature;
s4: cutting a polydopamine modified boron nitride nano sheet/polyimide composite fiber felt into samples with the length of 20mm multiplied by 20mm, taking three samples, filling the three samples into a die, and carrying out compression molding on a small flat vulcanizing machine to prepare the BNNS@PDA/PI composite material, wherein the compression molding temperature is 300 ℃, the compression molding pressure is 7MPa, and the compression molding time is 13min, so that the polydopamine modified boron nitride nano sheet/polyimide composite fiber heat-conducting film is prepared, wherein BNNS@PDA accounts for 7.6% of the mass of PAA.
The tensile strength coefficient of the polydopamine modified boron nitride nano sheet/polyimide composite fiber heat conduction film prepared in the embodiment is 15.5Mpa, and the heat conductivity is 0.31W/(m.K).
Example 11
The preparation method of the polydopamine modified boron nitride nano sheet/polyimide composite fiber heat conduction film comprises the following steps:
S1: and (3) preparing a polyamic acid solution, namely adding p-phenylenediamine into N-methylpyrrolidone under ice water bath conditions, stirring to completely dissolve the p-phenylenediamine, adding 3,3', 4' -benzophenone tetracarboxylic dianhydride for a plurality of times, stirring to dissolve and react completely after adding 3,3', 4' -benzophenone tetracarboxylic dianhydride for each time, adding the next batch of 3,3', 4' -benzophenone tetracarboxylic dianhydride, wherein the total amount of 3,3', 4' -benzophenone tetracarboxylic dianhydride added for each batch is 0.15g, and continuously stirring until the polymerization reaction is complete after all 3,3', 4' -benzophenone tetracarboxylic dianhydride is added to obtain a polyamic acid solution.
S2: preparing polydopamine modified boron nitride nanosheets, adding Tris solid powder into a mixed solution of deionized water and ethanol, and uniformly mixing; adding Boron Nitride Nanosheets (BNNS), performing ultrasonic dispersion, stirring to uniformly disperse the nanosheets, adding dopamine powder, and stirring at room temperature until the solution is grey black; standing at room temperature, removing supernatant, precipitating, and drying to obtain polydopamine modified boron nitride nano-sheet (BNNS@PDA), wherein the mass ratio of the boron nitride nano-sheet to the dopamine is 2.5:1), and the polydopamine modified boron nitride nano-sheet has the diameter of 115nm and the thickness of 18nm.
S3: adding the polydopamine modified boron nitride nano-sheet into a polyamic acid solution, and stirring to obtain a polydopamine modified boron nitride nano-sheet/polyamic acid mixed solution, wherein the mass fraction of the polydopamine modified boron nitride nano-sheet in the polydopamine modified boron nitride nano-sheet/polyamic acid mixed solution is 30%;
s4: preparing a polydopamine modified boron nitride nano sheet/polyamide acid composite fiber felt by using a polydopamine modified boron nitride nano sheet/polyamide acid mixed solution through an electrostatic spinning method; wherein the temperature of a working chamber in the electrostatic spinning process is 25 ℃, the relative humidity of the environment is 60%, the voltage of a high-voltage power supply is 20kV, the distance from a needle to the center of a roller is 20cm, the rotating speed of the roller is 100m/min, and the collecting mode of an electrostatic spinning method is Z-shaped;
s3: vacuum-treating the polydopamine modified boron nitride nano sheet/polyamide acid composite fiber felt for 6 hours under the conditions that the vacuum degree is 0.1MPa and the temperature is 80 ℃, and then performing thermal imidization treatment on the polydopamine modified boron nitride nano sheet/polyamide acid composite fiber felt subjected to vacuum treatment under the conditions of 120 ℃/1 hour, 200 ℃/1 hour and 250 ℃/1 hour, wherein the heating rate is 5 ℃/min, and taking out the polydopamine modified boron nitride nano sheet/polyimide (BNNS@PDA/PI) composite fiber felt after cooling to room temperature;
S4: cutting a polydopamine modified boron nitride nano sheet/polyimide composite fiber felt into samples with the length of 20mm multiplied by 20mm, taking three samples, filling the three samples into a die, and carrying out compression molding on a small flat vulcanizing machine to prepare the BNNS@PDA/PI composite material, wherein the compression molding temperature is 310 ℃, the compression molding pressure is 9MPa, and the compression molding time is 15min, so that the polydopamine modified boron nitride nano sheet/polyimide composite fiber heat-conducting film is prepared, wherein BNNS@PDA accounts for 6% of the mass of PAA.
The tensile strength coefficient of the polydopamine modified boron nitride nano sheet/polyimide composite fiber heat conduction film prepared in the embodiment is 27.5Mpa, and the heat conductivity is 0.45W/(m.K).
Example 12
The preparation method of the polydopamine modified boron nitride nano sheet/polyimide composite fiber heat conduction film comprises the following steps:
s1: and (3) preparing a polyamic acid solution, adding 4, 4-diaminodiphenyl ether and 4, 4-diaminobiphenyl into a mixed solution of N-methylpyrrolidone and dimethyl sulfoxide under the ice water bath condition, stirring to completely dissolve the 4, 4-diaminodiphenyl ether and the 4, 4-diaminobiphenyl, adding the hexafluorodianhydride for a plurality of times, stirring to completely dissolve and react after each addition of the hexafluorodianhydride, adding the next batch of the hexafluorodianhydride, wherein the added amount of the hexafluorodianhydride in each batch is 0.15g, and continuously stirring until the polymerization reaction is complete after all the hexafluorodianhydride is added to obtain a polyamic acid solution.
S2: preparing polydopamine modified boron nitride nanosheets, adding Tris solid powder into a mixed solution of deionized water and ethanol, and uniformly mixing; adding Boron Nitride Nanosheets (BNNS), performing ultrasonic dispersion, stirring to uniformly disperse the nanosheets, adding dopamine powder, and stirring at room temperature until the solution is grey black; standing at room temperature, removing supernatant, precipitating, and drying to obtain polydopamine modified boron nitride nano-sheet (BNNS@PDA), wherein the mass ratio of the boron nitride nano-sheet to the dopamine is 2.2:0.7, and the polydopamine modified boron nitride nano-sheet has the diameter of 120nm and the thickness of 20nm.
S3: adding the polydopamine modified boron nitride nano-sheet into a polyamic acid solution, and stirring to obtain a polydopamine modified boron nitride nano-sheet/polyamic acid mixed solution, wherein the mass fraction of the polydopamine modified boron nitride nano-sheet in the polydopamine modified boron nitride nano-sheet/polyamic acid mixed solution is 20%;
s4: preparing a polydopamine modified boron nitride nano sheet/polyamide acid composite fiber felt by using a polydopamine modified boron nitride nano sheet/polyamide acid mixed solution through an electrostatic spinning method; wherein the temperature of a working chamber in the electrostatic spinning process is 25 ℃, the relative humidity of the environment is 60%, the voltage of a high-voltage power supply is 25kV, the distance from a needle to the center of a roller is 20cm, the rotating speed of the roller is 120m/min, and the collecting mode of an electrostatic spinning method is Z-shaped;
S3: vacuum-treating the polydopamine modified boron nitride nano sheet/polyamide acid composite fiber felt for 6 hours under the conditions that the vacuum degree is 0.1MPa and the temperature is 80 ℃, and then performing thermal imidization treatment on the polydopamine modified boron nitride nano sheet/polyamide acid composite fiber felt subjected to vacuum treatment under the conditions of 120 ℃/1 hour, 200 ℃/1 hour and 250 ℃/1 hour, wherein the heating rate is 5 ℃/min, and taking out the polydopamine modified boron nitride nano sheet/polyimide (BNNS@PDA/PI) composite fiber felt after cooling to room temperature;
s4: cutting a polydopamine modified boron nitride nano sheet/polyimide composite fiber felt into samples with the length of 20mm multiplied by 20mm, taking three samples, filling the three samples into a die, and carrying out compression molding on a small flat vulcanizing machine to prepare the BNNS@PDA/PI composite material, wherein the compression molding temperature is 320 ℃, the compression molding pressure is 10MPa, and the compression molding time is 15min, so that the polydopamine modified boron nitride nano sheet/polyimide composite fiber heat-conducting film is prepared, wherein BNNS@PDA accounts for 5.5% of the mass of PAA.
The tensile strength coefficient of the polydopamine modified boron nitride nano sheet/polyimide composite fiber heat conduction film prepared in the embodiment is 37.1Mpa, and the heat conductivity is 0.65W/(m.K).
The invention also protects the application of the polyimide film prepared by the method in the field of electronic packaging, the film has good mechanical property, insulating property and high temperature resistance, the service life of the film is effectively prolonged, and the use reliability of devices and equipment is ensured.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the polydopamine modified boron nitride nano sheet/polyimide composite fiber heat conduction film is characterized by comprising the following steps of:
s1: adding the polydopamine modified boron nitride nano-sheet into a polyamic acid solution, and stirring to obtain a polydopamine modified boron nitride nano-sheet/polyamic acid mixed solution;
s2: preparing a polydopamine modified boron nitride nano sheet/polyamide acid composite fiber felt by using the polydopamine modified boron nitride nano sheet/polyamide acid mixed solution through an electrostatic spinning method; the collecting mode in the electrostatic spinning process is Z-shaped;
S3: carrying out thermal imidization treatment on the polydopamine modified boron nitride nano-sheet/polyamide acid composite fiber felt to obtain polydopamine modified boron nitride nano-sheet/polyimide composite fiber felt;
s4: and carrying out compression molding on a plurality of layers of the polydopamine modified boron nitride nano-sheet/polyimide composite fiber felt to obtain the polydopamine modified boron nitride nano-sheet/polyimide composite fiber heat conducting film.
2. The method for preparing the polydopamine modified boron nitride nano sheet/polyimide composite fiber heat conducting film according to claim 1, which is characterized in that the preparation process of the polyamic acid solution is as follows: under the ice water bath condition, adding diamine monomer into polar aprotic solvent, stirring to dissolve diamine monomer completely, adding dianhydride monomer, and continuously stirring until polymerization reaction is complete to obtain polyamic acid solution.
3. The method for preparing the polydopamine modified boron nitride nano sheet/polyimide composite fiber heat conduction film according to claim 2, which is characterized in that the diamine monomer is one or a mixture of more of 4, 4-diaminodiphenyl ether, 4-diaminobiphenyl and p-phenylenediamine in any proportion; the dianhydride monomer is one or a mixture of more of pyromellitic anhydride, hexafluorodianhydride and 3,3', 4' -benzophenone tetracarboxylic dianhydride in any proportion.
4. The method for preparing the polydopamine modified boron nitride nano sheet/polyimide composite fiber heat conducting film according to claim 2, wherein the polar aprotic solvent is one or a mixture of more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide in any proportion.
5. The method for preparing the polydopamine modified boron nitride nano sheet/polyimide composite fiber heat conducting film according to claim 2, wherein dianhydride monomer is added in a plurality of batches, after each dianhydride monomer is added, the dianhydride monomer is stirred to be dissolved and completely reacted, and then the dianhydride monomer in the next batch is added.
6. The method for preparing the polydopamine modified boron nitride nano sheet/polyimide composite fiber heat conducting film according to claim 1, which is characterized in that in the electrostatic spinning method, the voltage is 15 kV-25 kV.
7. The method for preparing the polydopamine modified boron nitride nano-sheet/polyimide composite fiber heat conduction film according to claim 1, which is characterized in that before the polydopamine modified boron nitride nano-sheet/polyamide acid composite fiber felt is subjected to thermal imidization treatment, the polydopamine modified boron nitride nano-sheet/polyamide acid composite fiber felt is subjected to vacuum treatment; the conditions of the vacuum treatment are as follows: vacuum degree is 0.08-0.1 MPa, temperature is 60-80 ℃ and time is 4-6 h.
8. The method for preparing the polydopamine modified boron nitride nano sheet/polyimide composite fiber heat conducting film according to claim 1, which is characterized in that the temperature of compression molding is 290-320 ℃, the pressure is 5-10 MPa, and the time is 10-15 min.
9. A polydopamine modified boron nitride nanosheet/polyimide composite fiber heat conducting film, characterized in that the film is prepared by the method of any one of claims 1-8; the tensile strength coefficient of the polydopamine modified boron nitride nano sheet/polyimide composite fiber heat conduction film is 7.1-36.8 Mpa, and the heat conductivity is 0.21-0.64W/(m.K).
10. Use of the polydopamine modified boron nitride nano-sheet/polyimide composite fiber heat conducting film prepared by the method of any one of claims 1-8 in the field of electronic packaging.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211718146.0A CN116061525A (en) | 2022-12-29 | 2022-12-29 | Polydopamine modified boron nitride nano-sheet/polyimide composite fiber heat conduction film and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211718146.0A CN116061525A (en) | 2022-12-29 | 2022-12-29 | Polydopamine modified boron nitride nano-sheet/polyimide composite fiber heat conduction film and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116061525A true CN116061525A (en) | 2023-05-05 |
Family
ID=86176156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211718146.0A Pending CN116061525A (en) | 2022-12-29 | 2022-12-29 | Polydopamine modified boron nitride nano-sheet/polyimide composite fiber heat conduction film and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116061525A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118241379A (en) * | 2024-05-27 | 2024-06-25 | 深圳市首航新能源股份有限公司 | Preparation method of composite film, composite film and application of composite film |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328618A (en) * | 2007-06-18 | 2008-12-24 | 中国科学院理化技术研究所 | Electrostatic spinning machine with special reticulate pattern electrode and application method thereof |
| CN103802411A (en) * | 2014-02-19 | 2014-05-21 | 苏州大学 | Electrospun aramid 1313 nanofiber/polylactic acid composite material and preparation method for same |
| CN104358029A (en) * | 2014-10-17 | 2015-02-18 | 华中科技大学 | Method and device for preparing micro-nano corrugated structure by electrostatic spinning |
| CN105040123A (en) * | 2015-09-11 | 2015-11-11 | 中国人民解放军军事医学科学院卫生装备研究所 | Method for preparing aqueous polyurethane fibers via static spinning |
| CN105803542A (en) * | 2016-04-19 | 2016-07-27 | 上海科涤环保科技有限公司 | Reciprocating type continuous roller receiving device capable of being used for electrostatic spinning |
| CN110228248A (en) * | 2019-05-10 | 2019-09-13 | 上海交通大学 | A kind of high thermal conductivity anisotropic polymer based composites and preparation method thereof |
| CN211570844U (en) * | 2019-12-25 | 2020-09-25 | 北京化工大学 | Sawtooth type electrostatic spinning device capable of periodically changing electric field |
| CN112026175A (en) * | 2020-09-09 | 2020-12-04 | 厦门理工学院 | Light source heating assembly capable of being used for micro-nano three-dimensional structure forming and preparation device |
| CN112746339A (en) * | 2020-12-04 | 2021-05-04 | 浙江农林大学暨阳学院 | Low-filtration-resistance fiber membrane electrospinning device and preparation method thereof |
| CN114583386A (en) * | 2022-03-22 | 2022-06-03 | 中国石油大学(华东) | Lithium-sulfur battery composite integrated diaphragm, preparation method thereof and lithium-sulfur battery |
| CN114750491A (en) * | 2022-05-24 | 2022-07-15 | 陕西科技大学 | Polydopamine modified boron nitride nanosheet/polyimide heat-conducting and insulating composite film and preparation method and application thereof |
| US20220257371A1 (en) * | 2019-04-18 | 2022-08-18 | Dietmar Hutmacher | Mew tissue scaffold |
-
2022
- 2022-12-29 CN CN202211718146.0A patent/CN116061525A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328618A (en) * | 2007-06-18 | 2008-12-24 | 中国科学院理化技术研究所 | Electrostatic spinning machine with special reticulate pattern electrode and application method thereof |
| CN103802411A (en) * | 2014-02-19 | 2014-05-21 | 苏州大学 | Electrospun aramid 1313 nanofiber/polylactic acid composite material and preparation method for same |
| CN104358029A (en) * | 2014-10-17 | 2015-02-18 | 华中科技大学 | Method and device for preparing micro-nano corrugated structure by electrostatic spinning |
| CN105040123A (en) * | 2015-09-11 | 2015-11-11 | 中国人民解放军军事医学科学院卫生装备研究所 | Method for preparing aqueous polyurethane fibers via static spinning |
| CN105803542A (en) * | 2016-04-19 | 2016-07-27 | 上海科涤环保科技有限公司 | Reciprocating type continuous roller receiving device capable of being used for electrostatic spinning |
| US20220257371A1 (en) * | 2019-04-18 | 2022-08-18 | Dietmar Hutmacher | Mew tissue scaffold |
| CN110228248A (en) * | 2019-05-10 | 2019-09-13 | 上海交通大学 | A kind of high thermal conductivity anisotropic polymer based composites and preparation method thereof |
| CN211570844U (en) * | 2019-12-25 | 2020-09-25 | 北京化工大学 | Sawtooth type electrostatic spinning device capable of periodically changing electric field |
| CN112026175A (en) * | 2020-09-09 | 2020-12-04 | 厦门理工学院 | Light source heating assembly capable of being used for micro-nano three-dimensional structure forming and preparation device |
| CN112746339A (en) * | 2020-12-04 | 2021-05-04 | 浙江农林大学暨阳学院 | Low-filtration-resistance fiber membrane electrospinning device and preparation method thereof |
| CN114583386A (en) * | 2022-03-22 | 2022-06-03 | 中国石油大学(华东) | Lithium-sulfur battery composite integrated diaphragm, preparation method thereof and lithium-sulfur battery |
| CN114750491A (en) * | 2022-05-24 | 2022-07-15 | 陕西科技大学 | Polydopamine modified boron nitride nanosheet/polyimide heat-conducting and insulating composite film and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 巩桂芬;卜程程;段宏伟: "聚酰胺酸质量分数对聚酰亚胺纤维直径的影响", 哈尔滨商业大学学报(自然科学版), no. 005, 31 December 2012 (2012-12-31), pages 601 - 605 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118241379A (en) * | 2024-05-27 | 2024-06-25 | 深圳市首航新能源股份有限公司 | Preparation method of composite film, composite film and application of composite film |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | High permittivity nanocomposites fabricated from electrospun polyimide/BaTiO3 hybrid nanofibers | |
| CN102911360B (en) | Graphene modified polyimide-based composite and preparation method thereof | |
| CN111546722B (en) | Reinforced high-thermal-conductivity mica tape and preparation method thereof | |
| CN114854087B (en) | Polyimide composite material with double heat-conducting networks and preparation method thereof | |
| Zhou et al. | Fabrication, thermal, and dielectric properties of self-passivated Al/epoxy nanocomposites | |
| KR101503332B1 (en) | Polyimide film and preparation method thereof | |
| CN114750491A (en) | Polydopamine modified boron nitride nanosheet/polyimide heat-conducting and insulating composite film and preparation method and application thereof | |
| Yang et al. | Flexible h-BN/fluorinated poly (arylene ether nitrile) fibrous composite film with low dielectric constant and high thermal conductivity fabricated via coaxial electrospinning hot-pressing technique | |
| CN111155239B (en) | Preparation method of electrostatic spinning polyimide/MXene electromagnetic shielding film | |
| CN104961893A (en) | High-dielectric-constant polyimide and preparation method thereof | |
| Jin et al. | Enhancing high-frequency dielectric and mechanical properties of SiO2/PTFE composites from the interface fluorination | |
| CN116061525A (en) | Polydopamine modified boron nitride nano-sheet/polyimide composite fiber heat conduction film and preparation method and application thereof | |
| Zhang et al. | β-Cyclodextrin toughened polyimide composites toward all-organic dielectric materials | |
| CN101955667A (en) | Heat-resisting high-dielectric constant inorganic/polymer composite film | |
| Li et al. | Improved properties of PTFE composites filled with glass fiber modified by sol–gel method | |
| Tang et al. | High-temperature-resistant barium strontium titanate@ Ag/poly (arylene ether nitrile) composites with enhanced dielectric performance and high mechanical strength | |
| Chen et al. | Aramid-based electric heating films by incorporating carbon black | |
| Fang et al. | NH 2-functionalized carbon-coated Fe 3 O 4 core–shell nanoparticles for in situ preparation of robust polyimide composite films with high dielectric constant, low dielectric loss, and high breakdown strength | |
| Mao et al. | Preparation and characterization of PI/PVDF composite films with excellent dielectric property | |
| Ma et al. | High performance polyimide films containing benzimidazole moieties for thin film solar cells | |
| CN117987957A (en) | High-heat-conductivity high-insulation polyimide film and preparation method thereof | |
| Yang et al. | Remarkably enhanced dielectric properties in PVDF composites via engineering core@ shell structured ZnO@ PS nanoparticles | |
| Itenyo et al. | Modification of epoxy resin with reactive end-capped carboxylic imide oligomer for manufacture of glass-fiber reinforced composite | |
| CN117107516A (en) | Gamma-aminopropyl triethoxy silane modified silver nanowire/polyimide composite fiber heat conduction film and preparation method and application thereof | |
| CN108221460A (en) | A kind of preparation method of transparent hydrophilic aramid fiber precipitating film |
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 |