CN114808183A - Electrostatic spinning ink, high-thermal-conductivity fiber membrane and preparation method thereof - Google Patents
Electrostatic spinning ink, high-thermal-conductivity fiber membrane and preparation method thereof Download PDFInfo
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- CN114808183A CN114808183A CN202210238367.1A CN202210238367A CN114808183A CN 114808183 A CN114808183 A CN 114808183A CN 202210238367 A CN202210238367 A CN 202210238367A CN 114808183 A CN114808183 A CN 114808183A
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- 238000010041 electrostatic spinning Methods 0.000 title claims abstract description 94
- 239000000835 fiber Substances 0.000 title claims abstract description 65
- 239000012528 membrane Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 102
- 239000011347 resin Substances 0.000 claims abstract description 102
- 239000000945 filler Substances 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 239000003381 stabilizer Substances 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims description 78
- 239000007788 liquid Substances 0.000 claims description 58
- 238000002156 mixing Methods 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 30
- -1 glycidyl ester Chemical class 0.000 claims description 17
- 238000009987 spinning Methods 0.000 claims description 17
- 239000000725 suspension Substances 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000004321 preservation Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 8
- 238000007731 hot pressing Methods 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 229920002635 polyurethane Polymers 0.000 claims description 8
- 239000004814 polyurethane Substances 0.000 claims description 8
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 229920000647 polyepoxide Polymers 0.000 claims description 7
- 238000001523 electrospinning Methods 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 3
- 239000004697 Polyetherimide Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 229920000180 alkyd Polymers 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000004494 ethyl ester group Chemical group 0.000 claims description 3
- 239000004845 glycidylamine epoxy resin Substances 0.000 claims description 3
- 239000002113 nanodiamond Substances 0.000 claims description 3
- 229920005646 polycarboxylate Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920001601 polyetherimide Polymers 0.000 claims description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 2
- 239000011231 conductive filler Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 241000207199 Citrus Species 0.000 claims 1
- 235000020971 citrus fruits Nutrition 0.000 claims 1
- 208000012886 Vertigo Diseases 0.000 description 15
- 235000021355 Stearic acid Nutrition 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 10
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 10
- 239000008117 stearic acid Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 5
- 230000005684 electric field Effects 0.000 description 4
- 229920005749 polyurethane resin Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002520 smart material Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000005686 electrostatic field Effects 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- 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
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses electrostatic spinning ink, a high-thermal-conductivity fiber membrane and a preparation method thereof, wherein the electrostatic spinning ink comprises the following raw materials in parts by weight: 50-80 parts of main resin, 5-8 parts of heat-conducting filler, 65-80 parts of solvent, 5-8 parts of toughening resin, 10-15 parts of dispersant and 1-2 parts of stabilizer; the electrostatic spinning ink is subjected to electrostatic spinning and curing to obtain a high-thermal-conductivity fiber membrane; the high-thermal-conductivity fiber film prepared by the invention has the characteristics of low dielectric constant and high thermal conductivity, and when the temperature rises, the dielectric constant slightly changes and the dielectric loss is in a consistent acceptable range.
Description
Technical Field
The invention relates to the technical field of fiber membranes, in particular to an electrostatic spinning ink and high-thermal-conductivity fiber membrane and a preparation method thereof.
Background
Electrostatic spinning is a special fiber manufacturing process, polymer solution or melt is subjected to jet spinning in a strong electric field, under the action of the electric field, liquid drops at a needle head change from a spherical shape to a conical shape, and fiber filaments are obtained by extending from the tip of the conical shape. Polymer filaments of nanometer diameter can be produced by an electrospinning process.
The 5G communication adopts a millimeter wave band, and has the greatest advantages of high propagation speed and the following greatest disadvantages of poor penetration and high attenuation. Therefore, 5G requires that the dielectric constant and dielectric loss of the propagation medium material be small and stable over a wide frequency range. However, the current low dielectric constant materials generally have the following disadvantages: 1. the dielectric constant is large, usually above 2; 2. the weather resistance is poor; 3. the process is complicated. 4. It does not have high thermal conductivity, and when the temperature rises, the dielectric constant and the dielectric loss become large.
Dielectric constant: the main parameter reflecting the dielectric or polarization properties of piezoelectric smart material dielectrics under the action of an electrostatic field is usually denoted by epsilon. Piezoelectric elements for different purposes have different requirements on the dielectric constant of piezoelectric intelligent materials. When the shape and the size of the piezoelectric smart material are fixed, the dielectric constant c is determined by measuring the inherent capacitance CP of the piezoelectric smart material.
Dielectric loss: this refers to a phenomenon in which the dielectric itself generates heat due to partial consumption of electric energy in the alternating electric field. The reason is that the dielectric medium contains carriers capable of conducting electricity, and under the action of an external electric field, conductive current is generated, a part of electric energy is consumed, and the electric energy is converted into heat energy. One of the indexes for indicating the quality of an insulating material (e.g., insulating oil)
Therefore, the electrostatic spinning ink, the high-thermal-conductivity fiber membrane and the preparation method thereof have wide market prospects.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the electrostatic spinning ink, the high-thermal-conductivity fiber film and the preparation method thereof, and the prepared fiber film has low dielectric constant and high thermal conductivity, and the dielectric constant slightly changes and the dielectric loss is in a consistent acceptable range when the temperature is increased.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the electrostatic spinning ink comprises the following raw materials in parts by weight:
50-80 parts of main resin, 5-8 parts of heat-conducting filler, 65-80 parts of solvent, 5-8 parts of toughening resin, 10-15 parts of dispersant and 1-2 parts of stabilizer.
Further, the main resin is selected from any one or more of polyester polyurethane, acrylic polyurethane, alkyd polyurethane, polyether polyurethane, glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin and bisphenol A epoxy resin;
further, the heat conducting filler is selected from any one or more of nano diamond, carbide (silicon carbide), ferroelectric ceramic, metal oxide (aluminum oxide and magnesium oxide) and boron nitride;
further, the dispersant is selected from any one or more of polycarboxylate, poly (meth) acrylic acid derivative, maleic anhydride copolymer and polyoxyethylene alkylphenol ether;
further, the toughening resin is selected from any one or more of polysulfone resin, polyether sulfone resin, polyether imide resin and polyether ketone resin;
further, the solvent is selected from any one or more of dimethylformamide, dimethylacetamide, ethyl ester, butanone and toluene;
further, the stabilizer comprises pentaerythritol ester and stearic acid, specifically 0.8-1.5 parts of pentaerythritol ester and 0.2-0.5 part of stearic acid.
Similarly, the invention also provides a high-thermal-conductivity fiber membrane obtained by carrying out electrostatic spinning treatment and curing treatment on the electrostatic spinning ink.
The preparation method of the high-thermal-conductivity fiber membrane comprises the following steps
S1, preparation of electrostatic spinning ink
S11, mixing the main resin with a part of solvent, and stirring and dispersing for 2-8 hours at the temperature of 60-80 ℃ to obtain a main resin dispersion liquid;
s12, mixing the toughening resin with a part of solvent, and stirring and dispersing for 0.5-4h at 70-90 ℃ to obtain a toughening resin dispersion liquid;
s13, mixing the heat-conducting filler with the rest solvent, and stirring and dispersing for 0.5-2h to obtain a heat-conducting filler suspension;
s14, mixing the main resin dispersion liquid obtained in the step S11 with the toughening resin dispersion liquid obtained in the step S12, and stirring and dispersing for 0.5-1h to obtain a mixed resin dispersion liquid;
s15, mixing the mixed resin dispersion liquid obtained in the step S14 with the heat-conducting filler suspension liquid obtained in the step S13, adding a dispersing agent and a stabilizing agent, and stirring and dispersing for 1-2 hours to obtain electrostatic spinning ink;
s2. electrostatic spinning
Carrying out electrostatic spinning on the electrostatic spinning ink solution by adopting electrostatic spinning equipment to obtain an electrostatic spinning fiber film;
s3, curing
And taking down the spun electrostatic spinning fiber film, cutting, hot-pressing at 80-130 ℃ under the pressure of 15-40PSI for 15-30min, carrying out temperature programming and heat preservation on the hot-pressed fiber film, and cooling to room temperature to obtain the high-thermal-conductivity fiber film.
Further, in the electrostatic spinning process in step S2, the process parameters are as follows: the air humidity is 30-80%, the advancing speed of the injection pump is 0.2-3ml/h, the spinning pillow is a flat needle head with 0.1-1mm, the high-voltage direct-current power supply is 5-22KV, the distance between the spinning needle head and the roller is 5-20cm, and the rotating speed of the roller is 100-.
Further, the programmed temperature raising and heat preservation process of the step S3 is to raise the temperature from room temperature to 120-180 ℃ within 30-60 min; preserving the heat for 30-60min at the temperature of 120-; heating to 180 ℃ at the temperature of 120-350 ℃ within 30-60 min; keeping the temperature at 350 ℃ for 30-60min at 250-.
In the electrostatic spinning process, the main resin is a film forming substance with low dielectric constant performance, is crosslinked through a polymer chain, extruded and drawn into filaments in an electrostatic field to form fibers, and is stacked to form a film;
the heat-conducting filler provides high heat-conducting property and low dielectric property, can reduce the dielectric constant, stabilize the temperature of the fiber film and keep the stability of the dielectric constant;
the solvent is a diluent, is used for uniformly dispersing the main resin, the toughening resin, the heat-conducting filler and the dispersing agent, and simultaneously adjusts the ink to proper viscosity, thereby being beneficial to pushing out the ink during electrostatic spinning and adjusting the thickness of the cellosilk;
the toughening resin and the main resin are mutually crosslinked, so that the toughness of the fiber yarns and the strength of the fiber film after film forming are improved;
the curing agent is a film-forming assistant, which can crosslink the polymer chains of the resin or accelerate the crosslinking of the polymer chains of the resin, so that the invention has better physical properties, such as: toughness, tensile strength, water resistance, weather resistance, and the like;
the active group at one end of the macromolecular chain of the dispersant coats the heat-conducting filler, and the other end of the macromolecular chain is wound with the resin, so that the heat-conducting filler is uniformly dispersed in the resin dispersion liquid, and the storage stability is improved.
The stabilizer uses pentaerythritol ester and stearic acid, wherein the pentaerythritol ester has a relatively higher melting point than the main resin, contains a large amount of active carbonyl groups, can be connected to the molecular chain of the main resin to inhibit the degradation of the main resin, and the stearic acid is added to help prevent the coking in the curing process.
The invention has the beneficial effects that:
the fiber film prepared by the invention has lower dielectric constant, higher heat conductivity coefficient and low dielectric loss at room temperature; at 110-120 deg.C, the thermal conductivity is slightly increased, the dielectric constant is also slightly increased, and the dielectric loss can be controlled at 10 -1 Below, within acceptable ranges.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
The electrostatic spinning ink comprises the following raw materials in parts by weight:
70 parts of polyester polyurethane resin
6 parts of nano diamond
Dimethylformamide 70 parts
6 parts of polysulfone orange ester resin
Polycarboxylate (BASF)0.14 part
Pentaerythritol ester 1 part and stearic acid 0.4 part
The preparation method of the high-thermal-conductivity fiber membrane comprises the following steps
S1, preparation of electrostatic spinning ink
S11, mixing main resin and part of solvent in a reaction bottle, and stirring and dispersing at 70 ℃ at a dispersion speed of 800rpm for 5 hours to obtain main resin dispersion liquid;
s12, mixing the toughening resin with part of the solvent in a reaction bottle, and stirring and dispersing at the dispersion speed of 800rpm for 2 hours at the temperature of 80 ℃ to obtain a toughening resin dispersion liquid;
s13, mixing the heat-conducting filler with the rest solvent in a reaction bottle, and stirring and dispersing for 1h at a dispersion speed of 8rpm to obtain a heat-conducting filler suspension;
s14, mixing the main resin dispersion liquid obtained in the step S11 with the toughening resin dispersion liquid obtained in the step S12, stirring and dispersing for 0.7h at a dispersion speed of 1500rpm to obtain a mixed resin dispersion liquid;
s15, mixing the mixed resin dispersion liquid obtained in the step S14 with the heat-conducting filler suspension liquid obtained in the step S13, adding a dispersing agent and a stabilizing agent, stirring and dispersing for 1.5 hours at a dispersion speed of 2000rpm, and obtaining electrostatic spinning ink;
s2. electrostatic spinning
Carrying out electrostatic spinning on the electrostatic spinning ink solution by adopting electrostatic spinning equipment to obtain an electrostatic spinning fiber film; the electrostatic spinning process comprises the following process parameters: the air humidity is 50%, the advancing speed of the injection pump is 1.5ml/h, the spinning pillow is a flat needle head with the diameter of 0.5mm, the high-voltage direct-current power supply is 20KV, the distance between the spinning needle head and the roller is 10-12cm, and the rotating speed of the roller is 900 rpm.
S3, curing
And taking down the spun electrostatic spinning fiber film, cutting, hot-pressing at 90-95 ℃ under the pressure of 25PSI for 20min, carrying out temperature programming and heat preservation on the hot-pressed fiber film, and cooling to room temperature to obtain the high-thermal-conductivity fiber film. The temperature programming and heat preservation process is that the temperature is raised from room temperature to 150 ℃ within 40 min; keeping the temperature at 150 ℃ for 50 min; heating to 300 deg.C at 150 deg.C within 40 min; keeping the temperature at 300 ℃ for 50 min.
Example 2
The electrostatic spinning ink comprises the following raw materials in parts by weight:
50 parts of acrylic polyurethane resin
5 parts of silicon carbide
Dimethylacetamide 65 parts
Polyether sulfone resin 5 parts
10 parts of poly (meth) acrylic acid derivative
0.8 part of pentaerythritol ester and 0.2 part of stearic acid
The preparation method of the high-thermal-conductivity fiber membrane comprises the following steps
S1, preparation of electrostatic spinning ink
S11, mixing main resin and partial solvent in a reaction bottle, and stirring and dispersing at a dispersion speed of 400pm at 60 ℃ for 2h to obtain main resin dispersion liquid;
s12, mixing the toughening resin with part of the solvent in a reaction bottle, and stirring and dispersing at 70 ℃ and a dispersion speed of 400rpm for 0.5h to obtain a toughening resin dispersion liquid;
s13, mixing the heat-conducting filler with the rest solvent in a reaction bottle, stirring and dispersing for 0.5h at a dispersion speed of 400rpm to obtain a heat-conducting filler suspension;
s14, mixing the main resin dispersion liquid obtained in the step S11 and the toughening resin dispersion liquid obtained in the step S12, stirring and dispersing for 0.5h at a dispersion speed of 1000rpm to obtain a mixed resin dispersion liquid;
s15, mixing the mixed resin dispersion liquid obtained in the step S14 with the heat-conducting filler suspension liquid obtained in the step S13, adding a dispersing agent and a stabilizing agent, stirring and dispersing for 1 hour at the dispersion speed of 1000rpm, and obtaining the electrostatic spinning ink;
s2. electrostatic spinning
Carrying out electrostatic spinning on the electrostatic spinning ink solution by adopting electrostatic spinning equipment to obtain an electrostatic spinning fiber film; the electrostatic spinning process comprises the following process parameters: the air humidity is 30%, the propelling speed of the injection pump is 0.2ml/h, the spinning pillow is a flat needle head with the diameter of 0.1mm, the high-voltage direct-current power supply is 5KV, the distance between the spinning needle head and the roller is 5cm, and the rotating speed of the roller is 100 rpm.
S3, curing
And taking down the spun electrostatic spinning fiber film, cutting, hot-pressing for 15min at 80 ℃ under the pressure of 15PSI, carrying out temperature programming and heat preservation on the hot-pressed fiber film, and cooling to room temperature to obtain the high-thermal-conductivity fiber film. The temperature programming and heat preservation process is that the temperature is raised from room temperature to 120 ℃ within 300 min; keeping the temperature at 120 ℃ for 30 min; heating to 250 deg.C at 120 deg.C within 30-60 min; keeping the temperature at 250 ℃ for 30 min.
Example 3
The electrostatic spinning ink comprises the following raw materials in parts by weight:
80 parts of alkyd polyurethane resin
8 parts of ferroelectric ceramic
80 portions of ethyl ester
8 parts of polyetherimide resin
Maleic anhydride copolymer 15 parts
Pentaerythritol ester 1.5 parts and stearic acid 0.5 part
The preparation method of the high-thermal-conductivity fiber membrane comprises the following steps
S1, preparation of electrostatic spinning ink
S11, mixing main resin and part of solvent in a reaction bottle, and stirring and dispersing at 80 ℃ and a dispersion speed of 1000rpm for 8 hours to obtain main resin dispersion liquid;
s12, mixing the toughening resin with a part of solvent, and stirring and dispersing for 4 hours at 90 ℃ at a dispersion speed of 1000rpm to obtain a toughening resin dispersion liquid;
s13, mixing the heat-conducting filler with the rest solvent, stirring and dispersing for 2 hours at a dispersion speed of 1000rpm to obtain a heat-conducting filler suspension;
s14, mixing the main resin dispersion liquid obtained in the step S11 and the toughening resin dispersion liquid obtained in the step S12, stirring and dispersing for 1 hour at a dispersion speed of 2000rpm to obtain a mixed resin dispersion liquid;
s15, mixing the mixed resin dispersion liquid obtained in the step S14 with the heat-conducting filler suspension liquid obtained in the step S13, adding a dispersing agent and a stabilizing agent, stirring and dispersing for 2 hours at a dispersion speed of 3000rpm, and obtaining the electrostatic spinning ink;
s2. electrostatic spinning
Carrying out electrostatic spinning on the electrostatic spinning ink solution by adopting electrostatic spinning equipment to obtain an electrostatic spinning fiber film; the electrostatic spinning process comprises the following process parameters: the air humidity is 80%, the propelling speed of the injection pump is 3ml/h, the spinning pillow is a flat needle head with the diameter of 1mm, the high-voltage direct-current power supply is 22KV, the distance between the spinning needle head and the roller is 20cm, and the rotating speed of the roller is 1500 rpm.
S3, curing
And taking down the spun electrostatic spinning fiber film, cutting, hot-pressing at 130 ℃ under the pressure of 40PSI for 30min, carrying out temperature programming and heat preservation on the hot-pressed fiber film, and cooling to room temperature to obtain the high-thermal-conductivity fiber film. The programmed heating and heat preservation processes are that the temperature is raised from room temperature to 180 ℃ within 60 min; keeping the temperature at 180 ℃ for 60 min; heating to 350 deg.C at 180 deg.C within 60 min; keeping the temperature at 350 ℃ for 60 min.
Example 4
The electrostatic spinning ink comprises the following raw materials in parts by weight:
30 parts of polyether polyurethane resin and 25 parts of glycidyl ether epoxy resin
6 portions of alumina
68 parts of butanone and toluene
Polyether ketone resin 6 parts
11 parts of polyoxyethylene alkylphenol ether
0.9-1.5 parts of pentaerythritol ester and 0.3 parts of stearic acid
The preparation method of the high-thermal-conductivity fiber membrane comprises the following steps
S1, preparation of electrostatic spinning ink
S11, mixing main resin and part of solvent in a reaction bottle, and stirring and dispersing at 65 ℃ and a dispersion speed of 500rpm for 3 hours to obtain main resin dispersion liquid;
s12, mixing the toughening resin with a part of solvent, and stirring and dispersing at 75 ℃ at a dispersion speed of 5rpm for 1h to obtain a toughening resin dispersion liquid;
s13, mixing the heat-conducting filler with the rest solvent, stirring and dispersing for 0.6h at a dispersion speed of 500rpm to obtain a heat-conducting filler suspension;
s14, mixing the main resin dispersion liquid obtained in the step S11 with the toughening resin dispersion liquid obtained in the step S12, stirring and dispersing for 0.6h at a dispersion speed of 1100rpm to obtain a mixed resin dispersion liquid;
s15, mixing the mixed resin dispersion liquid obtained in the step S14 with the heat-conducting filler suspension liquid obtained in the step S13, adding a dispersing agent and a stabilizing agent, stirring and dispersing for 1.1h at the dispersing speed of 1200rpm, and obtaining the electrostatic spinning ink;
s2. electrostatic spinning
Carrying out electrostatic spinning on the electrostatic spinning ink solution by adopting electrostatic spinning equipment to obtain an electrostatic spinning fiber film; the electrostatic spinning process comprises the following process parameters: air humidity is 32-35%, the propelling speed of an injection pump is 0.3-0.5ml/h, a spinning pillow is a flat needle head with 0.2-0.3mm, a high-voltage direct-current power supply is 6-8KV, the distance between the spinning needle head and a roller is 7-10cm, and the rotating speed of the roller is 400 rpm.
S3, curing
And taking down the spun electrostatic spinning fiber film, cutting, hot-pressing at 90 ℃ and under the pressure of 20PSI for 19min, carrying out temperature programming and heat preservation on the hot-pressed fiber film, and cooling to room temperature to obtain the high-thermal-conductivity fiber film. The programmed heating and heat preservation processes are that the temperature is raised to 130 ℃ from the room temperature within 35 min; keeping the temperature at 130 ℃ for 35 min; heating to 260 ℃ at 130 ℃ within 35 min; the temperature is maintained at 260 ℃ for 35 min.
Example 5
The electrostatic spinning ink comprises the following raw materials in parts by weight:
30 parts of glycidyl ester epoxy resin and 45 parts of glycidyl amine epoxy resin
Magnesium oxide 7 parts
78 parts of toluene
2 parts of polysulfone orange ester resin and 5 parts of polyether sulfone resin
2 parts of poly (methyl) acrylic acid derivative and 12 parts of maleic anhydride copolymer
Pentaerythritol ester 1.4 parts and stearic acid 0.4 part
The preparation method of the high-thermal-conductivity fiber membrane comprises the following steps
S1, preparation of electrostatic spinning ink
S11, mixing main resin and part of solvent in a reaction bottle, and stirring and dispersing at the dispersion speed of 900rpm at 78 ℃ for 7 hours to obtain main resin dispersion liquid;
s12, mixing the toughening resin with a part of solvent, and stirring and dispersing at 85 ℃ at a dispersion speed of 900rpm for 3.5 hours to obtain a toughening resin dispersion liquid;
s13, mixing the heat-conducting filler with the rest solvent, stirring and dispersing for 1.8h at the dispersion speed of 900rpm to obtain a heat-conducting filler suspension;
s14, mixing the main resin dispersion liquid obtained in the step S11 with the toughening resin dispersion liquid obtained in the step S12, stirring and dispersing for 0.9h at a dispersion speed of 1900rpm to obtain a mixed resin dispersion liquid;
s15, mixing the mixed resin dispersion liquid obtained in the step S14 with the heat-conducting filler suspension liquid obtained in the step S13, adding a dispersing agent and a stabilizing agent, stirring and dispersing for 1.9h at the dispersion speed of 2800rpm to obtain electrostatic spinning ink;
s2. electrostatic spinning
Carrying out electrostatic spinning on the electrostatic spinning ink solution by adopting electrostatic spinning equipment to obtain an electrostatic spinning fiber film; the electrostatic spinning process comprises the following process parameters: air humidity is 70-75%, the advancing speed of an injection pump is 2-2.5ml/h, a spinning pillow is a flat needle head with 0.6-0.8mm, a high-voltage direct-current power supply is 15-18KV, the distance between the spinning needle head and a roller is 11-14cm, and the rotating speed of the roller is 1100 rpm.
S3, curing
And taking down the spun electrostatic spinning fiber film, cutting, hot-pressing for 28min at the temperature of 120 ℃ and under the pressure of 35PSI, carrying out temperature programming and heat preservation on the hot-pressed fiber film, and cooling to room temperature to obtain the high-thermal-conductivity fiber film. The programmed heating and heat preservation processes are that the temperature is raised from the room temperature to 170 ℃ within 55 min; keeping the temperature at 170 ℃ for 50 min; heating to 340 ℃ at 170 ℃ within 50 min; the temperature is maintained at 340 ℃ for 50 min.
Example 6
The electrostatic spinning ink comprises the following raw materials in parts by weight:
80 parts of bisphenol A type epoxy resin
5 parts of boron nitride
Butanone 30 parts and toluene 49 parts
3 parts of etherimide resin and 5 parts of polyether ketone resin
10 portions of polyoxyethylene alkylphenol ether
0.8 part of pentaerythritol ester and 0.2 part of stearic acid
The preparation method of the high-thermal-conductivity fiber membrane comprises the following steps
S1, preparation of electrostatic spinning ink
S11, mixing main resin and part of solvent in a reaction bottle, and stirring and dispersing at the dispersion speed of 400rpm for 8 hours at the temperature of 80 ℃ to obtain main resin dispersion liquid;
s12, mixing the toughening resin with a part of solvent, and stirring and dispersing at 70 ℃ at a dispersion speed of 1000rpm for 0.5h to obtain a toughening resin dispersion liquid;
s13, mixing the heat-conducting filler with the rest solvent, stirring and dispersing for 2 hours at a dispersion speed of 400rpm to obtain a heat-conducting filler suspension;
s14, mixing the main resin dispersion liquid obtained in the step S11 and the toughening resin dispersion liquid obtained in the step S12, stirring and dispersing for 0.5h at a dispersion speed of 2000rpm to obtain a mixed resin dispersion liquid;
s15, mixing the mixed resin dispersion liquid obtained in the step S14 with the heat-conducting filler suspension liquid obtained in the step S13, adding a dispersing agent and a stabilizing agent, stirring and dispersing for 2 hours at the dispersion speed of 1000rpm, and obtaining the electrostatic spinning ink;
s2. electrostatic spinning
Carrying out electrostatic spinning on the electrostatic spinning ink solution by adopting electrostatic spinning equipment to obtain an electrostatic spinning fiber film; the electrostatic spinning process comprises the following process parameters: the air humidity is 30%, the propelling speed of the injection pump is 3ml/h, the spinning pillow is a flat needle head with the diameter of 1mm, the high-voltage direct-current power supply is 5KV, the distance between the spinning needle head and the roller is 5cm, and the rotating speed of the roller is 1500 rpm.
S3, curing
And taking down the spun electrostatic spinning fiber film, cutting, hot-pressing for 15min at 80 ℃ under the pressure of 40PSI, carrying out temperature programming and heat preservation on the hot-pressed fiber film, and cooling to room temperature to obtain the high-thermal-conductivity fiber film. The programmed heating and heat preservation processes are that the temperature is increased from room temperature to 180 ℃ within 30 min; keeping the temperature at 180 ℃ for 30 min; heating to 250 deg.C at 180 deg.C within 60 min; keeping the temperature at 250 ℃ for 60 min.
Comparative example 1
No heat conductive filler was added, and the remaining conditions were the same as in example 1;
comparative example 2
No stabilizer was added, and the remaining conditions were the same as in example 1;
tests the high thermal conductivity fiber membranes prepared in examples 1 to 6 and comparative examples 1 to 2 were subjected to the following performance tests, and the results are summarized in table 1.
And (3) performance detection: 1. detecting the dielectric constant, the thermal conductivity and the dielectric loss rate at room temperature; 2. detecting the dielectric constant, the thermal conductivity and the dielectric loss rate at 110-120 ℃.
From table 1 above, it can be seen that the fiber films prepared in examples 1-6 have a lower dielectric constant, a higher thermal conductivity and a low dielectric loss at room temperature; at 110-120 deg.C, the thermal conductivity is slightly increased, the dielectric constant is also slightly increased, the whole is still less than 2, and the dielectric loss is 10 -1 Below, the range is acceptable.
After the stabilizer is lacked, the thermal conductivity coefficient is obviously reduced and the dielectric loss is obviously increased at high temperature, which shows that the fiber film without the stabilizer can be degraded or coked at high temperature, so that the thermal conductivity coefficient is obviously reduced and the dielectric loss is obviously increased.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (10)
1. The electrostatic spinning ink is characterized by comprising the following raw materials in parts by weight:
50-80 parts of main resin, 5-8 parts of heat-conducting filler, 65-80 parts of solvent, 5-8 parts of toughening resin, 10-15 parts of dispersant and 1-2 parts of stabilizer.
2. The electrospinning ink of claim 1, wherein the host resin is selected from any one or more of polyester polyurethane, acrylic polyurethane, alkyd polyurethane, polyether polyurethane, glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, and bisphenol a epoxy resin.
3. An electrospinning ink according to claim 1, wherein the thermally conductive filler is selected from any one or more of nanodiamond, carbide, ferroelectric ceramic, metal oxide, boron nitride.
4. An electrospinning ink according to claim 1, wherein the dispersant is selected from any one or more of polycarboxylate, poly (meth) acrylic acid derivative, maleic anhydride copolymer and polyoxyethylene alkylphenol ether.
5. The electrospinning ink according to claim 1, wherein the toughening resin is selected from any one or more of polysulfone and citrus ester resins, polyethersulfone resins, polyetherimide resins, and polyetherketone resins.
6. An electrospinning ink according to claim 1, wherein the solvent is selected from any one or any combination of dimethylformamide, dimethylacetamide, ethyl ester, butanone and toluene.
7. A highly thermally conductive fiber membrane, characterized in that the electrospun ink of any one of claims 1 to 6 is used to prepare a highly thermally conductive fiber membrane.
8. A method for preparing the high thermal conductive fiber membrane of claim 7, comprising the steps of:
s1, preparation of electrostatic spinning ink
S11, mixing the main resin with a part of solvent, and stirring and dispersing for 2-8 hours at the temperature of 60-80 ℃ to obtain a main resin dispersion liquid;
s12, mixing the toughening resin with a part of solvent, and stirring and dispersing for 0.5-4h at 70-90 ℃ to obtain a toughening resin dispersion liquid;
s13, mixing the heat-conducting filler with the rest solvent, and stirring and dispersing for 0.5-2h to obtain a heat-conducting filler suspension;
s14, mixing the main resin dispersion liquid obtained in the step S11 with the toughening resin dispersion liquid obtained in the step S12, and stirring and dispersing for 0.5-1h to obtain a mixed resin dispersion liquid;
s15, mixing the mixed resin dispersion liquid obtained in the step S14 with the heat-conducting filler suspension liquid obtained in the step S13, adding a dispersing agent and a stabilizing agent, and stirring and dispersing for 1-2 hours to obtain electrostatic spinning ink;
s2. electrostatic spinning
Carrying out electrostatic spinning on the electrostatic spinning ink solution by adopting electrostatic spinning equipment to obtain an electrostatic spinning fiber film;
s3, curing
And taking down the spun electrostatic spinning fiber film, cutting, hot-pressing at 80-130 ℃ under the pressure of 15-40PSI for 15-30min, carrying out temperature programming and heat preservation on the hot-pressed fiber film, and cooling to room temperature to obtain the high-thermal-conductivity fiber film.
9. The method for preparing a fiber membrane with high thermal conductivity according to claim 8, wherein in the step S2, electrostatic spinning is performed, and the process parameters are as follows: the air humidity is 30-80%, the advancing speed of the injection pump is 0.2-3ml/h, the spinning pillow is a flat needle head with 0.1-1mm, the high-voltage direct-current power supply is 5-22KV, the distance between the spinning needle head and the roller is 5-20cm, and the rotating speed of the roller is 100-.
10. The method for preparing the fiber membrane with high thermal conductivity according to claim 8, wherein the temperature raising and maintaining process of step S3 is raising the temperature from room temperature to 180 ℃ within 30-60 min; preserving the heat for 30-60min at the temperature of 120-; heating to 180 ℃ at the temperature of 120-350 ℃ within 30-60 min; keeping the temperature at 350 ℃ for 30-60min at 250-.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1951987A (en) * | 2006-11-20 | 2007-04-25 | 吉林大学 | Method for preparing low dielectric constant high polymer nanometer fiber membrane using electric spinning method |
| CN103937157A (en) * | 2014-03-05 | 2014-07-23 | 浙江华正新材料股份有限公司 | Halogen-free resin composition and method for manufacturing prepreg and laminated board by using halogen-free resin composition |
| CN108794998A (en) * | 2017-04-27 | 2018-11-13 | 比亚迪股份有限公司 | Low dielectric resin composition and low dielectric resin metallic composite and preparation method thereof and information technoloy equipment |
| CN109135283A (en) * | 2018-06-25 | 2019-01-04 | 广东格瑞新材料股份有限公司 | A kind of PPS material and preparation method thereof for electric-device housing |
| US20200239759A1 (en) * | 2017-08-28 | 2020-07-30 | Kanto Denka Kogyo Co., Ltd. | Thermally conductive particle-filled fiber |
| CN111732778A (en) * | 2020-07-09 | 2020-10-02 | 中节能(唐山)环保装备有限公司 | Preparation method of high-thermal-conductivity composite material |
-
2022
- 2022-03-11 CN CN202210238367.1A patent/CN114808183A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1951987A (en) * | 2006-11-20 | 2007-04-25 | 吉林大学 | Method for preparing low dielectric constant high polymer nanometer fiber membrane using electric spinning method |
| CN103937157A (en) * | 2014-03-05 | 2014-07-23 | 浙江华正新材料股份有限公司 | Halogen-free resin composition and method for manufacturing prepreg and laminated board by using halogen-free resin composition |
| CN108794998A (en) * | 2017-04-27 | 2018-11-13 | 比亚迪股份有限公司 | Low dielectric resin composition and low dielectric resin metallic composite and preparation method thereof and information technoloy equipment |
| US20200239759A1 (en) * | 2017-08-28 | 2020-07-30 | Kanto Denka Kogyo Co., Ltd. | Thermally conductive particle-filled fiber |
| CN109135283A (en) * | 2018-06-25 | 2019-01-04 | 广东格瑞新材料股份有限公司 | A kind of PPS material and preparation method thereof for electric-device housing |
| CN111732778A (en) * | 2020-07-09 | 2020-10-02 | 中节能(唐山)环保装备有限公司 | Preparation method of high-thermal-conductivity composite material |
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Application publication date: 20220729 |