CN106589812A - Fiber-reinforced epoxy heat-conductive material and preparation method thereof - Google Patents
Fiber-reinforced epoxy heat-conductive material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
Abstract
A fiber-reinforced epoxy heat-conductive material disclosed in the present invention consists of the following raw materials in parts by weight: 1-2 parts of alkenyl succinic anhydride, 37-40 parts of hexagonal boron nitride, 8-10 parts of methylhexahydrophthalic anhydride, 0.4-1 part of neodymium acetylacetonate, 0.7-1 part of octadecylamine, 4-6 parts of 3,5-diaminobenzoic acid, 2-3 parts of triphenyl phosphite, 0.3-0.5 part of pyridine, 32-40 parts of N-methylpyrrolidone, 100-110 parts of epoxy resin E40, 3-4 parts of cellulose phosphate, 1-3 parts of tetrakis(hydroxymethyl)phosphonium sulfate, 3-5 parts of triethyl acetylcitrate, 0.1-0.2 part of diphenylimidazoline, 2-3 parts of magnesium stearate, 0.1-0.2 part of hexamethylphosphoramide and 8-10 parts of diatomaceous earth. Cellulose phosphate added to the fiber-reinforced epoxy heat-conductive material can improve the toughness and strength of the finished material efficiently and can increase the compatibility of the materials.
Description
Technical field
The present invention relates to Heat Conduction Material technical field, more particularly to a kind of fibre enhancement epoxy Heat Conduction Material and its preparation side
Method.
Background technology
Polymer Composites with High Thermal Conductivity as a kind of functional material of great application prospect, due to there is good heat
Conductive performance, thus play in many manufacturing industry such as microelectronics, Aeronautics and Astronautics, military equipment, electrical equipment and electrical and high-tech area
Very important effect.Particularly in recent years, with electronic integration technology high speed development, packing density is improved rapidly, electronics
Element, thousands of times of logic circuit volume ground reduces, electronic instrument and equipment is increasingly ultralight, thin, short, little direction is developed,
Under high-frequency work frequency, semiconductor operating thermal environment to high temperature direction is moved rapidly;Now, the heat that electronic devices and components are produced is fast
Speed accumulation and increase, will make components and parts remain to normally reliably run, and radiating in time becomes the key of restriction service life
Technology.Therefore with electronic devices and components miniaturization, high performance, it is desirable to which material proposes requirements at the higher level to heat conductivility.At present
General polymeric material cannot meet the demand of development.Exploitation has Thermal conductivity, while and with higher Jie
The polymer matrix composite of electrical property and processability is electric for microelectronics, Aero-Space, military equipment and motor is promoted
The fields such as device fast development important in inhibiting；
Hexagonal boron nitride is a kind of III-V important race's chemicals, belongs to hexagonal crystal system, is most common in boron nitride there is shape
State, it has the similar layer structure with graphite, have the title of white graphite.Each layer of hexagonal AlN is former by B atoms and N
The hexagonal circulus of the spaced plane of son, and B atoms and N atoms are one by SP2 hydridization Covalent bonding togethers
Rise, and combine by Van der Waals force between layers, therefore hexagonal AlN is stablized per Rotating fields, but it is easy to stripping between layers
From.BN materials have many excellent performances, such as:High heat conduction, electric insulation, high temperature resistant, the anti-oxidant, coefficient of expansion are low, friction
Coefficient is low, chemical stability is good, processability is good, with good wave many advantages, such as, therefore be widely used in
The high-tech such as machinery, metallurgy, electronics, space flight and aviation is led the way.Over the years, the nano material such as BN nanotubes and nanometer sheet with
The discovery of CNT and Graphene also becomes the focus of current research.The technology of preparing of BN nanotubes is constantly developed, it is existing
The side such as arc discharge method, laser ablation method, mechanical attrition method, CNT template, chemical vapour deposition technique is being explored
Method can successfully prepare BN nanotubes, and do substantial amounts of research to its sense dough and application；
Epoxy resin has excellent mechanical property, electrical property, adhesive property and thermally-stabilised, be widely used to Aero-Space,
The field such as electric.Epoxy resin is various in style, and what this work was selected is cycloaliphatic epoxy resin, due to aliphatic ring oxygen tree
Epoxide group in fat molecular structure is not from expoxy propane, and epoxy radicals is connected directly between on alicyclic ring, so alicyclic epoxy
Resin compared with bisphenol-A type epoxy resin, with good heat endurance, excellent electrical insulation capability and weather resisteant, height
Security many advantages, such as.But the thermal conductivity factor of epoxy resin relatively low (0.23 W/m K), heat dispersion is poor, difficult
To meet the fast development of microelectric technique and encapsulation technology；
The thermal conductivity factor of polymer matrix composite is not only relevant with the thermal conductivity factor that it constitutes each phase, but also with each component
Relative amount, form, distribution and interaction are relevant.Filler grain content, shape of particle, distribution etc. all can be led to system
Hot coefficient is produced a very large impact.At present, many researchers are according to minimum thermal resistance method, Thermal self-ignition and homogenize method scheduling theory,
The model of many prediction binary system thermal conductivities is set up, big multi-model is suitable only for corresponding system, and universality is not high.
The content of the invention
The object of the invention is exactly to make up the defect of prior art, there is provided a kind of fibre enhancement epoxy Heat Conduction Material and its
Preparation method.
The present invention is achieved by the following technical solutions：
A kind of fibre enhancement epoxy Heat Conduction Material, it is made up of the raw material of following weight parts：
Alkenyl succinic anhydride 1-2, hexagonal boron nitride 37-40, methylhexahydrophthalic anhydride 8-10, acetylacetone,2,4-pentanedione neodymium 0.4-1,
Octadecylamine 0.7-1,3,5- diaminobenzoic acid 4-6, triphenyl phosphite 2-3, pyridine 0.3-0.5,1-METHYLPYRROLIDONE 32-
40th, epoxy resin E40100-110, cellulose phosphate 3-4, tetrakis hydroxymetyl phosphonium sulfuric 1-3, ATEC 3-5, two
Benzylimidazoline 0.1-0.2, magnesium stearate 2-3, HMPA 0.1-0.2, diatomite 8-10.
A kind of preparation method of described fibre enhancement epoxy Heat Conduction Material, comprises the following steps：
（1）Above-mentioned diatomite is calcined into 1-2 hours at 650-700 DEG C, is cooled down, fine powder is worn into, with above-mentioned alkenyl succinic anhydride
Mixing, in being added to the deionized water of compound weight 10-13 times, it is 65-70 DEG C to rise high-temperature, insulated and stirred 40-50 minute,
Filter, precipitation is washed 2-3 time, air drying, in being added to the sodium hydroxide solution of 10-13mol/l, stirring reaction 1.7-2
Hour, filter, by precipitation washing 2-3 time, 100-120 minutes are dried at vacuum 50-60 DEG C, obtain modification infusorial earth；
（2）Above-mentioned hexagonal boron nitride, modification infusorial earth are mixed, the N of compound weight 35-40 times, N- dimethyl methyls is added to
In acid amides, ultrasonic 100-120 minutes, it is centrifuged in the centrifuge of 5000-8000rpm, collects upper solution, suction filtration, by filter cake
It is complete as in vacuum drying oven, being dried at 60-70 DEG C, obtain stripping boron nitride；
（3）By above-mentioned stripping boron nitride, octadecylamine mix, as 190-200 DEG C of oil bath in, be passed through nitrogen, insulated and stirred 90-
100 hours, discharging was cooled to room temperature, added the tetrahydrofuran of compound weight 10-12 times, stirred 100-130 minutes, filtered,
Precipitation methyl alcohol is washed 3-4 time, is placed in 110-120 DEG C of vacuum drying oven and is dried 100-150 minutes, obtain octadecylamine grafting nitrogen
Change boron；
（4）Above-mentioned diphenyl-imidazole quinoline is added in the absolute ethyl alcohol of its weight 10-14 times, 80-90 DEG C of constant temperature is sent to
In water-bath, above-mentioned magnesium stearate, insulated and stirred 10-20 minute, discharging is added to mix with above-mentioned tetrakis hydroxymetyl phosphonium sulfuric, stir
To normal temperature, alcohol dispersion liquid is obtained；
（5）By above-mentioned cellulose phosphate, octadecylamine grafting boron nitride mixing, in being added to alcohol dispersion liquid, ultrasonic 3-5 minutes, mistake
Filter, precipitation absolute ethyl alcohol, deionized water are washed 3-4 time successively, and 1-2 hours are vacuum dried at 50-60 DEG C, must be modified and be connect
Branch boron nitride；
（6）Above-mentioned grafting boron nitride is taken, in being added to 1-METHYLPYRROLIDONE, is stirred, add above-mentioned 3,5- diaminobenzenes
Formic acid, triphenyl phosphite, pyridine, are passed through nitrogen, and 3-4 hours are reacted at 100-110 DEG C, and discharging cooling is added to quality
Than carrying out precipitating in the methanol solvate for 0.1% lithium chloride, filter to isolate precipitation, with DMA, methyl alcohol according to
Secondary washing 3-4 time, is vacuum dried 2-3 hours at 90-100 DEG C, obtains hyperbranched modified boron nitride；
（7）Above-mentioned acetylacetone,2,4-pentanedione neodymium, epoxy resin E40 are mixed, 1-2 hours are stirred at 80-90 DEG C, be added to compound weight
In the acetone of 7-10 times of amount, above-mentioned diphenyl-imidazole quinoline is added, ultrasonically treated 10-20 minutes, add above-mentioned hyperbranched modified nitrogen
Change boron, ultrasonic 20-30 minutes, as 70-75 DEG C of oil bath in, acetone solvent volatilization is clean, add remaining each raw material, stir
Mix uniform, in being placed in steel mold, first the precuring 100-110 minutes at 135-140 DEG C, then temperature be raised to into 165-170 DEG C,
Solidification 10-15 hours, cooling is obtained final product.
It is an advantage of the invention that：The present invention can be efficiently peeled off hexagonal AlN powder initially with the method for ultrasound centrifugation,
This is because inside BN, the hexatomic ring in each layer is relatively independent, there is no the phenomenon for misplacing between them, and perpendicular
Can be regarded as on straight direction it is parallel, meanwhile, combined in the form of very strong covalent bond between the atom in layer, thus
Then combined in the form of weaker Van der Waals force between compact conformation, but each layer, due to its layer of BN powder and layer relatively
Weak adhesion and in larger distance, so each interlayer of BN powder relatively easily slides and peels off in the presence of ultrasonic wave；So
The BN nanometer sheets peeled off using octadecylamine molecular modification afterwards, because the end group amino in octadecylamine is that electron rich serves as Lewis
Acid, and B atoms are that electron deficient serves as Lewis alkali in BN nanometer sheets, by the mutual of the non-covalent bond of Lewis soda acids
Effect octadecylamine molecule can be particularly well adsorbed in BN nanometer sheets surface, it is modified after BN nanometer sheets surface octadecylamine
Long-chain molecule can occur molecular entanglement and produce a good interface interaction in Curing Process of Epoxy with epoxy molecule,
Many physical crosslinking points are formed, its heat conductivility is enhanced, hyperbranched being modified finally is passed through again and is distributed to epoxy resin-base
In, and with good dispersiveness and compatibility, because the end group of the Hyperbranched Aromatic Polyamides of hyperbranched modified nitridation boron surface
There is substantial amounts of amino group, chemical reaction can occur with the epoxide group of epoxy resin, enhance modified boron nitride and asphalt mixtures modified by epoxy resin
Interaction force between fat interface, this action effect increased the chemical crosslinking point in epoxy resin cure network, asphalt mixtures modified by epoxy resin
Crosslinking points increase the interface resistance that can be reduced between modified boron nitride and epoxy resin in fat three-dimensional network, substantially increase multiple
The heat conductivility of condensation material.Present invention adds cellulose phosphate, can effectively improve toughness, the intensity of finished-product material, carry
The compatibility of high each material.
Specific embodiment
A kind of fibre enhancement epoxy Heat Conduction Material, it is made up of the raw material of following weight parts：
Alkenyl succinic anhydride 1, hexagonal boron nitride 37, methylhexahydrophthalic anhydride 8, the diaminobenzene first of octadecylamine 0.7,3,5
Acid 4, triphenyl phosphite 2, pyridine 0.3,1-METHYLPYRROLIDONE 32, epoxy resin E40100, cellulose phosphate 3, four hydroxyl first
Base sulfuric acid phosphorus 1, ATEC 3, diphenyl-imidazole quinoline 0.1, magnesium stearate 2, HMPA 0.1, diatom
Soil 8, acetylacetone,2,4-pentanedione neodymium 0.4.
A kind of preparation method of described fibre enhancement epoxy Heat Conduction Material, comprises the following steps：
（1）Above-mentioned diatomite is calcined 1 hour at 650 DEG C, is cooled down, wear into fine powder, mixed with above-mentioned alkenyl succinic anhydride, plus
Enter in the deionized water of 10 times of compound weight, it is 65 DEG C to rise high-temperature, and insulated and stirred 40 minutes is filtered, will precipitation washing 2
It is secondary, air drying, in being added to the sodium hydroxide solution of 10mol/l, stirring reaction 1.7 hours is filtered, by precipitation washing 2 times,
It is dried 100 minutes at 50 DEG C of vacuum, obtains modification infusorial earth；
（2）Above-mentioned hexagonal boron nitride, modification infusorial earth are mixed, the DMF of 35 times of compound weight is added to
In, ultrasound 100 minutes is centrifuged in the centrifuge of 5000rpm, collects upper solution, suction filtration, by filter cake as vacuum drying oven
In, it is dried completely at 60 DEG C, obtain stripping boron nitride；
（3）Above-mentioned stripping boron nitride, octadecylamine are mixed, as 190 DEG C of oil baths in, be passed through nitrogen, insulated and stirred 90 hours,
Discharging is cooled to room temperature, adds the tetrahydrofuran of 10 times of compound weight, stirs 100 minutes, filters, and precipitation methyl alcohol is washed into 3
It is secondary, it is placed in in 110 DEG C of vacuum drying oven and is dried 100 minutes, obtain octadecylamine grafting boron nitride；
（4）Above-mentioned diphenyl-imidazole quinoline is added in the absolute ethyl alcohol of 10 times of its weight, in being sent to 80 DEG C of water bath with thermostatic control,
Add above-mentioned magnesium stearate, insulated and stirred 10 minutes, discharging to mix with above-mentioned tetrakis hydroxymetyl phosphonium sulfuric, stir to normal temperature, obtain alcohol
Dispersion liquid；
（5）By above-mentioned cellulose phosphate, octadecylamine grafting boron nitride mixing, in being added to alcohol dispersion liquid, ultrasound 3 minutes is filtered,
Precipitation absolute ethyl alcohol, deionized water are washed successively 3 times, is vacuum dried 1 hour at 50 DEG C, must be modified grafting boron nitride；
（6）Above-mentioned grafting boron nitride is taken, in being added to N methyl pyrrolidones, is stirred, add above-mentioned 3,5 diaminobenzene first
Acid, triphenyl phosphite, pyridine, are passed through nitrogen, react 3 hours at 100 DEG C, discharging cooling, are added to mass ratio for 0.1%
Lithium chloride methanol solvate in carry out precipitating, filter to isolate precipitation, with N, N dimethyl acetamide, methyl alcohol wash successively 3
It is secondary, it is vacuum dried 2 hours at 90 DEG C, obtain hyperbranched modified boron nitride；
（7）Above-mentioned acetylacetone,2,4-pentanedione neodymium, epoxy resin E40 are mixed, is stirred 1 hour at 80 DEG C, be added to 7 times of compound weight
Acetone in, add above-mentioned diphenyl-imidazole quinoline, ultrasonically treated 10 minutes, add above-mentioned hyperbranched modified boron nitride, ultrasound 20
Minute, as 70 DEG C of oil baths in, acetone solvent volatilization is clean, add remaining each raw material, stir, be placed in steel mold
In, first precuring 100 minutes at 135 DEG C, are then raised to 165 DEG C by temperature, solidify 10 hours, and cooling is obtained final product.
Performance test：
Its thermal conductivity factor is 0.57 W/mK at 25 DEG C.
Claims (2)
1. a kind of fibre enhancement epoxy Heat Conduction Material, it is characterised in that it is made up of the raw material of following weight parts：
Alkenyl succinic anhydride 1-2, hexagonal boron nitride 37-40, methylhexahydrophthalic anhydride 8-10, acetylacetone,2,4-pentanedione neodymium 0.4-1,
Octadecylamine 0.7-1,3,5- diaminobenzoic acid 4-6, triphenyl phosphite 2-3, pyridine 0.3-0.5,1-METHYLPYRROLIDONE 32-
40th, epoxy resin E40100-110, cellulose phosphate 3-4, tetrakis hydroxymetyl phosphonium sulfuric 1-3, ATEC 3-5, two
Benzylimidazoline 0.1-0.2, magnesium stearate 2-3, HMPA 0.1-0.2, diatomite 8-10.
2. a kind of preparation method of fibre enhancement epoxy Heat Conduction Material as claimed in claim 1, it is characterised in that including following
Step：
（1）Above-mentioned diatomite is calcined into 1-2 hours at 650-700 DEG C, is cooled down, fine powder is worn into, with above-mentioned alkenyl succinic anhydride
Mixing, in being added to the deionized water of compound weight 10-13 times, it is 65-70 DEG C to rise high-temperature, insulated and stirred 40-50 minute,
Filter, precipitation is washed 2-3 time, air drying, in being added to the sodium hydroxide solution of 10-13mol/l, stirring reaction 1.7-2
Hour, filter, by precipitation washing 2-3 time, 100-120 minutes are dried at vacuum 50-60 DEG C, obtain modification infusorial earth；
（2）Above-mentioned hexagonal boron nitride, modification infusorial earth are mixed, the N of compound weight 35-40 times, N- dimethyl methyls is added to
In acid amides, ultrasonic 100-120 minutes, it is centrifuged in the centrifuge of 5000-8000rpm, collects upper solution, suction filtration, by filter cake
It is complete as in vacuum drying oven, being dried at 60-70 DEG C, obtain stripping boron nitride；
（3）By above-mentioned stripping boron nitride, octadecylamine mix, as 190-200 DEG C of oil bath in, be passed through nitrogen, insulated and stirred 90-
100 hours, discharging was cooled to room temperature, added the tetrahydrofuran of compound weight 10-12 times, stirred 100-130 minutes, filtered,
Precipitation methyl alcohol is washed 3-4 time, is placed in 110-120 DEG C of vacuum drying oven and is dried 100-150 minutes, obtain octadecylamine grafting nitrogen
Change boron；
（4）Above-mentioned diphenyl-imidazole quinoline is added in the absolute ethyl alcohol of its weight 10-14 times, 80-90 DEG C of constant temperature is sent to
In water-bath, above-mentioned magnesium stearate, insulated and stirred 10-20 minute, discharging is added to mix with above-mentioned tetrakis hydroxymetyl phosphonium sulfuric, stir
To normal temperature, alcohol dispersion liquid is obtained；
（5）By above-mentioned cellulose phosphate, octadecylamine grafting boron nitride mixing, in being added to alcohol dispersion liquid, ultrasonic 3-5 minutes, mistake
Filter, precipitation absolute ethyl alcohol, deionized water are washed 3-4 time successively, and 1-2 hours are vacuum dried at 50-60 DEG C, must be modified and be connect
Branch boron nitride；
（6）Above-mentioned grafting boron nitride is taken, in being added to 1-METHYLPYRROLIDONE, is stirred, add above-mentioned 3,5- diaminobenzenes
Formic acid, triphenyl phosphite, pyridine, are passed through nitrogen, and 3-4 hours are reacted at 100-110 DEG C, and discharging cooling is added to quality
Than carrying out precipitating in the methanol solvate for 0.1% lithium chloride, filter to isolate precipitation, with DMA, methyl alcohol according to
Secondary washing 3-4 time, is vacuum dried 2-3 hours at 90-100 DEG C, obtains hyperbranched modified boron nitride；
（7）Above-mentioned acetylacetone,2,4-pentanedione neodymium, epoxy resin E40 are mixed, 1-2 hours are stirred at 80-90 DEG C, be added to compound weight
In the acetone of 7-10 times of amount, above-mentioned diphenyl-imidazole quinoline is added, ultrasonically treated 10-20 minutes, add above-mentioned hyperbranched modified nitrogen
Change boron, ultrasonic 20-30 minutes, as 70-75 DEG C of oil bath in, acetone solvent volatilization is clean, add remaining each raw material, stir
Mix uniform, in being placed in steel mold, first the precuring 100-110 minutes at 135-140 DEG C, then temperature be raised to into 165-170 DEG C,
Solidification 10-15 hours, cooling is obtained final product.
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| CN201611068119.8A CN106589812A (en) | 2016-11-29 | 2016-11-29 | Fiber-reinforced epoxy heat-conductive material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112795140A (en) * | 2021-01-04 | 2021-05-14 | 中变集团上海变压器有限公司 | Epoxy resin coil for transformer and processing technology thereof |
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| CN103172973A (en) * | 2013-03-26 | 2013-06-26 | 上海交通大学 | High thermal-conductivity polymer composite material and preparation method thereof |
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| CN103172973A (en) * | 2013-03-26 | 2013-06-26 | 上海交通大学 | High thermal-conductivity polymer composite material and preparation method thereof |
| CN105885404A (en) * | 2016-06-06 | 2016-08-24 | 淮南曹庵润龙塑业有限公司 | Fiber modified nylon mould material and preparation method thereof |
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| CN112795140A (en) * | 2021-01-04 | 2021-05-14 | 中变集团上海变压器有限公司 | Epoxy resin coil for transformer and processing technology thereof |
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