CN107298858A - A kind of graphene oxide toughening model+composition and preparation method thereof - Google Patents
A kind of graphene oxide toughening model+composition and preparation method thereof Download PDFInfo
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- CN107298858A CN107298858A CN201710565222.1A CN201710565222A CN107298858A CN 107298858 A CN107298858 A CN 107298858A CN 201710565222 A CN201710565222 A CN 201710565222A CN 107298858 A CN107298858 A CN 107298858A
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- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The present invention relates to a kind of preparation method of graphene oxide toughening model+composition, step is as follows：1) graphene oxide water solution is prepared；2) bimaleimide resin containing tertiary amine groups is prepared；3) graphene oxide toughening model+composition.The present invention has advantages below：1) the problem of unmodified graphene oxide disperses uneven in bimaleimide resin base body is overcome；2) physics, chemical modification need not be carried out to graphene oxide, thus preparation technology is simple, it is easy to operate, cost is low, beneficial to the industrial applications of graphene oxide.Nano composite material prepared by the present invention, graphene oxide is uniformly dispersed in bimaleimide resin composition；The overall performance of composite is improved, and can be widely applied to the technical fields such as Aero-Space, ship automobile, traffic, building, microelectronics Packaging.
Description
Technical field
The present invention relates to high performance resin based nano composite material and preparation method thereof, graphite oxide is especially that by
The preparation method of alkene graphene oxide toughening model+dispersed in resin matrix.
Background technology
Bimaleimide resin base carbon fibre composite has high specific strength, high ratio modulus, good manufacturability, resistance to
The excellent properties such as burn into high temperature resistant, thermal oxidation resistance, fire-retardant, low hydroscopicity, are widely used in the numerous areas such as Aero-Space.So
And, the performance of composite depends not only on the species and performance of reinforcement carbon fiber, also with bimaleimide resin base body
There is very big relation, the water ratio limit effect of its intensity, toughness, heat resistance and bimaleimide resin and carbon fiber all can
Performance to composite has a huge impact.Bimaleimide resin is as many thermosetting resins, its solidfied material
It there are problems that matter is crisp, tensile strength is small, shock resistance due to crosslink density height.Pass through allyl compound, ring
The modifications such as oxygen tree fat, cyanate ester can improve the toughness of bimaleimide resin solidfied material to a certain extent, but still can not be same
When meet advanced component to material hardness, intensity, heat resistance high request.Therefore, a kind of suitable modifying agent is found to come to double
It is a job highly significant that maleimide resin, which is modified,.
Graphene is the Two-dimensional Carbon atomic crystal of monoatomic thickness, it is considered to be the base of fullerene, CNT and graphite
This construction unit, graphene has high conductivity, high-termal conductivity, high rigidity, high intensity, low thermal coefficient of expansion, high major diameter
Than the specific surface area with super large, graphene is widely used to improve the performance of polymeric matrix.But graphene is neither hydrophilic
Also not oleophylic, its surface limits its application in some fields in chemical reaction inertia.Graphene oxide is used as graphene
A kind of derivative, not only maintains the two-dimensional structure and excellent mechanical property of graphene, and abundant hydroxyl is contained on its surface
Base, carboxyl, epoxide group isoreactivity functional group can participate in chemical reaction, and this makes shape between graphene oxide and polymeric matrix
It is possibly realized into good compatibility, also carrying out physics, chemical modification for graphene oxide provides the foundation.Graphene oxide changes
Property polymer matrix composites turn into international forward position that field of compound material gets most of the attention in recent years and focus.
At present, a pass of the excellent graphene oxide of processability/bimaleimide resin base nano composite material
Key technology difficult point is how to realize that graphene oxide is dispersed in bimaleimide resin base body, makes graphene oxide
Good interface is formed between resin matrix, with good cohesive force, so that stress effectively is delivered into graphite oxide
On alkene, the purpose of activeness and quietness is realized.At present, mainly have by carrying out chemical modification to graphene oxide in its surface grafting
Machine functional group, then realizes that graphene oxide is scattered in bimaleimide resin by the mechanical agitation of strength.Li
(Journal of Materials Science,2015,50:5402-5410) by γ-methacryloxypropyl trimethoxy
Base silane is chemically grafted on graphene oxide, has obtained the graphene oxide (MPTS-GO) of silane-functionalized, then will
MPTS-GO, which is added in bimaleimide resin, is made graphene/bismaleimide resin composite material.Chen Zhiming is (high
Molecular material scientific and engineering, 2012,11 (11):169-172) then chemistry is carried out to graphene oxide by isocyanates to repair
Decorations, form substantial amounts of carbamate, amide groups, carboxyl isoreactivity functional group in surface of graphene oxide, make graphene oxide
Good interface phase is formed between bimaleimide resin.As a result show, prepared graphene oxide/bismaleimide
The mechanical property of polyimide resin nano composite material is greatly enhanced, while the heat resistance of composite is also changed
It is kind.But, these methods are required for carrying out multistep organic chemical reactionses, and reaction scheme length, purification step are more, and energy consumption is big；And
Need to use substantial amounts of N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), thionyl chloride equal solvent or toxicity larger
Organic reagent, the long processing period of these debirs is unfavorable to environment, also increases cost.These unfavorable factors are very big
Ground, which hinders graphene oxide toughness reinforcing, strengthens the large-scale production and application of BMI High performance nanometer composite material.
Due to there is problem above, graphene oxide toughness reinforcing enhancing bimaleimide resin and its carbon fiber composite
The performance of material is improved and production application is also greatly limited.
Glycidyl amine type epoxy resin contains tertiary amine groups, and diamine compound can be with bimaleimide resin, ring
Oxygen tree fat occurs to chemically react and generates tertiary amine groups, and tertiary amine groups then can be with the carboxyl on graphene oxide with the shape of ionic bond
Formula interacts, and graphene oxide is transferred to resin phase by aqueous phase.Diglycidyl ether type epoxy resin, epoxy novolac tree
Fat, allyl compound, cyanate ester can adjust dissolubility, viscosity, gel time of bimaleimide resin composition etc.
Processing characteristics, the mechanical property such as toughness, intensity, modulus, hardness, dielectric properties such as dielectric constant, dielectric loss and corrosion-resistant
Performance, fire resistance, wet-hot aging performance etc..
The content of the invention
It is an object of the present invention to overcome the above-mentioned technical problems, and to provide a kind of graphene oxide Bismaleimide Composite
Resin combination and preparation method thereof, can efficiently solve above-mentioned technical problem.
The technical scheme for solving above-mentioned technical problem is as follows：
A kind of graphene oxide toughening model+composition is provided, the bimaleimide resin composition
For the mixture of the bimaleimide resin comprising graphene oxide, containing tertiary amine groups；The described span containing tertiary amine groups carrys out acyl
Imide resin is by least one of modifying agent such as glycidyl amine type epoxy resin, diamine compound, glycidol ether
At least one of toughener such as type epoxy resin, novolac epoxy resin, allyl compound, cyanate ester are to BMI
Resin modified is obtained.
Particularly, wherein：The mass ratio of graphene oxide and bimaleimide resin containing tertiary amine groups is：0.0001~
0.3；
There is provided a kind of preparation method of graphene oxide toughening model+composition, specific steps simultaneously
It is as follows：
1) graphene oxide water solution is prepared
It is ultrasonically treated to graphene oxide and the progress of the mixture of deionized water under the conditions of 0~50 DEG C, obtain aoxidizing stone
Black aqueous solution；
2) bimaleimide resin containing tertiary amine groups is prepared
Modifying agent, toughener and bimaleimide resin are mixed, by mixture in 50~200 DEG C of temperature conditionss
Under, in the inert gas environment such as argon gas or nitrogen carry out 20~150min of melt process, obtain the bismaleimide containing tertiary amine groups
Polyimide resin；Modifying agent is at least one of glycidyl amine type epoxy resin, diamine compound；Modifying agent with before modified
The mass ratio of bimaleimide resin is 0.1~1；Toughener is diglycidyl ether type epoxy resin, novolac epoxy resin, alkene
At least one of compound, cyanate ester；The mass ratio of toughener and bimaleimide resin before modified is less than etc.
In 1；
3) graphene oxide toughening model+composition
By step 1) prepare graphene oxide water solution and step 2) prepare the BMI tree containing tertiary amine groups
Fat, is mixed under 25~100 DEG C of temperature conditionss, and removes water through pervaporation, vacuum distillation or freeze-drying, obtains oxygen
The bimaleimide resin composition of graphite alkene toughness reinforcing；Graphene oxide and bimaleimide resin containing tertiary amine groups
Mass ratio is：0.0001~0.3.
Further, step 3) in mixing speed be 200~15000r/min, the stir process time be 10~
100min。
Further, step 1) in supersonic frequency be 1~100kHz；The ultrasonic time is 5~150min.
Further, step 1) in graphene oxide be single-layer graphene oxide, multilayer graphene oxide at least
It is a kind of；The concentration of the graphene oxide water solution is 1~10mg/mL.
Further, step 2) bimaleimide resin be diphenyl-methane type BMI, diphenyl ether type
BMI, alkyl type BMI, to penylene type BMI, penylene type BMI, neighbour
Penylene type BMI, diphenyl sulphone (DPS) type BMI or di- benzene-type span carry out at least one of first acid imide.
Further, step 2) glycidyl amine type epoxy resin be triglycidyl group para-aminophenol, four contracting
Water glycerine MDA, four glycidol diaminodiphenyl sulfides, four glycidol diaminodiphenyl ethers, four shrink sweet
The oily cyclohexan of diaminourea two, four glycidol diaminourea hexichol fluorenes, N, N, N ', N '-four glycidyl group -3,3 '-diethyl -
4,4 '-MDA, N, N, N ', N '-four glycidyl group -3,3 '-dimethyl -4,4 '-MDA, N,
At least one of N, N ', N '-four glycidyl group -3,3 ', 5,5 '-tetramethyl -4,4 '-MDA.
Further, step 2) diamine compound preferably 1,6- hexamethylene diamines, cyclohexanediamine, p-phenylenediamine, isophthalic
Diamines, benzidine, MDA, diaminodiphenyl sulfide, diaminodiphenyl ether, '-two of 3,3 '-diethyl -4,4
Diaminodiphenylmethane, 3,3 '-dimethyl -4,4 '-MDA, 3,3 ', 5,5 '-tetramethyl -4,4 '-diaminourea hexichol
At least one of methane, the cyclohexan of diaminourea two, diaminourea hexichol fluorenes.
Further, step 2) the diglycidyl ether type epoxy resin be the trade mark E54, E51, E44, E21 or E20 ring
At least one of oxygen tree fat.The novolac epoxy resin is the trade mark JF-45, JF-43, F-51, F-50, F-48, F-44 phenol
At least one of formaldehyde epoxy resin.
Further, step 2) allyl compound be chavicol, 2,2 '-diallyl bisphenol, bisphenol-A
At least one of diallyl ether.
Further, step 2) the preferred bisphenol A cyanate ester of cyanate ester, bisphenol b type cyanate, bisphenol-f type cyanic acid
Ester, tetramethyl bisphenol-f type cyanate, bis-phenol M types cyanate, phenolic cyanate, cyclopentadiene cyanate or two (4- cyanic acid ester groups
At least one of phenyl) ethane.
Further, step 2) temperature when being melted is 50~200 DEG C, the melt process time is 20~
150min；The inert atmosphere is at least one of argon gas, nitrogen.
The present invention has advantages below：
The preparation method 1 of graphene oxide toughening model+composition of the present invention) can be effective
Ground solves the problem of graphene oxide is reunited in bimaleimide resin, disperses uneven；2) need not be to graphite oxide
Alkene carries out physics, chemical modification, thus preparation technology is simple, it is easy to operate, beneficial to the industrial applications of graphene oxide；3) not
Organic solvent is needed to use, cost is reduced, environmental pollution is reduced.Graphene oxide toughness reinforcing span of the present invention carrys out acyl
Imide resin composition, graphene oxide is uniformly dispersed in matrix resin, and the overall performance of resin cured matter is improved, and is
Prepare the matrix resin that High performance nanometer composite material of future generation, resin-based carbon fiber composite provide function admirable.
Embodiment
By following preferred example, the present invention is described in further detail, unless otherwise instructed, following tool
The consumption of each material is mass content in body embodiment.
Example 1：
Each raw material is weighed by following portions by weight：
100 parts of N, N ' -4,4 '-diphenyl methane dimaleimide
3,3 '-dimethyl -4,4 ' 30 parts of-MDA
3 parts of graphene oxide
300 parts of deionized water
Graphene oxide toughening model+composition is prepared as follows：
Graphene oxide and deionized water, and the ultrasonically treated 8min under the conditions of 0 DEG C, 80kHz are weighed first, can be obtained
Required graphene oxide water solution.
Secondly, N, N ' -4,4 '-diphenyl methane dimaleimide, 3,3 '-dimethyl -4,4 '-diaminourea hexichol first are weighed
Alkane, mixture is well mixed and isothermal reaction 20min under the conditions of 140 DEG C, argon gas, required bismaleimide can be obtained
Polyimide resin composition.
Finally, under 25 DEG C of temperature conditionss, with 3000r/min mixing speed by the graphene oxide water solution of preparation and
Bimaleimide resin composition stirs, and stops stirring after 10min, and remove in mixture by Rotary Evaporators
Deionized water, can obtain the bimaleimide resin composition of graphene oxide toughness reinforcing.
Example 2：
Each raw material is weighed by following portions by weight：
100 parts of N, N ' -4,4 '-Diphenyl Ether Bismaleimide
75 parts of 2,2 '-diallyl bisphenol
10 parts of four glycidol MDAs (AG-80 epoxy resin)
1 part of graphene oxide
100 parts of deionized water
Graphene oxide toughening model+composition is prepared as follows：
First, graphene oxide and deionized water, and the ultrasonically treated 10min under the conditions of 30 DEG C, 1kHz are weighed, institute is obtained
The graphene oxide water solution needed, it is standby.
Secondly, four glycidol MDAs, 2,2 '-diallyl double A and N, N are weighed ' -4,4 '-hexichol
Ether BMI, mixture is well mixed and isothermal reaction 30min under the conditions of 130 DEG C, argon gas, double needed for obtaining
Maleimide resin composition, is cooled to room temperature standby.
Finally, under 50 DEG C of temperature conditionss, with 500r/min mixing speed to the graphene oxide water solution of preparation and
Bimaleimide resin is stirred 20min, and water layer is become colorless by brown, stops stirring, and pass through rotary evaporation
Instrument is handled mixture, is removed the deionized water in mixture, can be obtained the bismaleimide of graphene oxide toughness reinforcing
Polyimide resin composition.
Example 3：
Each raw material is weighed by following portions by weight：
100 parts of N, N ' -4,4 '-diphenyl methane dimaleimide
50 parts of 4,4 '-MDA
10 parts of JF45 novolac epoxy resins
10 parts of triglycidyl group para-aminophenol
0.2 part of graphene oxide
20 parts of deionized water
Graphene oxide toughening model+composition is prepared as follows：
Weigh N, N ' -4,4 '-diphenyl methane dimaleimide, 4,4 '-MDA, JF45 epoxy novolac trees
Fat and triglycidyl group para-aminophenol (AFG-90 epoxy resin), mixture is well mixed under 130 DEG C, condition of nitrogen gas
And isothermal reaction 30min, required bimaleimide resin composition can be obtained.
Graphene oxide and deionized water, and the ultrasonically treated 5min under the conditions of 10 DEG C, 50kHz are weighed, institute can be obtained
The graphene oxide water solution needed.Afterwards, under the conditions of 25 DEG C, 1000r/min, by graphene oxide water solution with 20mL/min
Speed be added dropwise in the bimaleimide resin of preparation, after graphene aqueous solution completion of dropwise addition to be oxidized, continue to stir
Mix 10min.Stop after stirring, stand and extract the residual deionized water in the deionized water in mixture, residue and then pass through
Rotary Evaporators are removed, and can obtain the bimaleimide resin composition of graphene oxide toughness reinforcing.
Example 4：
Each raw material is weighed by following portions by weight：
100 parts of N, N ' -4,4 '-Diphenyl Ether Bismaleimide
60 parts of double A types cyanate ester
20 parts of E51 epoxy resin
20 parts of triglycidyl group para-aminophenol
3 parts of graphene oxide
200 parts of deionized water
Graphene oxide toughening model+composition is prepared as follows：
Graphene oxide and deionized water, and the ultrasonically treated 20min under the conditions of 10 DEG C, 100kHz are weighed first, can be with
Obtain required graphene oxide water solution.
Secondly, N, N ' -4,4 '-Diphenyl Ether Bismaleimide, double A types cyanate ester, E51 epoxy resin and three contractings are weighed
Water glyceryl para-aminophenol (AFG-90 epoxy resin), mixture is well mixed under 120 DEG C, condition of nitrogen gas and constant temperature is anti-
40min is answered, required bimaleimide resin composition can be obtained.
Finally, under 30 DEG C of temperature conditionss, with 1500r/min mixing speed by the graphene oxide water solution of preparation and
Bimaleimide resin composition stirs 15min, stops stirring, stands and extract the deionized water in mixture, Zhi Houtong
The method for crossing vacuum distillation removes the deionized water remained in mixture, can obtain the bismaleimide of graphene oxide toughness reinforcing
Polyimide resin composition.
Example 5：
Each raw material is weighed by following portions by weight：
N, N ' -4,4 ' -100 parts of diphenyl sulphone (DPS) BMI
40 parts of 4,4 '-MDA
N, N, N ' N '-four glycidyl group -3,3 '-diethyl -4,4 ' 10 parts of-MDA
0.1 part of graphene oxide
50 parts of deionized water
Graphene oxide toughening model+composition is prepared as follows：
Graphene oxide and deionized water, and the ultrasonically treated 15min under the conditions of 0 DEG C, 20kHz are weighed first, can be obtained
To required graphene oxide water solution.
Secondly, N, N ' -4,4 '-diphenyl sulphone (DPS) BMI, 4,4 '-MDA, N, N, N are weighed ' N '-four
Mixture is well mixed by glycidyl -3,3 '-diethyl -4,4 '-MDA under the conditions of 140 DEG C, argon gas
And isothermal reaction 30min, required bimaleimide resin composition can be obtained.
Finally, under 25 DEG C of temperature conditionss, with 700r/min mixing speed by the graphene oxide water solution of preparation and
Bimaleimide resin composition stirs, and stops stirring after 12min, stands and the deionized water in withdraw mix,
The deionized water remained in mixture is removed by freeze drier afterwards, the span that can obtain graphene oxide toughness reinforcing carrys out acyl
Imide resin composition.
Claims (10)
1. a kind of preparation method of graphene oxide toughening model+composition, is comprised the following steps that：
1) graphene oxide water solution is prepared
It is ultrasonically treated to graphene oxide and the progress of the mixture of deionized water under the conditions of 0~50 DEG C, obtain graphene oxide
The aqueous solution；
2) bimaleimide resin containing tertiary amine groups is prepared
Modifying agent, toughener and bimaleimide resin are mixed, by mixture under 50~200 DEG C of temperature conditionss, argon
20~150min of melt process is carried out in the inert gas environment such as gas or nitrogen, the BMI tree containing tertiary amine groups is obtained
Fat；Modifying agent is at least one of glycidyl amine type epoxy resin, diamine compound；Modifying agent and span before modified
The mass ratio of bismaleimide resin is 0.1~1；Toughener is diglycidyl ether type epoxy resin, novolac epoxy resin, pi-allyl
At least one of compound, cyanate ester；The mass ratio of toughener and bimaleimide resin before modified is less than or equal to 1；
3) graphene oxide toughening model+composition
By step 1) prepare graphene oxide water solution and step 2) prepare the bimaleimide resin containing tertiary amine groups,
Mix, and remove water under 25~100 DEG C of temperature conditionss through pervaporation, vacuum distillation or freeze-drying, obtain aoxidizing stone
The bimaleimide resin composition of black alkene toughness reinforcing；The quality of graphene oxide and bimaleimide resin containing tertiary amine groups
Than for：0.0001~0.3.
2. a kind of preparation method of graphene oxide toughening model+composition as claimed in claim 1, its
It is characterised by：Step 3) in mixing speed be 200~15000r/min, the stir process time be 10~100min.
3. a kind of preparation method of graphene oxide toughening model+composition as claimed in claim 1, its
It is characterised by：Step 1) in supersonic frequency be 1~100kHz；The ultrasonic time is 5~150min.
4. a kind of preparation method of graphene oxide toughening model+composition as claimed in claim 1, its
It is characterised by：Step 1) in graphene oxide at least one of for single-layer graphene oxide, multilayer graphene oxide；It is described
The concentration of graphene oxide water solution is 1~10mg/mL.
5. a kind of preparation method of graphene oxide toughening model+composition as claimed in claim 1, its
It is characterised by：Step 2) bimaleimide resin is that diphenyl-methane type BMI, diphenyl ether type span carry out acyl
It is imines, alkyl type BMI, double to penylene type BMI, a penylene type BMI, adjacent penylene type
Maleimide, diphenyl sulphone (DPS) type BMI or di- benzene-type span carry out at least one of first acid imide.
6. a kind of preparation method of graphene oxide toughening model+composition as claimed in claim 1, its
It is characterised by：Step 2) glycidyl amine type epoxy resin be triglycidyl group para-aminophenol, four glycidols two
Diaminodiphenylmethane, four glycidol diaminodiphenyl sulfides, four glycidol diaminodiphenyl ethers, four glycidol diaminourea
Two cyclohexans, four glycidol diaminourea hexichol fluorenes, N, N, N ', N '-four glycidyl group -3,3 '-'-two of diethyl -4,4
Diaminodiphenylmethane, N, N, N ', N '-four glycidyl group -3,3 '-dimethyl -4,4 '-MDA, N, N, N ',
At least one of N '-four glycidyl group -3,3 ', 5,5 '-tetramethyl -4,4 '-MDA.
7. a kind of preparation method of graphene oxide toughening model+composition as claimed in claim 1, its
It is characterised by：Step 2) the preferred 1,6- hexamethylene diamines of diamine compound, cyclohexanediamine, p-phenylenediamine, m-phenylene diamine (MPD), biphenyl
Diamines, MDA, diaminodiphenyl sulfide, diaminodiphenyl ether, 3,3 '-diethyl -4,4 '-diaminourea hexichol first
Alkane, 3,3 '-dimethyl -4,4 '-MDA, 3,3 ', 5,5 '-tetramethyl -4,4 '-MDA, diamino
At least one of the cyclohexan of base two, diaminourea hexichol fluorenes.
8. a kind of preparation method of graphene oxide toughening model+composition as claimed in claim 1, its
It is characterised by：Step 2) the diglycidyl ether type epoxy resin for the trade mark E54, E51, E44, E21 or E20 epoxy resin in
At least one；The novolac epoxy resin is the trade mark JF-45, JF-43, F-51, F-50, F-48, F-44 epoxy novolac tree
At least one of fat.
9. a kind of preparation method of graphene oxide toughening model+composition as claimed in claim 1, its
It is characterised by：Step 2) allyl compound be chavicol, 2,2 '-diallyl bisphenol, bisphenol-A diallyl
At least one of ether.
10. a kind of preparation method of graphene oxide toughening model+composition as claimed in claim 1, its
It is characterised by：Step 2) the preferred bisphenol A cyanate ester of cyanate ester, bisphenol b type cyanate, bisphenol-f type cyanate, tetramethyl
Bisphenol-f type cyanate, bis-phenol M types cyanate, phenolic cyanate, cyclopentadiene cyanate or two (4- cyanatephenyls) ethane
At least one of.
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| CN110452414A (en) * | 2019-08-23 | 2019-11-15 | 哈尔滨工业大学 | A kind of preparation method of high starch breeding alkene enhancing bismaleimide resin based composites |
| CN113265049A (en) * | 2021-04-16 | 2021-08-17 | 黄必霞 | High-flexibility antistatic synthetic resin and preparation method thereof |
| CN113913107A (en) * | 2021-08-25 | 2022-01-11 | 浙江儒商科技有限公司 | Preparation method of bismaleimide self-lubricating wear-resistant swash plate |
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| CN110283528A (en) * | 2019-06-27 | 2019-09-27 | 浙江儒商科技有限公司 | A kind of preparation method of the wear-resistant self-lubricating swash plate based on bismaleimide |
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| CN113913107A (en) * | 2021-08-25 | 2022-01-11 | 浙江儒商科技有限公司 | Preparation method of bismaleimide self-lubricating wear-resistant swash plate |
| CN114015349A (en) * | 2021-12-21 | 2022-02-08 | 东莞宇隆电工材料有限公司 | Enameled wire anti-aging coating |
| CN114015349B (en) * | 2021-12-21 | 2022-04-15 | 东莞宇隆电工材料有限公司 | Enameled wire anti-aging coating |
| CN116178954A (en) * | 2022-12-15 | 2023-05-30 | 常州天启新新科技有限公司 | Bismaleimide resin composite material for carbon fiber prepreg tape and preparation method thereof |
| CN116178954B (en) * | 2022-12-15 | 2023-10-03 | 常州天启新新科技有限公司 | Bismaleimide resin composite material for carbon fiber prepreg tape and preparation method thereof |
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