CN114381039A - Ceramic filler, preparation method thereof and epoxy resin composite material containing ceramic filler - Google Patents
Ceramic filler, preparation method thereof and epoxy resin composite material containing ceramic filler Download PDFInfo
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- CN114381039A CN114381039A CN202210065819.0A CN202210065819A CN114381039A CN 114381039 A CN114381039 A CN 114381039A CN 202210065819 A CN202210065819 A CN 202210065819A CN 114381039 A CN114381039 A CN 114381039A
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- epoxy resin
- resin composite
- porcelain
- composite material
- filler
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 126
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 126
- 239000002131 composite material Substances 0.000 title claims abstract description 87
- 239000000945 filler Substances 0.000 title claims abstract description 76
- 239000000919 ceramic Substances 0.000 title abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 51
- 229910052580 B4C Inorganic materials 0.000 claims abstract description 35
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000010703 silicon Substances 0.000 claims abstract description 35
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 35
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 4
- 239000011247 coating layer Substances 0.000 claims abstract 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 62
- 239000000203 mixture Substances 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 45
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 44
- 238000001035 drying Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 24
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 claims description 22
- 229940083037 simethicone Drugs 0.000 claims description 22
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 19
- -1 allyl benzoxazine Chemical compound 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 13
- 230000004907 flux Effects 0.000 claims description 6
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 238000002679 ablation Methods 0.000 abstract description 17
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 13
- 239000003063 flame retardant Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 7
- 239000000779 smoke Substances 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 239000002341 toxic gas Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 31
- 239000000843 powder Substances 0.000 description 20
- 238000005303 weighing Methods 0.000 description 20
- 239000012046 mixed solvent Substances 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000000967 suction filtration Methods 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 5
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 5
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 239000004843 novolac epoxy resin Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229920002866 paraformaldehyde Polymers 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 125000000746 allylic group Chemical group 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 230000008054 signal transmission Effects 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000007130 inorganic reaction Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- 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
- C08K3/02—Elements
-
- 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
-
- 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
- C08K3/02—Elements
- C08K2003/023—Silicon
-
- 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
- C08K2003/387—Borates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a porcelain forming filler, a preparation method thereof and an epoxy resin composite material containing the same. The porcelain forming filler comprises boron carbide, simple substance silicon, fluxing agent, zinc borate and allyl polybenzoxazine forming a coating layer. The epoxy resin composite material disclosed by the invention generates a high-strength compact ceramic body in a high-temperature ablation environment, so that heat is prevented from being transferred to the interior, and the interior of the material is prevented from being further damaged; meanwhile, the ceramic layer formed in the ablation process can also prevent volatile matters such as toxic gas and the like in the epoxy resin from escaping, so that the flame retardant property of the epoxy resin can be effectively improved, and the thermal degradation rate and the smoke forming rate are reduced.
Description
Technical Field
The invention relates to the field of epoxy resin composite materials. In particular, the invention relates to a porcelain forming filler, a preparation method thereof and an epoxy resin composite material containing the same.
Background
The epoxy resin has excellent insulating property, bonding property, thermal stability and mechanical property, so that the epoxy resin is widely applied to the fields of automobile body primer, automobile electrical component copper clad plates, welding spot welding glue, new energy automobile battery package materials and the like.
However, epoxy resins have poor flame retardant properties, low Limiting Oxygen Index (LOI), are extremely flammable, and produce a large amount of black smoke during combustion, limiting their application in areas where flame retardancy is required. Therefore, the flame retardant modification of the epoxy resin has very important theoretical and practical significance.
CN107022169B discloses a resin composition containing (a) an epoxy resin, (B) a curing agent, (C) a fluorine atom-containing alkoxysilane compound, and (D) an inorganic filler. The composition has flame retardant properties due to the presence of (C) a fluorine atom-containing alkoxysilane compound.
CN112694714A discloses an epoxy resin composition comprising a first epoxy resin, a benzoxazine, a curing agent and optionally a filler. Wherein the benzoxazine plays a role in flame retardance.
CN101418204B discloses a halogen-free flame-retardant adhesive, which is composed of resin, inorganic filler, curing accelerator and solvent, and is characterized in that the ratio of the resin to the inorganic filler to the curing accelerator to the solvent is as follows according to the mass ratio: 100 parts of resin, 20-60 parts of inorganic filler, 0.1-5 parts of curing accelerator and 50-150 parts of solvent; the resin is a composition comprising 35-50 parts of benzoxazine resin, 25-45 parts of multifunctional epoxy resin and 10-25 parts of linear phenolic resin according to the mass ratio; the multifunctional epoxy resin in the resin component is as follows: phenol novolac epoxy resin, biphenyl novolac epoxy resin, o-cresol novolac epoxy resin, bisphenol a novolac epoxy resin, or a composite of two of them. Wherein the benzoxazine plays a role in flame retardance.
There remains a need in the art to improve the flame retardant properties of epoxy resins.
Disclosure of Invention
The invention aims to improve the flame retardant property of the epoxy resin.
The inventor finds that: by combining the specific ceramic-forming filler with the epoxy resin, the flame retardant properties of the epoxy resin can be improved.
Thus, according to a first aspect of the present invention there is provided a porcelain forming filler comprising boron carbide, elemental silicon, a fluxing agent, zinc borate and a coating forming allyl polybenzoxazine.
According to a second aspect of the present invention, there is provided a method of preparing the above-described porcelain-forming filler, comprising the steps of:
I) mixing boron carbide, simple substance silicon, a fluxing agent and zinc borate to obtain a mixture;
II) dispersing the obtained mixture and allyl benzoxazine into a solvent, heating to 120-160 ℃, reacting for 2-6 h, continuously heating to 180-200 ℃, reacting for 1-4 h, and cooling the reaction system to room temperature; and
III) separating and drying the obtained product to obtain the porcelain forming filler.
According to a third aspect of the present invention, there is provided an epoxy resin composite comprising an epoxy resin and the above-mentioned porcelain-forming filler.
According to a fourth aspect of the present invention, there is provided an automobile part which is produced using the above epoxy resin composite material.
In a high-temperature ablation environment, the ceramic-forming filler per se or the cracking residue of the epoxy resin matrix generates a series of pyrolysis reactions to generate a high-strength compact ceramic body, so that heat is prevented from being transferred to the interior, and the interior of the material is prevented from being further damaged; meanwhile, the ceramic layer formed in the ablation process can also prevent volatile matters such as toxic gas and the like in the epoxy resin from escaping, so that the flame retardant property of the epoxy resin can be effectively improved, and the thermal degradation rate and the smoke forming rate are reduced. In addition, the ceramic body formed during ablation is stronger and can also prevent the epoxy matrix from collapsing.
Drawings
The invention will be described and explained in more detail below with reference to the drawings, in which:
FIG. 1 shows a scanning electron micrograph of the ceramic-forming filler prepared in example 1;
FIG. 2 shows a scanning electron micrograph of the ceramic-forming filler prepared in example 2 after ablation at 1000 ℃;
FIG. 3 shows the apparent morphology of the epoxy resin composite material prepared in example 3 after ablation at 1000 ℃.
Detailed Description
Various aspects of the invention and still further objects, features and advantages will be more fully apparent hereinafter.
According to a first aspect of the present invention there is provided a ceramic forming filler comprising boron carbide, elemental silicon, a fluxing agent, zinc borate and a coating forming allyl polybenzoxazine.
Preferably, the fluxing agent is sodium carbonate.
Preferably, the mass ratio of boron carbide, elemental silicon, fluxing agent and zinc borate is 30: 20-50: 15-25: 5-25.
The allylic polybenzoxazine is at least partially coated with a mixture of boron carbide, elemental silicon, flux, and zinc borate, and preferably, is completely coated with a mixture of boron carbide, elemental silicon, flux, and zinc borate.
Preferably, the mass ratio of the total mass of the boron carbide, the elemental silicon, the fluxing agent and the zinc borate to the allyl benzoxazine is 1: 0.1-0.4.
Preferably, the inorganic component of the ceramic forming material consists of boron carbide, elemental silicon, a fluxing agent and zinc borate.
According to a second aspect of the present invention, there is provided a method of preparing the above-described porcelain-forming filler, comprising the steps of:
I) mixing boron carbide, simple substance silicon, a fluxing agent and zinc borate to obtain a mixture;
II) dispersing the obtained mixture and allyl benzoxazine into a solvent, heating to 120-160 ℃, reacting for 2-6 h, continuously heating to 180-200 ℃, reacting for 1-4 h, and cooling the reaction system to room temperature; and
III) separating and drying the obtained product to obtain the porcelain forming filler.
Preferably, the fluxing agent is sodium carbonate.
Preferably, the boron carbide, the elemental silicon, the flux and the zinc borate are dried before step I).
Preferably, the drying is performed under vacuum.
Preferably, the drying is carried out at 40-60 ℃.
The temperature at which the mixing is carried out is not particularly limited. The mixing may be carried out at room temperature.
If drying is performed prior to mixing, the mixing may be performed after drying, with or without cooling.
Preferably, the mixing is performed by milling, for example by ball milling.
Preferably, in the step II), the mass ratio of boron carbide, elemental silicon, flux and zinc borate is 30: 20-50: 15-25: 5-25.
The allylic benzoxazines described in this application have the following structural formula:
the allylic benzoxazine can be prepared as follows:
weighing phenol and paraformaldehyde with a molar ratio of 1:2, dissolving the phenol and the paraformaldehyde in a proper amount of toluene, adding the mixture into a reaction container, and dropwise adding allylamine with the mass of phenol and the like under the stirring condition of 40-60 ℃. After the dropwise addition, the reaction is carried out for 8 to 12 hours at the temperature of between 70 and 90 ℃, after the reaction is finished, dichloromethane, NaOH aqueous solution (such as NaOH aqueous solution with the concentration of 30wt.%) and saturated NaCl aqueous solution are sequentially used for extraction, and finally, the pressure reduction and the suction filtration are carried out, and the solvent is removed to obtain the yellow viscous allyl benzoxazine.
Preferably, the solvent used in step II) is selected from the group consisting of simethicone, chloroform and mixtures thereof.
More preferably, the solvent used in step II) is a mixture of simethicone and chloroform, wherein the mass ratio of simethicone to chloroform is 1-3: 2-8.
Preferably, the mass ratio of the mixture to the allyl benzoxazine is 1: 0.1-0.4.
Preferably, the mass ratio of the mixture to the solvent is 1: 3-8.
The separation in step III) may employ filtration, centrifugation or a combination thereof.
The invention utilizes the allyl polybenzoxazine to form the allyl polybenzoxazine to coat the inorganic ceramic powder by ring opening on the surface of the ceramic filler, and the allyl polybenzoxazine has higher carbon residue rate and can participate in the inorganic reaction process of the ceramic filler, thereby being beneficial to forming a ceramic body and improving the flame retardant property of the material.
According to a third aspect of the present invention, there is provided an epoxy resin composite comprising an epoxy resin and the above-mentioned porcelain-forming filler.
The kind of the epoxy resin is not particularly limited and may be any type of epoxy resin commonly used in the art.
As examples of the epoxy resin, there may be mentioned E-51 type epoxy resin, E-44 type epoxy resin, bisphenol F type epoxy resin, polyphenol type glycidyl ether epoxy resin and the like.
The weight ratio of the epoxy resin to the porcelain forming filler is 100: 30-80.
The composite material further comprises a curing agent. More preferably, the curing agent is an amine curing agent.
As examples of the curing agent, p-phenylenediamine, 4 '-diaminodiphenyl ether, 4' -diaminodiphenylmethane, and the like can be mentioned.
Preferably, the curing agent is selected from the group consisting of p-phenylenediamine, 4 '-diaminodiphenyl ether, 4' -diaminodiphenylmethane, and combinations thereof.
Preferably, the weight ratio of the epoxy resin to the curing agent is 100: 15-30.
The epoxy resin composite material may be formed into a desired part by curing under certain conditions.
The inventors have found that epoxy resin composites containing the ceramic-forming filler form a ceramic body with some strength during ablation rather than ash.
Meanwhile, the inventor finds that the epoxy resin composite material containing the porcelain forming filler can form a compact ceramic body at a lower temperature (for example, 1000 ℃).
The ceramic filler shell allyl polybenzoxazine can improve the flame retardant property of epoxy resin, can also obviously improve the interface effect, thereby improving the mechanical strength of a matrix material, and can also improve the heat resistance of the material, so that the property of a ceramic body formed by the epoxy resin at high temperature is improved.
The oxygen index of the epoxy resin composite material can be 33-39%, and the ablation line change rate can be-2.6% -1.1%.
In addition, articles prepared from the epoxy resin composites of the present invention have higher characteristic signal transmission rates than epoxy resins without the addition of a ceramic filler.
According to a fourth aspect of the present invention, there is provided an automobile part which is produced using the above epoxy resin composite material.
The epoxy resin composite material can be further compounded with a reinforcing material such as carbon fiber to obtain a fiber reinforced resin composite material.
The parts can be, for example, an automobile battery pack upper cover plate, an automobile suspension, an ignition coil and the like.
The upper cover plate of the automobile battery pack prepared from the epoxy resin composite material can effectively improve the flame retardant property of the upper cover plate, and the formed ceramic body can play a role in protecting the battery and the circuit.
The terms "comprising" and "including" as used herein encompass the case where other elements not explicitly mentioned are also included or included and the case where they consist of the mentioned elements.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the event that a definition of a term in this specification conflicts with a meaning commonly understood by those skilled in the art to which the invention pertains, the definition set forth herein shall govern.
Unless otherwise indicated, all numbers expressing quantities of ingredients, temperatures, and so forth used in the specification and claims are to be understood as being modified by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth herein are approximations that can vary depending upon the desired properties to be obtained.
Examples
The conception, specific structure, and technical effects of the present invention will be further described in conjunction with the embodiments and the accompanying drawings so that those skilled in the art can fully understand the objects, features, and effects of the present invention. It will be understood by those skilled in the art that the embodiments herein are for illustrative purposes only and the scope of the present invention is not limited thereto.
Example 1
Allylbenzoxazine was prepared as follows:
9.4g of phenol and 6.6g of paraformaldehyde were added to a three-necked flask containing 60ml of toluene with stirring at room temperature, and the temperature was raised to 50 ℃. 5.7g of allylamine were added dropwise. After the dropwise addition, the temperature is raised to 90 ℃ for reaction for 8h, and the reaction product is cooled to room temperature. Then dichloromethane, NaOH aqueous solution (with the concentration of 30wt.%) and saturated NaCl aqueous solution are used for extraction in sequence, and finally the solvent is removed by vacuum filtration to obtain yellow viscous allyl benzoxazine.
An epoxy resin composite was prepared as follows:
s1: preparation of the mixture
Respectively placing boron carbide powder, powdered silicon, sodium carbonate and zinc borate in a drying oven, carrying out vacuum drying for 2h at 50 ℃ under a vacuum condition, and then adding boron carbide powder: and (3) powdered silicon: sodium carbonate: adding the zinc borate into a ball mill according to the mass ratio of 30:30:20:20, and uniformly mixing to obtain a mixture.
S2: forming a porcelain forming filler
Weighing 10g of mixture, 1g of allyl benzoxazine and 30g of mixed solvent of simethicone and chloroform (10 g of simethicone in the solvent and 20g of chloroform in the solvent), adding into a reaction kettle, mechanically stirring and dispersing, heating to 120 ℃ for reaction for 4h, continuously heating to 180 ℃ for reaction for 2h, and cooling the reaction system to room temperature under the stirring condition.
S3: separated into porcelain filler
And (4) washing a product obtained in the step S2 by using chloroform, carrying out suction filtration, and drying to obtain the porcelain forming filler.
FIG. 1 shows a scanning electron micrograph of the ceramic-forming filler prepared in example 1.
As can be seen from fig. 1: the boron carbide powder, the powdered silicon, the sodium carbonate and the zinc borate in a certain proportion are coated by the polybenzoxazine to form the microencapsulated ceramic filler.
S4: preparation of epoxy resin composite
And weighing 100g of epoxy resin E-44, 80g of the porcelain forming filler and 20g of curing agent p-phenylenediamine, and uniformly stirring to obtain the epoxy resin composite material.
S5: curing of epoxy resin composites
Pouring the epoxy resin composite material into a mould, curing for 3h at 120 ℃, 3h at 150 ℃ and 2h at 170 ℃ to prepare the cured epoxy resin composite material.
Example 2
Allylbenzoxazine was prepared as follows:
9.4g of phenol and 6.6g of paraformaldehyde were added to a three-necked flask containing 60ml of toluene with stirring at room temperature, and the temperature was raised to 40 ℃. 5.7g of allylamine were added dropwise. After the dropwise addition, the temperature is raised to 100 ℃ for reaction for 10h, and the reaction product is cooled to room temperature. Then dichloromethane, NaOH aqueous solution (with the concentration of 30wt.%) and saturated NaCl aqueous solution are used for extraction in sequence, and finally the solvent is removed by vacuum filtration to obtain yellow viscous allyl benzoxazine.
An epoxy resin composite was prepared as follows:
s1: preparation of the mixture
Respectively placing boron carbide powder, powdered silicon, sodium carbonate and zinc borate in a drying oven, carrying out vacuum drying for 2h at 50 ℃ under a vacuum condition, and then adding boron carbide powder: and (3) powdered silicon: sodium carbonate: adding the zinc borate into a ball mill according to the mass ratio of 30:40:20:10, and uniformly mixing to obtain a mixture.
S2: forming a porcelain forming filler
Weighing 10g of mixture, 2g of allyl benzoxazine and 30g of mixed solvent of simethicone and chloroform (10 g of simethicone and 20g of chloroform in the mixed solvent), adding into a reaction kettle, mechanically stirring and dispersing, heating to 120 ℃ for reaction for 4h, continuously heating to 180 ℃ for reaction for 2h, and cooling the reaction system to room temperature under the stirring condition.
S3: separated into porcelain filler
And (4) washing a product obtained in the step S2 by using chloroform, carrying out suction filtration, and drying to obtain the porcelain forming filler.
FIG. 2 shows a scanning electron micrograph of the ceramic-forming filler prepared in example 2 after ablation at 1000 ℃.
As can be seen from fig. 2: the ceramic-forming filler forms a dense ceramic body in an ablation environment of 1000 ℃.
S4: preparation of epoxy resin composite
And weighing 100g of epoxy resin E-44, 80g of the porcelain forming filler and 20g of curing agent p-phenylenediamine, and uniformly stirring to obtain the epoxy resin composite material.
S5: curing of epoxy resin composites
Pouring the epoxy resin composite material into a mould, curing for 3h at 120 ℃, 3h at 150 ℃ and 2h at 170 ℃ to prepare the cured epoxy resin composite material.
Example 3
An epoxy resin composite was prepared as follows:
s1: preparation of the mixture
Respectively placing boron carbide powder, powdered silicon, sodium carbonate and zinc borate in a drying oven, carrying out vacuum drying for 2h at the temperature of 60 ℃ under the vacuum condition, and then adding boron carbide powder: and (3) powdered silicon: sodium carbonate: adding the zinc borate in a mass ratio of 30:40:15:15 into a ball mill, and uniformly mixing to obtain a mixture.
S2: forming a porcelain forming filler
Weighing 10g of the mixture, 1.5g of allyl benzoxazine (prepared according to the steps described in example 1) and 40g of mixed solvent of simethicone and chloroform (12 g of simethicone and 28g of chloroform in the mixed solvent) into a reaction kettle, mechanically stirring and dispersing, heating to 130 ℃ for reaction for 4 hours, continuously heating to 190 ℃ for reaction for 3 hours, and cooling the reaction system to room temperature under the stirring condition.
S3: separated into porcelain filler
And (4) washing a product obtained in the step S2 by using chloroform, carrying out suction filtration, and drying to obtain the porcelain forming filler.
S4: preparation of epoxy resin composite
And weighing 100g of epoxy resin E-51, 60g of the porcelain forming filler and 30g of curing agent 4, 4' -diaminodiphenyl ether, and uniformly stirring to obtain the epoxy resin composite material.
S5: curing of epoxy resin composites
Pouring the epoxy resin composite material into a mould, curing for 3h at 150 ℃, 3h at 160 ℃ and 2h after 190 ℃ to prepare the cured epoxy resin composite material.
FIG. 3 shows the apparent morphology of the epoxy resin composite material prepared in example 3 after ablation at 1000 ℃.
As can be seen from fig. 3: the resulting composite material can form a dense ceramic body in an ablation environment of 1000 ℃.
Example 4
An epoxy resin composite was prepared as follows:
s1: preparation of the mixture
Respectively placing boron carbide powder, powdered silicon, sodium carbonate and zinc borate in a drying oven, carrying out vacuum drying for 2h at 40 ℃ under a vacuum condition, and then adding boron carbide powder: and (3) powdered silicon: sodium carbonate: adding the zinc borate in a mass ratio of 30:20:25:25 into a ball mill, and uniformly mixing to obtain a mixture.
S2: forming a porcelain forming filler
Weighing 10g of the mixture, 2g of allyl benzoxazine (prepared according to the steps described in example 1) and 40g of mixed solvent of simethicone and chloroform (12 g of simethicone in the solvent and 28g of chloroform), adding the mixture into a reaction kettle, mechanically stirring and dispersing, heating to 130 ℃ for reaction for 4 hours, continuously heating to 190 ℃ for reaction for 3 hours, and cooling the reaction system to room temperature under the stirring condition.
S3: separated into porcelain filler
And (4) washing a product obtained in the step S2 by using chloroform, carrying out suction filtration, and drying to obtain the porcelain forming filler.
S4: preparation of epoxy resin composite
And weighing 100g of epoxy resin E-51, 60g of the porcelain forming filler and 30g of curing agent 4, 4' -diaminodiphenyl ether, and uniformly stirring to obtain the epoxy resin composite material.
S5: curing of epoxy resin composites
Pouring the epoxy resin composite material into a mould, curing for 3h at 150 ℃, 3h at 160 ℃ and 2h after 190 ℃ to prepare the cured epoxy resin composite material.
Example 5
An epoxy resin composite was prepared as follows:
s1: preparation of the mixture
Respectively placing boron carbide powder, powdered silicon, sodium carbonate and zinc borate in a drying oven, carrying out vacuum drying for 2h at 40 ℃ under a vacuum condition, and then adding boron carbide powder: and (3) powdered silicon: sodium carbonate: adding the zinc borate in a mass ratio of 30:20:25:25 into a ball mill, and uniformly mixing to obtain a mixture.
S2: forming a porcelain forming filler
Weighing 10g of the mixture, 1.5g of allyl benzoxazine (prepared according to the steps described in example 1) and 60g of mixed solvent of simethicone and chloroform (24 g of simethicone and 36g of chloroform in the mixed solvent) into a reaction kettle, mechanically stirring and dispersing, heating to 130 ℃ for reaction for 4 hours, continuously heating to 190 ℃ for reaction for 3 hours, and cooling the reaction system to room temperature under the stirring condition.
S3: separated into porcelain filler
And (4) washing a product obtained in the step S2 by using chloroform, carrying out suction filtration, and drying to obtain the porcelain forming filler.
S4: preparation of epoxy resin composite
And weighing 100g of epoxy resin E-44, 60g of the porcelain forming filler and 25g of curing agent 4, 4' -diaminodiphenyl ether, and uniformly stirring to obtain the epoxy resin composite material.
S5: curing of epoxy resin composites
Pouring the epoxy resin composite material into a mould, curing for 3h at 150 ℃, 3h at 160 ℃ and 2h after 190 ℃ to prepare the cured epoxy resin composite material.
Example 6
An epoxy resin composite was prepared as follows:
s1: preparation of the mixture
Respectively placing boron carbide powder, powdered silicon, sodium carbonate and zinc borate in a drying oven, carrying out vacuum drying for 2h at 40 ℃ under a vacuum condition, and then adding boron carbide powder: and (3) powdered silicon: sodium carbonate: adding the zinc borate in a mass ratio of 30:20:25:25 into a ball mill, and uniformly mixing to obtain a mixture.
S2: forming a porcelain forming filler
Weighing 10g of the mixture, 3g of allyl benzoxazine (prepared according to the steps described in example 1) and 60g of mixed solvent of simethicone and chloroform (24 g of simethicone and 36g of chloroform in the mixed solvent) into a reaction kettle, mechanically stirring and dispersing, heating to 130 ℃ for reaction for 4 hours, continuously heating to 190 ℃ for reaction for 3 hours, and cooling the reaction system to room temperature under the stirring condition.
S3: separated into porcelain filler
And (4) washing a product obtained in the step S2 by using chloroform, carrying out suction filtration, and drying to obtain the porcelain forming filler.
S4: preparation of epoxy resin composite
And weighing 100g of epoxy resin E-44, 30g of the porcelain forming filler and 30g of curing agent 4, 4' -diaminodiphenylmethane, and uniformly stirring to obtain the epoxy resin composite material.
S5: curing of epoxy resin composites
Pouring the epoxy resin composite material into a mould, curing for 3h at 150 ℃, 3h at 160 ℃ and 2h after 190 ℃ to prepare the cured epoxy resin composite material.
Example 7
An epoxy resin composite was prepared as follows:
s1: preparation of the mixture
Respectively placing boron carbide powder, powdered silicon, sodium carbonate and zinc borate in a drying oven, carrying out vacuum drying for 2h at 40 ℃ under a vacuum condition, and then adding boron carbide powder: and (3) powdered silicon: sodium carbonate: adding the zinc borate into a ball mill according to the mass ratio of 30:50:15:5, and uniformly mixing to obtain a mixture.
S2: forming a porcelain forming filler
Weighing 10g of the mixture, 3.5g of allyl benzoxazine (prepared according to the steps described in example 1) and 60g of mixed solvent of simethicone and chloroform (24 g of simethicone and 36g of chloroform in the mixed solvent) into a reaction kettle, mechanically stirring and dispersing, heating to 130 ℃ for reaction for 4 hours, continuously heating to 190 ℃ for reaction for 3 hours, and cooling the reaction system to room temperature under the stirring condition.
S3: separated into porcelain filler
And (4) washing a product obtained in the step S2 by using chloroform, carrying out suction filtration, and drying to obtain the porcelain forming filler.
S4: preparation of epoxy resin composite
And weighing 100g of epoxy resin E-44, 30g of the porcelain forming filler and 30g of curing agent 4, 4' -diaminodiphenylmethane, and uniformly stirring to obtain the epoxy resin composite material.
S5: curing of epoxy resin composites
Pouring the epoxy resin composite material into a mould, curing for 3h at 140 ℃, curing for 3h at 160 ℃, and curing for 2h after 180 ℃ to prepare the cured epoxy resin composite material.
Example 8
An epoxy resin composite was prepared as follows:
s1: preparation of the mixture
Respectively placing boron carbide powder, powdered silicon, sodium carbonate and zinc borate in a drying oven, carrying out vacuum drying for 2h at 40 ℃ under a vacuum condition, and then adding boron carbide powder: and (3) powdered silicon: sodium carbonate: adding the zinc borate into a ball mill according to the mass ratio of 30:50:15:5, and uniformly mixing to obtain a mixture.
S2: forming a porcelain forming filler
Weighing 10g of the mixture, 3g of allyl benzoxazine (prepared according to the steps described in example 1) and 50g of simethicone and chloroform solvent (10 g of simethicone in the solvent and 40g of chloroform) into a reaction kettle, mechanically stirring and dispersing, heating to 140 ℃ for reaction for 4h, continuously heating to 200 ℃ for reaction for 3h, and cooling the reaction system to room temperature under the stirring condition.
S3: separated into porcelain filler
And (4) washing a product obtained in the step S2 by using chloroform, carrying out suction filtration, and drying to obtain the porcelain forming filler.
S4: preparation of epoxy resin composite
And weighing 100g of epoxy resin E-44, 70g of the porcelain forming filler and 30g of curing agent 4, 4' -diaminodiphenylmethane, and uniformly stirring to obtain the epoxy resin composite material.
Pouring into a mould, curing at 140 ℃ for 3h, curing at 160 ℃ for 3h, and post-curing at 180 ℃ for 2h to prepare the epoxy resin composite material.
Example 9
An epoxy resin composite was prepared as follows:
s1: preparation of the mixture
Respectively placing boron carbide powder, powdered silicon, sodium carbonate and zinc borate in a drying oven, carrying out vacuum drying for 2h at 40 ℃ under a vacuum condition, and then adding boron carbide powder: and (3) powdered silicon: sodium carbonate: adding the zinc borate into a ball mill according to the mass ratio of 30:50:15:5, and uniformly mixing to obtain a mixture.
S2: forming a porcelain forming filler
Weighing 10g of the mixture, 2g of allyl benzoxazine (prepared according to the steps described in example 1) and 50g of the mixed solvent of simethicone and chloroform (10 g of simethicone in the mixed solvent and 40g of chloroform) into a reaction kettle, mechanically stirring and dispersing, heating to 140 ℃ for reaction for 4 hours, continuously heating to 200 ℃ for reaction for 3 hours, and cooling the reaction system to room temperature under the stirring condition.
S3: separated into porcelain filler
And (4) washing a product obtained in the step S2 by using chloroform, carrying out suction filtration, and drying to obtain the porcelain forming filler.
S4: preparation of epoxy resin composite
Weighing 100g of epoxy resin E-51, 70g of the porcelain forming filler and 25g of curing agent 4, 4' -diaminodiphenylmethane, and uniformly stirring to obtain the epoxy resin composite material.
S5: curing of epoxy resin composites
Pouring the epoxy resin composite material into a mould, curing for 3h at 140 ℃, curing for 3h at 160 ℃, and curing for 2h after 180 ℃ to prepare the cured epoxy resin composite material.
Comparative example 1
Weighing 100g of epoxy resin E-51 and 25g of curing agent 4, 4' -diaminodiphenylmethane, and uniformly stirring to obtain the epoxy resin composite material.
Pouring the epoxy resin composite material into a mould, curing for 3h at 140 ℃, curing for 3h at 160 ℃, and curing for 2h after 180 ℃ to prepare the cured epoxy resin composite material.
The epoxy resin composites prepared in examples 1 to 9 and comparative example 1 were tested for their properties, wherein:
the mechanical properties of the composite material are measured according to GB/T528-.
The test results are summarized in table 1.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | Example 9 | Comparison of Example (b) | |
| Tensile strength- MPa | 68.5 | 68.4 | 70.5 | 70.4 | 70.1 | 72.8 | 72.7 | 69.2 | 69.5 | 73.5 |
| Elongation at break Rate/%) | 2.5 | 2.6 | 2.8 | 2.8 | 3.1 | 2.9 | 2.9 | 2.7 | 2.7 | 2.8 |
| Oxygen index/% | 38 | 39 | 35 | 35 | 35 | 33 | 33 | 38 | 38 | 24 |
| Strength of ablation body degree/MPa | 76.2 | 79.6 | 79.9 | 75.3 | 75.3 | 74.6 | 80.3 | 80.5 | 80.5 | / |
| Vertical flame retardation and the like Stage | UL94V-0 | UL94V-0 | UL94V-0 | UL94V-0 | UL94V-0 | UL94V-0 | UL94V-0 | UL94V-0 | UL94V-0 | UL94 V-2 |
| Post ablation appearance | Hard and dense Does not crack | Hard and dense Does not crack | Hard and dense Does not crack | Hard and dense Does not crack | Hard and dense Does not crack | Hard and dense Does not crack | Hard and dense Does not crack | Hard and dense Does not crack | Hard and dense Does not crack | / |
| Ablation line variation Rate/%) | -1.1 | -1.2 | -1.5 | -2.4 | -1.8 | -2.3 | -2.6 | -1.3 | -1.3 | -3.5 |
| Characteristic signal transmission Percent of passing% | 65.2 | 65.3 | 52.4 | 49.8 | 47.5 | 47.1 | 45.6 | 62.3 | 62.3 | 30.1 |
As can be seen from table 1: the oxygen index of the epoxy resin composite material can be 33-39%, the ablation line change rate can be-2.6% -1.1%, and the flame retardant grade can reach V-0.
Furthermore, it has been found that: compared with the epoxy resin without the added porcelain filler, the product prepared from the epoxy resin composite material has higher characteristic signal transmittance.
The foregoing describes only exemplary embodiments or examples of the present invention and is not intended to limit the invention. The present invention may be modified and varied by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention are included in the scope of the claims of the present application.
Claims (13)
1. The porcelain forming filler is characterized by comprising boron carbide, simple substance silicon, fluxing agent, zinc borate and allyl polybenzoxazine forming a coating layer.
2. Porcelain forming filler according to claim 1, characterized in that the fluxing agent is sodium carbonate.
3. The porcelain forming filler according to claim 1 or 2, wherein the mass ratio of boron carbide, elemental silicon, flux, zinc borate is 30: 20-50: 15-25: 5-25.
4. A porcelain forming filler according to any of claims 1 to 3, characterized in that the mass ratio of the total mass of boron carbide, elemental silicon, flux and zinc borate to the mass of allylbenzoxazine is 1: 0.1-0.4.
5. A method for preparing a porcelain-forming filler according to any one of claims 1 to 4, characterized by comprising the steps of:
I) mixing boron carbide, simple substance silicon, a fluxing agent and zinc borate to obtain a mixture;
II) dispersing the obtained mixture and allyl benzoxazine into a solvent, heating to 120-160 ℃, reacting for 2-6 h, continuously heating to 180-200 ℃, reacting for 1-4 h, and cooling the reaction system to room temperature; and
III) separating and drying the obtained product to obtain the porcelain forming filler.
6. The process according to claim 5, wherein the solvent used in step II) is selected from the group consisting of simethicone, chloroform and mixtures thereof.
7. The method according to claim 5 or 6, wherein the mass ratio of the mixture to the solvent is 1: 3-8.
8. An epoxy resin composite material, characterized by comprising an epoxy resin and the porcelain forming filler according to any one of claims 1 to 4.
9. The epoxy composite of claim 8, wherein the weight ratio of the epoxy to the porcelainizing filler is 100: 30-80.
10. The epoxy resin composite according to claim 8 or 9, further comprising a curing agent.
11. The epoxy composite of claim 10, wherein the curing agent is selected from the group consisting of p-phenylenediamine, 4 '-diaminodiphenyl ether, 4' -diaminodiphenylmethane, and combinations thereof.
12. The epoxy resin composite according to claim 10 or 11, wherein the weight ratio of the epoxy resin to the curing agent is preferably 100: 15-30.
13. An automotive part, characterized by being produced using the epoxy resin composite material according to any one of claims 8 to 12.
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