CN114381039B - Porcelain filler, preparation method thereof and epoxy resin composite material containing porcelain filler - Google Patents
Porcelain filler, preparation method thereof and epoxy resin composite material containing porcelain filler Download PDFInfo
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- CN114381039B CN114381039B CN202210065819.0A CN202210065819A CN114381039B CN 114381039 B CN114381039 B CN 114381039B CN 202210065819 A CN202210065819 A CN 202210065819A CN 114381039 B CN114381039 B CN 114381039B
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- epoxy resin
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 131
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 131
- 239000002131 composite material Substances 0.000 title claims abstract description 88
- 239000000945 filler Substances 0.000 title claims abstract description 67
- 229910052573 porcelain Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- 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
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 35
- 239000010703 silicon Substances 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
- 238000000034 method Methods 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 5
- 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 49
- 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
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- -1 allyl benzoxazine Chemical compound 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 229940008099 dimethicone Drugs 0.000 claims description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 abstract description 29
- 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 14
- 239000003063 flame retardant Substances 0.000 abstract description 14
- 238000002679 ablation Methods 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 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
- 239000000843 powder Substances 0.000 description 39
- 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 description 16
- 229940083037 simethicone Drugs 0.000 description 16
- 239000012046 mixed solvent Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 238000000967 suction filtration Methods 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 9
- 238000000643 oven drying Methods 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 238000010907 mechanical stirring Methods 0.000 description 7
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 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
- 125000000746 allylic group Chemical group 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 235000013824 polyphenols Nutrition 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 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
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920002866 paraformaldehyde Polymers 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 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 2
- 238000001000 micrograph 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
- 229920002545 silicone oil Polymers 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
- 150000001412 amines Chemical group 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000005253 cladding 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
- 230000006837 decompression Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 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
- 239000003094 microcapsule Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- 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 filler, a preparation method thereof and an epoxy resin composite material containing the porcelain filler. The porcelain-forming filler comprises boron carbide, elemental silicon, fluxing agent, zinc borate and allyl type polybenzoxazine forming a coating layer. The epoxy resin composite material generates a high-strength compact ceramic body in a high-temperature ablation environment, thereby preventing heat from being transferred to the inside and avoiding the inside of the material from being further damaged; meanwhile, the ceramic layer formed in the ablation process can also prevent volatile matters such as toxic gases and the like in the interior from escaping, so that the flame retardant property of the epoxy resin can be effectively improved, and the thermal degradation rate and the smoke formation 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 filler, a preparation method thereof and an epoxy resin composite material containing the porcelain filler.
Background
The epoxy resin has excellent insulating property, adhesive property, thermal stability and mechanical property, so the epoxy resin is widely applied in the fields of automobile body priming paint, automobile electrical element copper cladding plates, welding spot welding glue, new energy automobile battery packaging materials and the like.
However, epoxy resins have poor flame retardant properties, low Limiting Oxygen Index (LOI), are highly flammable, and produce a large amount of black smoke when burned, limiting their use in areas where flame retardancy is desired. 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) an alkoxysilane compound containing fluorine atoms, and (D) an inorganic filler. The composition has flame retardant properties due to the presence of (C) an alkoxysilane compound containing a fluorine atom.
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 consists 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 by 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: any one or two of phenol type phenolic epoxy resin, biphenyl type phenolic epoxy resin, o-cresol type phenolic epoxy resin and bisphenol A type phenolic epoxy resin. 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 epoxy resin.
The inventors found that: by combining specific porcelain-forming fillers 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 allylic polybenzoxazine forming a coating.
According to a second aspect of the present invention there is provided a method of preparing a porcelain filler as described above comprising the steps of:
I) Mixing boron carbide, simple substance silicon, fluxing agent and zinc borate to obtain a mixture;
II) dispersing the obtained mixture and allyl benzoxazine into a solvent, heating to 120-160 ℃ to react for 2-6 h, continuously heating to 180-200 ℃ to react 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 a porcelain filler as described above.
According to a fourth aspect of the present invention, there is provided an automotive part prepared using the epoxy resin composite material described above.
In the high-temperature ablation environment, the ceramic filler itself or the cracking residue of the epoxy resin matrix generates a series of pyrolysis reactions to generate a high-strength compact ceramic body, thereby preventing heat from being transferred to the inside and avoiding the inside of the material from being further damaged; meanwhile, the ceramic layer formed in the ablation process can also prevent volatile matters such as toxic gases and the like in the interior from escaping, so that the flame retardant property of the epoxy resin can be effectively improved, and the thermal degradation rate and the smoke formation rate are reduced. In addition, the ceramic body formed in the ablation process has higher strength and can also prevent the epoxy resin matrix from collapsing.
Drawings
The invention is described and explained in more detail below with reference to the attached drawing figures, wherein:
FIG. 1 shows a scanning electron microscope picture of the porcelain filler prepared in example 1;
FIG. 2 shows a scanning electron microscope image of the ceramic filler prepared in example 2 after 1000℃ablation;
FIG. 3 shows the apparent morphology of the epoxy resin composite prepared in example 3 after ablation at 1000 ℃.
Detailed Description
Various aspects, as well as further objects, features, and advantages of the present invention will be more fully apparent hereinafter.
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 allylic polybenzoxazine forming a coating.
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, fluxing agent, and zinc borate, preferably fully coated with a mixture of boron carbide, elemental silicon, fluxing agent, and zinc borate.
Preferably, the mass ratio of the total mass of boron carbide, elemental silicon, fluxing agent and zinc borate to allylbenzoxazine is 1:0.1-0.4.
Preferably, the inorganic component of the porcelain-forming material consists of boron carbide, elemental silicon, fluxing agent and zinc borate.
According to a second aspect of the present invention there is provided a method of preparing a porcelain filler as described above comprising the steps of:
I) Mixing boron carbide, simple substance silicon, fluxing agent and zinc borate to obtain a mixture;
II) dispersing the obtained mixture and allyl benzoxazine into a solvent, heating to 120-160 ℃ to react for 2-6 h, continuously heating to 180-200 ℃ to react 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, elemental silicon, fluxing agent and zinc borate are dried prior to step I).
Preferably, the drying is performed under vacuum.
Preferably, the drying is performed at 40-60 ℃.
The temperature at which the mixing is carried out is not particularly limited. The mixing may be performed at room temperature.
If the drying is performed before the mixing, the mixing may be performed after the 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, fluxing agent and zinc borate is 30:20-50:15-25:5-25.
The allylic benzoxazine disclosed by the application has the following structural formula:
the allylic benzoxazine may be prepared as follows:
Weighing phenol and paraformaldehyde in a molar ratio of 1:2, dissolving in a proper amount of toluene, adding into a reaction container, and dropwise adding allylamine with mass such as phenol under the stirring condition of 40-60 ℃. After the dripping is finished, the mixture is reacted for 8 to 12 hours at the temperature of 70 to 90 ℃, after the reaction is finished, dichloromethane, naOH aqueous solution (for example, naOH aqueous solution with the concentration of 30wt percent) and saturated NaCl aqueous solution are sequentially used for extraction, and finally, the yellow sticky allyl benzoxazine is obtained by decompression and suction filtration and solvent removal.
Preferably, the solvent used in step II) is selected from the group consisting of dimethicone, chloroform and mixtures thereof.
More preferably, the solvent used in step II) is a mixture of dimethicone and chloroform, wherein the mass ratio of dimethicone to chloroform is 1-3:2-8.
Preferably, the mass ratio of the mixture to the allylbenzoxazine 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 allyl benzoxazine to open loop on the surface of the porcelain-forming filler to form allyl polybenzoxazine to coat the inorganic ceramic powder, and the allyl polybenzoxazine has higher carbon residue rate and can participate in the inorganic reaction process of the porcelain-forming filler, thereby being beneficial to the formation of ceramic bodies 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 a porcelain filler as described above.
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 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' -diaminodiphenyl methane 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 composite material may be cured under certain conditions to form the desired part.
The inventors have found that epoxy composites containing the porcelain-forming filler form ceramic bodies with a certain strength rather than ash during the ablation process.
Meanwhile, the inventor finds that the epoxy resin composite material containing the porcelain filler can form a compact ceramic body at a lower temperature (for example, 1000 ℃).
The allyl polybenzoxazine of the ceramic filler shell not only can improve the flame retardant property of epoxy resin, but also can obviously improve the interface effect so as to improve the mechanical strength of a matrix material, and simultaneously can improve the heat resistance of the material, so that the ceramic body performance formed by the epoxy resin at high temperature is also 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, the characteristic signal transmittance of the article made from the epoxy resin composite of the present invention is higher than that of an epoxy resin without the addition of the porcelain filler.
According to a fourth aspect of the present invention, there is provided an automotive part prepared using the epoxy resin composite material described above.
The epoxy resin composite may be further compounded with a reinforcing material such as carbon fiber to obtain a fiber reinforced resin composite.
The components may be, for example, automotive battery pack top covers, automotive suspensions, ignition coils, 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 automobile battery pack, and the formed ceramic body can play a role in protecting batteries and circuits.
The terms "comprising" and "including" as used in the present application encompass the situation in which other elements not explicitly mentioned are also included or included as well as the situation in which they consist of the elements mentioned.
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. To the extent that the definitions of terms in this specification are inconsistent with the ordinary understanding of those skilled in the art to which this invention pertains, the definitions described herein control.
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 may 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 with reference to the embodiments and drawings so as to fully understand the objects, features, and effects of the present invention by those skilled in the art. It will be readily appreciated by those skilled in the art that the embodiments herein are for illustrative purposes only and that the scope of the present invention is not limited thereto.
Example 1
Allyl benzoxazine was prepared as follows:
9.4g of phenol and 6.6g of paraformaldehyde are added, with stirring at room temperature, to a three-necked flask containing 60ml of toluene, and the temperature is raised to 50 ℃. Then, 5.7g of acrylamide was added dropwise. After the completion of the dropwise addition, the temperature was raised to 90℃for reaction for 8 hours, and the mixture was cooled to room temperature. Then sequentially extracting with dichloromethane, naOH aqueous solution (with concentration of 30 wt%) and saturated NaCl aqueous solution, and finally removing solvent 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, powder silicon, sodium carbonate and zinc borate in an oven, and vacuum drying for 2 hours at 50 ℃ under vacuum condition, and then using the boron carbide powder: powder silicon: sodium carbonate: the mass ratio of zinc borate=30:30:20:20 is added into a ball mill to be mixed uniformly, and a mixture is obtained.
S2: forming porcelain filler
10G of the mixture, 1g of allylbenzoxazine and 30g of a mixed solvent of dimethyl silicone oil and chloroform (10 g of dimethyl silicone oil and 20g of chloroform in the solvent) are weighed and added into a reaction kettle, and after mechanical stirring and dispersion, the temperature is raised to 120 ℃ for reaction for 4 hours, the temperature is continuously raised to 180 ℃ for reaction for 2 hours, and the reaction system is cooled to room temperature under the stirring condition.
S3: separating into porcelain fillings
And (3) cleaning the 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 microscope picture of the porcelain filler prepared in example 1.
As can be seen from fig. 1: the microcapsule ceramic filler is formed by coating boron carbide powder, powder silicon, sodium carbonate and zinc borate with polybenzoxazine according to a certain proportion.
S4: preparation of epoxy resin composite
100G of epoxy resin E-44, 80g of the ceramic filler and 20g of curing agent p-phenylenediamine are weighed and stirred uniformly to obtain the epoxy resin composite material.
S5: curing of epoxy resin composites
Pouring the epoxy resin composite material into a mold, and curing at 120 ℃ for 3h, 150 ℃ for 3h and 170 ℃ for 2h to prepare the cured epoxy resin composite material.
Example 2
Allyl benzoxazine was prepared as follows:
9.4g of phenol and 6.6g of paraformaldehyde are added, with stirring at room temperature, to a three-necked flask containing 60ml of toluene, and the temperature is raised to 40 ℃. Then, 5.7g of acrylamide was added dropwise. After the completion of the dropwise addition, the temperature was raised to 100℃for 10 hours, and the mixture was cooled to room temperature. Then sequentially extracting with dichloromethane, naOH aqueous solution (with concentration of 30 wt%) and saturated NaCl aqueous solution, and finally removing solvent 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, powder silicon, sodium carbonate and zinc borate in an oven, and vacuum drying for 2 hours at 50 ℃ under vacuum condition, and then using the boron carbide powder: powder silicon: sodium carbonate: the mass ratio of zinc borate=30:40:20:10 is added into a ball mill to be mixed uniformly, and a mixture is obtained.
S2: forming porcelain filler
10G of the mixture, 2g of allylbenzoxazine and 30g of a mixed solvent of simethicone and chloroform (10 g of simethicone and 20g of chloroform in the mixed solvent) are weighed and added into a reaction kettle, and after mechanical stirring and dispersion, the temperature is raised to 120 ℃ for reaction for 4 hours, the temperature is continuously raised to 180 ℃ for reaction for 2 hours, and the reaction system is cooled to room temperature under the stirring condition.
S3: separating into porcelain fillings
And (3) cleaning the 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 microscope image of the ceramic filler prepared in example 2 after 1000℃ablation.
As can be seen from fig. 2: the ceramic-forming filler forms a dense ceramic body in an ablative environment at 1000 ℃.
S4: preparation of epoxy resin composite
100G of epoxy resin E-44, 80g of the ceramic filler and 20g of curing agent p-phenylenediamine are weighed and stirred uniformly to obtain the epoxy resin composite material.
S5: curing of epoxy resin composites
Pouring the epoxy resin composite material into a mold, and curing at 120 ℃ for 3h, 150 ℃ for 3h and 170 ℃ for 2h 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, powder silicon, sodium carbonate and zinc borate in an oven, and vacuum drying at 60 ℃ for 2 hours under vacuum condition, and then using the boron carbide powder: powder silicon: sodium carbonate: the mass ratio of zinc borate=30:40:15:15 is added into a ball mill to be mixed uniformly, and a mixture is obtained.
S2: forming porcelain filler
10G of the mixture, 1.5g of allylbenzoxazine (prepared according to the procedure described in example 1) and 40g of a mixed solvent of simethicone and chloroform (12 g of simethicone and 28g of chloroform in the mixed solvent) were weighed and added into a reaction kettle, and after mechanical stirring and dispersion, the temperature was raised to 130 ℃ for reaction for 4 hours, the temperature was further raised to 190 ℃ for reaction for 3 hours, and the reaction system was cooled to room temperature under stirring.
S3: separating into porcelain fillings
And (3) cleaning the 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
100G of epoxy resin E-51, 60g of the ceramic filler and 30g of curing agent 4,4' -diaminodiphenyl ether are weighed and uniformly stirred to obtain the epoxy resin composite material.
S5: curing of epoxy resin composites
Pouring the epoxy resin composite material into a mold, and curing at 150 ℃ for 3 hours, 160 ℃ for 3 hours and 190 ℃ for 2 hours to prepare the cured epoxy resin composite material.
FIG. 3 shows the apparent morphology of the epoxy resin composite 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 ablative environment at 1000 ℃.
Example 4
An epoxy resin composite was prepared as follows:
S1: preparation of the mixture
Respectively placing boron carbide powder, powder silicon, sodium carbonate and zinc borate in an oven, and vacuum drying for 2 hours at 40 ℃ under vacuum condition, and then using the boron carbide powder: powder silicon: sodium carbonate: the mass ratio of zinc borate=30:20:25:25 is added into a ball mill to be mixed uniformly, and a mixture is obtained.
S2: forming porcelain filler
10G of the mixture, 2g of allylbenzoxazine (prepared according to the procedure described in example 1) and 40g of a mixed solvent of simethicone and chloroform (12 g of simethicone in the solvent, 28g of chloroform) were weighed into a reaction kettle, and after mechanical stirring and dispersion, the temperature was raised to 130 ℃ for reaction 4 hours, the temperature was continuously raised to 190 ℃ for reaction 3 hours, and the reaction system was cooled to room temperature under stirring.
S3: separating into porcelain fillings
And (3) cleaning the 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
100G of epoxy resin E-51, 60g of the ceramic filler and 30g of curing agent 4,4' -diaminodiphenyl ether are weighed and uniformly stirred to obtain the epoxy resin composite material.
S5: curing of epoxy resin composites
Pouring the epoxy resin composite material into a mold, and curing at 150 ℃ for 3 hours, 160 ℃ for 3 hours and 190 ℃ for 2 hours 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, powder silicon, sodium carbonate and zinc borate in an oven, and vacuum drying for 2 hours at 40 ℃ under vacuum condition, and then using the boron carbide powder: powder silicon: sodium carbonate: the mass ratio of zinc borate=30:20:25:25 is added into a ball mill to be mixed uniformly, and a mixture is obtained.
S2: forming porcelain filler
10G of the mixture, 1.5g of allylbenzoxazine (prepared according to the procedure described in example 1) and 60g of a mixed solvent of simethicone and chloroform (24 g of simethicone and 36g of chloroform in the mixed solvent) were weighed and added into a reaction kettle, and after mechanical stirring and dispersion, the temperature was raised to 130 ℃ for reaction for 4 hours, the temperature was further raised to 190 ℃ for reaction for 3 hours, and the reaction system was cooled to room temperature under stirring.
S3: separating into porcelain fillings
And (3) cleaning the 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
100G of epoxy resin E-44, 60g of the ceramic filler and 25g of curing agent 4,4' -diaminodiphenyl ether are weighed and uniformly stirred to obtain the epoxy resin composite material.
S5: curing of epoxy resin composites
Pouring the epoxy resin composite material into a mold, and curing at 150 ℃ for 3 hours, 160 ℃ for 3 hours and 190 ℃ for 2 hours 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, powder silicon, sodium carbonate and zinc borate in an oven, and vacuum drying for 2 hours at 40 ℃ under vacuum condition, and then using the boron carbide powder: powder silicon: sodium carbonate: the mass ratio of zinc borate=30:20:25:25 is added into a ball mill to be mixed uniformly, and a mixture is obtained.
S2: forming porcelain filler
10G of the mixture, 3g of allylbenzoxazine (prepared according to the procedure described in example 1) and 60g of a mixed solvent of simethicone and chloroform (24 g of simethicone and 36g of chloroform in the mixed solvent) were weighed and added into a reaction kettle, the mixture was stirred mechanically and dispersed, the temperature was raised to 130 ℃ for reaction for 4 hours, the temperature was raised to 190 ℃ continuously for reaction for 3 hours, and the reaction system was cooled to room temperature under stirring.
S3: separating into porcelain fillings
And (3) cleaning the 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
100G of epoxy resin E-44, 30g of the ceramic filler and 30g of curing agent 4,4' -diaminodiphenyl methane are weighed and uniformly stirred to obtain the epoxy resin composite material.
S5: curing of epoxy resin composites
Pouring the epoxy resin composite material into a mold, and curing at 150 ℃ for 3 hours, 160 ℃ for 3 hours and 190 ℃ for 2 hours 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, powder silicon, sodium carbonate and zinc borate in an oven, and vacuum drying for 2 hours at 40 ℃ under vacuum condition, and then using the boron carbide powder: powder silicon: sodium carbonate: the mass ratio of zinc borate=30:50:15:5 is added into a ball mill to be mixed uniformly, and a mixture is obtained.
S2: forming porcelain filler
10G of the mixture, 3.5g of allylbenzoxazine (prepared according to the procedure described in example 1) and 60g of a mixed solvent of simethicone and chloroform (24 g of simethicone and 36g of chloroform in the mixed solvent) were weighed and added into a reaction kettle, and after mechanical stirring and dispersion, the temperature was raised to 130 ℃ for reaction for 4 hours, the temperature was further raised to 190 ℃ for reaction for 3 hours, and the reaction system was cooled to room temperature under stirring.
S3: separating into porcelain fillings
And (3) cleaning the 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
100G of epoxy resin E-44, 30g of the ceramic filler and 30g of curing agent 4,4' -diaminodiphenyl methane are weighed and uniformly stirred to obtain the epoxy resin composite material.
S5: curing of epoxy resin composites
Pouring the epoxy resin composite material into a mold, and curing at 140 ℃ for 3h, 160 ℃ for 3h and 180 ℃ for 2h 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, powder silicon, sodium carbonate and zinc borate in an oven, and vacuum drying for 2 hours at 40 ℃ under vacuum condition, and then using the boron carbide powder: powder silicon: sodium carbonate: the mass ratio of zinc borate=30:50:15:5 is added into a ball mill to be mixed uniformly, and a mixture is obtained.
S2: forming porcelain filler
10G of the mixture, 3g of allylbenzoxazine (prepared according to the procedure described in example 1) and 50g of a solvent of simethicone and chloroform (10 g of simethicone in the solvent, 40g of chloroform) were weighed into a reaction kettle, and after mechanical stirring and dispersion, the temperature was raised to 140 ℃ for reaction for 4 hours, the temperature was continuously raised to 200 ℃ for reaction for 3 hours, and the reaction system was cooled to room temperature under stirring.
S3: separating into porcelain fillings
And (3) cleaning the 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
100G of epoxy resin E-44, 70g of the ceramic filler and 30g of curing agent 4,4' -diaminodiphenyl methane are weighed and uniformly stirred to obtain the epoxy resin composite material.
Pouring the epoxy resin composite material into a mold, and curing at 140 ℃ for 3h, 160 ℃ for 3h and 180 ℃ for 2h to obtain 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, powder silicon, sodium carbonate and zinc borate in an oven, and vacuum drying for 2 hours at 40 ℃ under vacuum condition, and then using the boron carbide powder: powder silicon: sodium carbonate: the mass ratio of zinc borate=30:50:15:5 is added into a ball mill to be mixed uniformly, and a mixture is obtained.
S2: forming porcelain filler
10G of the mixture, 2g of allylbenzoxazine (prepared according to the procedure described in example 1) and 50g of a mixed solvent of simethicone and chloroform (10 g of simethicone and 40g of chloroform in the mixed solvent) were weighed and added into a reaction kettle, the mixture was stirred mechanically and dispersed, the temperature was raised to 140 ℃ for reaction for 4 hours, the temperature was raised to 200 ℃ continuously for reaction for 3 hours, and the reaction system was cooled to room temperature under stirring.
S3: separating into porcelain fillings
And (3) cleaning the 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
100G of epoxy resin E-51, 70g of the ceramic filler and 25g of curing agent 4,4' -diaminodiphenyl methane are weighed and stirred uniformly to obtain the epoxy resin composite material.
S5: curing of epoxy resin composites
Pouring the epoxy resin composite material into a mold, and curing at 140 ℃ for 3h, 160 ℃ for 3h and 180 ℃ for 2h to prepare the cured epoxy resin composite material.
Comparative example 1
100G of epoxy resin E-51 and 25g of curing agent 4,4' -diaminodiphenyl methane are weighed and stirred uniformly to obtain the epoxy resin composite material.
Pouring the epoxy resin composite material into a mold, and curing at 140 ℃ for 3h, 160 ℃ for 3h and 180 ℃ for 2h to prepare the cured epoxy resin composite material.
The epoxy resin composites prepared in examples 1-9 and comparative example 1 above were tested for various properties, wherein:
The mechanical properties of the composite material were determined according to GB/T528-2009 and according to GB/T529-2008, limiting oxygen index values (LOI) were tested according to GB/T10707-2008, the composite material was ablated at 1000 ℃ for 30min to form a ceramic body, and the flexural strength of the ceramic body was tested according to GB/T9341-2008.
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 | Comparative example | |
| 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/% | 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 |
| Ablation body strength/MPa | 76.2 | 79.6 | 79.9 | 75.3 | 75.3 | 74.6 | 80.3 | 80.5 | 80.5 | / |
| Vertical flame retardant rating | UL94V-0 | UL94V-0 | UL94V-0 | UL94V-0 | UL94V-0 | UL94V-0 | UL94V-0 | UL94V-0 | UL94V-0 | UL94V-2 |
| Post-ablative appearance | Hard, compact and cracking-free | Hard, compact and cracking-free | Hard, compact and cracking-free | Hard, compact and cracking-free | Hard, compact and cracking-free | Hard, compact and cracking-free | Hard, compact and cracking-free | Hard, compact and cracking-free | Hard, compact and cracking-free | / |
| Ablation line change rate/% | -1.1 | -1.2 | -1.5 | -2.4 | -1.8 | -2.3 | -2.6 | -1.3 | -1.3 | -3.5 |
| Characteristic signal transmittance/% | 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.
In addition, it was found that: compared with the epoxy resin without the porcelain filler, the characteristic signal transmittance of the product prepared by the epoxy resin composite material is higher.
The foregoing describes only exemplary embodiments or examples of the present application and is not intended to limit the present application. The present application is susceptible to various modifications and changes by those skilled in the art. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the application are within the scope of the following claims.
Claims (11)
1. A porcelain filler, which is characterized by comprising boron carbide, simple substance silicon, fluxing agent, zinc borate and allyl polybenzoxazine forming a coating layer, wherein the mass ratio of the boron carbide to the simple substance silicon to the fluxing agent to the zinc borate is 30:20-50:15-25:5-25, wherein the mass ratio of the total mass of boron carbide, elemental silicon, fluxing agent and zinc borate to the allyl benzoxazine is 1:0.1-0.4.
2. The porcelain filler of claim 1, wherein the fluxing agent is sodium carbonate.
3. A method of preparing a porcelain filler according to claim 1 or 2, comprising the steps of:
I) Mixing boron carbide, simple substance silicon, fluxing agent and zinc borate to obtain a mixture;
II) dispersing the obtained mixture and allyl benzoxazine into a solvent, heating to 120-160 ℃ for reaction for 2-6 h, continuously heating to 180-200 ℃ for reaction 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.
4. A process according to claim 3, characterized in that the solvent used in step II) is selected from the group consisting of dimethicone, chloroform and mixtures thereof.
5. The method according to claim 3 or 4, wherein the mass ratio of the mixture to the solvent is 1:3-8.
6. An epoxy resin composite material characterized by comprising an epoxy resin and the porcelain-forming filler according to claim 1 or 2.
7. The epoxy resin composite of claim 6, wherein the weight ratio of the epoxy resin to the porcelain filler is 100:30-80.
8. The epoxy resin composite of claim 6 or 7, further comprising a curing agent.
9. The epoxy resin composite of claim 8, wherein the curing agent is selected from the group consisting of p-phenylene diamine, 4 '-diaminodiphenyl ether, 4' -diaminodiphenyl methane, and combinations thereof.
10. The epoxy resin composite of claim 6 or 7, wherein the weight ratio of the epoxy resin to the curing agent is 100:15-30.
11. An automotive part, characterized in that it is produced using the epoxy resin composite material according to any one of claims 6 to 10.
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