CN115572457A - Environment-resistant and anti-aging epoxy resin system - Google Patents
Environment-resistant and anti-aging epoxy resin system Download PDFInfo
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- CN115572457A CN115572457A CN202210786289.9A CN202210786289A CN115572457A CN 115572457 A CN115572457 A CN 115572457A CN 202210786289 A CN202210786289 A CN 202210786289A CN 115572457 A CN115572457 A CN 115572457A
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- epoxy resin
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 83
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 83
- 230000003712 anti-aging effect Effects 0.000 title claims abstract description 12
- 239000004005 microsphere Substances 0.000 claims abstract description 49
- 230000032683 aging Effects 0.000 claims abstract description 43
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 42
- 230000007613 environmental effect Effects 0.000 claims abstract description 31
- 239000012784 inorganic fiber Substances 0.000 claims abstract description 30
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 15
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 15
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 20
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 18
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- -1 phenol aldehyde Chemical class 0.000 claims description 9
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 8
- 239000004917 carbon fiber Substances 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 229920002647 polyamide Polymers 0.000 claims description 8
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 5
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims description 4
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920000768 polyamine Polymers 0.000 claims description 3
- 239000004645 polyester resin Substances 0.000 claims description 3
- 229920001225 polyester resin Polymers 0.000 claims description 3
- 229920006295 polythiol Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- OBROYCQXICMORW-UHFFFAOYSA-N tripropoxyalumane Chemical compound [Al+3].CCC[O-].CCC[O-].CCC[O-] OBROYCQXICMORW-UHFFFAOYSA-N 0.000 claims description 3
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 2
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 2
- 229940009827 aluminum acetate Drugs 0.000 claims description 2
- 229920003986 novolac Polymers 0.000 claims description 2
- RQIHICWHMWNVSA-UHFFFAOYSA-N propan-1-ol;zirconium Chemical compound [Zr].CCCO RQIHICWHMWNVSA-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical group 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 239000000835 fiber Substances 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000002736 metal compounds Chemical class 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 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 4
- 150000001412 amines Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000003636 chemical group Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- VEGXEWGKYMMJKP-UHFFFAOYSA-N 1-hydroxypropyl acetate Chemical compound CCC(O)OC(C)=O VEGXEWGKYMMJKP-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 238000009755 vacuum infusion Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/057—Metal alcoholates
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/04—Epoxynovolacs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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)
- Epoxy Resins (AREA)
Abstract
The invention discloses an environment-resistant and anti-aging epoxy resin system, which comprises the following components, by weight, 100 parts of epoxy resin, a curing agent and inorganic fibers; 5-40 parts of metal oxide microspheres; 0.2 to 2 parts by weight of an organometallic compound. The epoxy resin system can obviously improve the environmental aging resistance of a cured product of the epoxy resin system, and also has the general properties of enough strength and the like. The epoxy resin systems of the present invention can be fabricated into articles by existing processing techniques.
Description
Technical Field
The invention relates to the field of thermosetting resin, in particular to an environment-resistant and anti-aging epoxy resin system.
Background
The epoxy resin forms a condensate with a three-dimensional network structure through the chemical crosslinking of the epoxy functional group and other functional groups, and has excellent comprehensive properties: including high strength, good heat resistance, excellent electrical properties, corrosion resistance, environmental aging resistance, good dimensional stability, etc., and is widely applied in the fields of electronics/electrics, energy, chemical industry, machinery, automobiles, rail transit, buildings, etc.
For example, chinese patent application CN201980052851.1 provides an epoxy resin system, the cured product of which has high storage stability, and is suitable for structural materials of aircraft bodies, interior materials, structural parts for aircraft engines, and the like, which require heat resistance, mechanical properties, and combustion characteristics under high temperature and high humidity conditions.
The Chinese patent application CN201911331076.1 provides an epoxy resin system, relates to an epoxy-organic silicon resin, and can improve the strength and toughness of an epoxy resin cured product and improve the temperature resistance and weather resistance of the epoxy resin cured product.
However, the quality of products is increasingly required, and there is a demand for further improvement in various properties of cured epoxy resins, such as environmental aging resistance. In particular, for products used outdoors for a long time, such as parts of automobiles, high-speed rails, wind power generation, solar power generation, buildings, and the like, it is necessary to resist damage caused by light, high humidity, and cold-heat alternation, and it is particularly necessary to enhance the environmental aging resistance.
Therefore, an epoxy resin system is lacking, and a cured product formed by the epoxy resin system has excellent environmental aging resistance and also has sufficient general-purpose properties such as strength and processability.
Disclosure of Invention
The invention provides an environment-resistant and aging-resistant epoxy resin system, wherein a condensate formed by the epoxy resin system has excellent environment aging resistance and also has general properties such as enough strength, processability and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
an environment-resistant and anti-aging epoxy resin system is characterized by comprising the following components,
100 parts by weight of epoxy resin, curing agent and inorganic fiber;
5-40 parts of metal oxide microspheres;
0.2 to 2 parts by weight of an organometallic compound.
The epoxy resin and the curing agent are basic resins of the epoxy resin system, and provide main mechanical properties of a cured product of the epoxy resin system. Wherein, the epoxy resin is oligomer containing epoxy functional group, and can form three-dimensional network thermosetting plastic when reacting with curing agent.
Among them, the epoxy resins are classified by chemical structure and can be classified into glycidyl ethers such as bisphenol a type, bisphenol F type, bisphenol S type, hydrogenated bisphenol a type, phenol aldehyde type, etc.; glycidyl esters such as diglycidyl phthalate and the like; glycidyl amines, such as tetraglycidyl diaminodiphenylmethane; alicyclic epoxy resins, epoxidized olefins, and the like.
In view of balancing environmental aging resistance, strength, processability, cost performance and the like, it is preferable that the epoxy resin is one or more of bisphenol a type, bisphenol F type, hydrogenated bisphenol a type, phenol type, alicyclic type epoxy resins.
More preferably, the epoxy resin comprises 50-80% of bisphenol F type epoxy resin and 20-50% of phenolic aldehyde type epoxy resin. The bisphenol F epoxy resin is generally prepared by reacting bisphenol F with epichlorohydrin. The phenolic epoxy resin is generally prepared by reacting phenolic novolac resin with epichlorohydrin. The proportion is beneficial to improving the environmental aging resistance of the epoxy resin system.
The curing agent is a compound capable of reacting with an epoxy functional group, and can be classified into polyamine types such as ethylenediamine, diethylenetriamine, m-phenylenediamine, bismaleimide and the like according to the chemical structure; acid anhydride type such as maleic anhydride, phthalic anhydride, pyromellitic dianhydride, etc.; and other curing agents such as phenolic, imidazole, polyamide, polyester resin, polyurethane and polythiol.
In view of balancing environmental aging resistance, strength, processability, cost performance and the like, it is preferable that the curing agent is one or more of polyamine type, acid anhydride type, phenol type, imidazole type, polyester resin type, polyamide type, polyurethane and polythiol type.
More preferably, the curing agent comprises 50 to 80 percent of imidazole type curing agent and 20 to 50 percent of polyamide type curing agent. The proportion is beneficial to improving the environmental aging resistance of the epoxy resin system.
The proportion of the epoxy resin and the curing agent is generally equal molar ratio of epoxy functional groups of the epoxy resin to effective functional groups of the curing agent, or slightly more effective functional groups of the curing agent, for example, within 10%, and can be regulated and controlled according to the prior art.
The inorganic fiber is chemical fiber prepared by taking inorganic matters as main raw materials, and comprises glass fiber, carbon fiber, boron fiber, ceramic fiber, metal fiber, alumina fiber, silicon carbide fiber and the like. In order to improve the environmental aging resistance and strength of the cured product of the epoxy resin system, the inorganic fiber is preferably one or more of a glass fiber and a carbon fiber, and more preferably a carbon fiber.
The reasonable forms of the inorganic fibers, such as long fibers, short fibers, powder, woven cloth and the like, and the content of the inorganic fibers can be selected according to the actual requirements of the cured product of the epoxy resin system, the processing mode and the like. In general, the longer the inorganic fiber is and the larger the content is, the better the environmental aging resistance and strength of the cured product is. However, depending on the processing method, it is sometimes necessary to use inorganic fibers such as short fibers and powders, and these inorganic fibers are also effective for improving the environmental aging resistance and strength of the cured product. The content of the inorganic fiber is preferably 5 to 50 parts by weight, more preferably 20 to 40 parts by weight, based on 100 parts by weight of the epoxy resin, the curing agent and the inorganic fiber.
Most preferably, the inorganic fiber is carbon fiber, and the content of the inorganic fiber is 20 to 40 parts by weight based on 100 parts by weight of the epoxy resin, the curing agent, and the inorganic fiber.
The metal oxide microspheres are spherical or spheroidal particles consisting essentially of a metal oxide, and contribute greatly to the improvement of the environmental aging resistance of a cured product, and also provide sufficient strength, processability and the like to the cured product.
The metal oxide microspheres may comprise one or more of zirconia, alumina, titania, copper oxide, etc. in terms of material. In view of further improving the environmental aging resistance of the cured product, it is preferable that the metal oxide microspheres are one or more of zirconia or alumina microspheres.
Morphologically, the metal oxide microspheres can include one or both of hollow microspheres and solid microspheres. Both can improve the environmental aging resistance of the cured product, and the hollow microspheres have the advantage of light weight compared with solid microspheres. The inventors have found that when both hollow microspheres and solid microspheres are present in the system, the environmental aging resistance is better. Furthermore, the hollow microspheres account for 3-30 parts by weight and the solid microspheres account for 2-10 parts by weight based on 100 parts by weight of the epoxy resin, the curing agent and the inorganic fibers.
The metal oxide microspheres may have an average particle size of 10nm to 1mm. Generally, the smaller the average particle size, the more difficult it is for the microspheres to disperse; the larger the average particle diameter is, on the one hand, the more likely it is to settle in the system and cause dispersion unevenness, and on the other hand, it is disadvantageous in terms of uniformity of material properties at a microscopic level, thereby causing poor environmental aging resistance. Further, the inventors found that when the average particle size of the hollow microspheres is less than 100nm and the average particle size of the solid microspheres is greater than 1 μm, the environmental aging resistance is better.
Further, it is preferred that the hollow microspheres comprise zirconia hollow microspheres, and preferably the solid microspheres comprise alumina solid microspheres.
Furthermore, the epoxy resin, the curing agent and the inorganic fiber preferably comprise 10 to 20 parts by weight of the zirconia hollow microspheres, and preferably comprise 5 to 10 parts by weight of the alumina solid microspheres, based on 100 parts by weight of the epoxy resin, the curing agent and the inorganic fiber.
Further, the epoxy resin curing agent and the inorganic fiber are preferably contained by 10 to 20 parts by weight of zirconia hollow microspheres with the average particle size of less than 100nm, and preferably contained by 5 to 10 parts by weight of alumina solid microspheres with the average particle size of more than 1 mu m, based on 100 parts by weight of the epoxy resin, the curing agent and the inorganic fiber;
the organic metal compound can obviously improve the adhesiveness and the dispersibility of a resin matrix and metal oxide microspheres in a cured product, thereby improving the environmental aging resistance, the strength and the processability of the cured product.
Preferably, the metal element in the organometallic compound is the same as the metal element in the metal oxide.
Preferably, the organometallic compound is acetylacetonato, acetoxy, propanolate.
Further preferably, the organometallic compound is one or more of zirconium acetylacetonate, zirconium acetate, zirconium propoxide, aluminum acetylacetonate, aluminum acetate, and aluminum propoxide.
0.2 to 2 parts by weight of an organic metal compound based on 100 parts by weight of the total of the epoxy resin, the curing agent and the inorganic fiber.
The organic metal compound is too little to improve the adhesion and the dispersibility of the resin matrix and the metal oxide microspheres in the cured product; when the amount of the organic metal compound is too large, the environmental aging resistance and the strength of the cured product are deteriorated. Preferably, the organometallic compound is present in an amount of 0.4 to 1.5 parts by weight based on 100 parts by weight of the total of the epoxy resin, the curing agent and the inorganic fiber.
More preferably, the organic metal compound and its content are 0.3-1 part by weight of zirconium propoxide and 0.1-0.5 part by weight of aluminum acetylacetonate, based on 100 parts by weight of the total of the epoxy resin, the curing agent and the inorganic fiber.
As a more preferred embodiment, the epoxy resin system of the present invention comprises the following components,
100 parts by weight of epoxy resin, curing agent and inorganic fiber,
wherein the epoxy resin comprises 50 to 80 percent of bisphenol F type and 20 to 50 percent of phenolic aldehyde type epoxy resin,
the curing agent comprises 50-80% of phenolic aldehyde type curing agent and 20-50% of polyamide type curing agent, the inorganic fiber is carbon fiber, and the content is 20-40 parts by weight;
10-20 parts by weight of zirconia hollow microspheres with the average particle size of less than 100 nm;
5-10 parts by weight of alumina solid microspheres with the average particle size of more than 1 mu m;
0.3 to 1 weight part of zirconium propanol;
0.1 to 0.5 weight portion of aluminum acetylacetonate.
The environment-resistant and anti-aging epoxy resin system can comprise an accelerator, a diluent, a solvent, a plasticizer, a toughening agent, a surfactant, a solubilizer, a coupling agent, a filler and the like according to the performance requirements during actual processing and use.
The invention also provides a cured product containing the environment-resistant and aging-resistant epoxy resin system, which can be applied to the fields of electronics/electricity, energy, chemical industry, machinery, automobile, rail transit, buildings and the like. Specific applications include structural materials for automobiles, bicycles, ships, and rail vehicles, transmission shafts, leaf springs, windmill blades, pressure vessels, flywheels, papermaking rolls, roofing materials, cables, and repair/reinforcement materials, and the like.
Compared with the prior art, the invention has the beneficial effects that:
1. the environment-resistant and anti-aging epoxy resin system can obviously improve the environment aging resistance of a condensate thereof and also has the general properties of enough strength and the like.
2. The environment-resistant and anti-aging epoxy resin system can be processed into products by the existing processing technology.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments.
The raw materials used in the examples and comparative examples were as follows:
[ epoxy resin ]
A1: bisphenol F type epoxy resin, available from DIC corporation
830, epoxy equivalent 170g/eq.
A2: phenol-novolac epoxy resin, available from DIC corporation
N-740, epoxy equivalent 180g/eq.
A3: bisphenol A epoxy resin, available from DIC corporation
850 g, epoxy equivalent 188g/eq.
[ SOLIDIFYING AGENT ]
B1: an imidazole-type curing agent, manufactured by Mitsubishi chemical corporation, jERCure-IBMI12, having an amine value of 405KOHmg/g.
B2: polyamide type curing agent, available from DIC corporation
B-065, active hydrogen equivalent 62g/eq. B3: an amine-based curing agent, manufactured by Mitsubishi chemical corporation, jERCure-ST11, having an amine value of 340KOHmg/g.
[ inorganic fibers ]
C1: carbon fiber powder fiber, MLD-30 manufactured by Toray Japan.
[ METAL OXIDE MICROSPHERES ]
D1: zirconia hollow microspheres with a particle size of 200nm were purchased from Sichuan iron craftsman scientific Co.
D2: alumina hollow microspheres, 250nm in particle size, were purchased from Sichuan iron craftsman scientific Co.
D3: zirconia solid microspheres, 20 μm in particle size, were purchased from Sichuan iron craftsman technologies, inc.
D4: alumina solid microspheres, 30 μm in size, were purchased from Sichuan iron craftsman scientific Co.
[ organometallic Compounds ]
E1: zirconium propoxide, available from national chemical group, ltd.
E2: aluminum propoxide, available from chemical reagents ltd, national pharmaceutical group.
E3: zirconium acetylacetonate, available from national chemical group, ltd.
E4: aluminum acetylacetonate, available from chemical reagents, inc., of the national pharmaceutical group.
The environmental aging treatment and test method of the molded articles prepared in each example and comparative example are as follows:
environmental aging treatment 1: cold and hot cycles
The samples were placed in a cold-hot circulation box and treated according to the following procedure: heating from 25 deg.C to 105 deg.C, maintaining the temperature for 8hr, cooling to-40 deg.C, maintaining the temperature for 8hr, heating to 25 deg.C, and cooling at a rate of 2 deg.C/min; this was taken as 1 cycle for a total of 100 cycles.
Environmental aging treatment 2: damp-heat aging
The sample was placed in a constant temperature and humidity chamber and treated at 85% RH for 1000hr at 85 ℃.
Environmental aging treatment 2: ultraviolet aging
The sample was placed in an ultraviolet aging oven and irradiated for 200 hours at a temperature of 85 ℃ and an illumination of 85% RH and an illuminance of 100mW/cm2 (light source: metal halide lamp, wavelength range: 295nm to 450nm, peak wavelength: 365 nm).
[ PROFILE ] of
The appearance of each sample before and after environmental aging treatment was visually observed. And judging whether the phenomena of yellowing, cracks, warping and the like exist. Those which did not have the above-mentioned phenomenon were regarded as good. The color of the film was found to be moderate, with slight yellowing, cracking, warping, etc. The film was marked as defective because of severe yellowing, cracking, warping, and the like.
[ tensile Strength Retention ]
The tensile strength of each sample was tested according to GB/T1447-2005 (type I bars) before and after environmental aging. The tensile strength retention was calculated as follows.
Tensile strength retention = tensile strength after environmental aging treatment/tensile strength before environmental aging treatment × 100%.
Examples 1 to 28 and comparative examples 1 to 3
The raw materials were mixed uniformly at room temperature according to the formulation shown in table 1 and defoamed to obtain an epoxy resin system. The molar ratio of the effective functional groups of the epoxy resin to the cured product is equal to the molar ratio of the effective functional groups of the cured product.
Taking an iron plate with a proper size, polishing the surface of a single iron plate to be smooth, and coating a release agent to be used as a mold. Then, a cured product of the epoxy resin system is formed on the surface of the mold by using a vacuum infusion method. The molding conditions were isothermal at 80 ℃ for 4 hours followed by 110 ℃ for 4 hours. And cutting out samples required by various performance tests from the molded product, and carrying out environmental aging treatment and performance tests. The test results are shown in Table 2.
As can be seen from the examples and comparative examples, the epoxy resin system of the present invention can be processed into articles by existing processing techniques, and the environmental aging resistance of the cured product can be significantly improved as compared with the comparative examples.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
TABLE 1
TABLE 2
Although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention, which is defined in the claims.
Claims (10)
1. An environment-resistant and anti-aging epoxy resin system is characterized by comprising the following components,
epoxy resin, curing agent and inorganic fiber mixture: 100 parts by weight;
metal oxide microspheres: 5-40 parts by weight;
an organometallic compound: 0.2 to 2 parts by weight.
2. The environment-friendly and anti-aging epoxy resin system as claimed in claim 1, wherein the epoxy resin is one or more of bisphenol A type, bisphenol F type, hydrogenated bisphenol A type, phenol aldehyde type, and ester ring type epoxy resin, and the curing agent is one or more of polyamine type, acid anhydride type, phenol aldehyde type, imidazole type, polyester resin type, polyamide type, polyurethane, and polythiol type.
3. The environment-friendly and anti-aging epoxy resin system as claimed in claim 2, wherein the epoxy resin comprises 50-80% bisphenol F type epoxy resin and 20-50% novolac type epoxy resin, and the curing agent comprises 50-80% imidazole type curing agent and 20-50% polyamide type curing agent.
4. The environmentally resistant and aging resistant epoxy resin system of claim 1, wherein the inorganic fiber is one or more of glass fiber and carbon fiber.
5. The environmentally resistant and aging resistant epoxy resin system of claim 1, wherein the metal oxide microspheres are one or more of zirconia microspheres or alumina microspheres.
6. The environment and aging resistant epoxy resin system of claim 1, wherein the metal oxide microspheres comprise hollow microspheres and solid microspheres, and the hollow microspheres are 3 to 30 parts by weight and the solid microspheres are 2 to 10 parts by weight based on 100 parts by weight of the epoxy resin, the curing agent and the inorganic fibers.
7. The environment-resistant and anti-aging epoxy resin system as claimed in claim 6, wherein the average particle size of the hollow microspheres is less than 100nm, and the average particle size of the solid microspheres is greater than 1 μm.
8. The environmentally resistant and aging resistant epoxy resin system of claim 1, wherein the organometallic compound is one or more of zirconium acetylacetonate, zirconium acetate, zirconium propoxide, aluminum acetylacetonate, aluminum acetate, and aluminum propoxide.
9. The environmental resistance and aging resistance epoxy resin system according to any one of claims 1 to 8, comprising the following components,
epoxy resin, curing agent, inorganic fiber mixture: the total amount of the components is 100 parts by weight,
zirconia hollow microspheres with average particle size less than 100 nm: 10-20 parts by weight;
alumina solid microspheres with average particle size greater than 1 μm: 5-10 parts by weight;
zirconium propanol: 0.3 to 1 part by weight;
aluminum acetylacetonate: 0.1 to 0.5 weight portion;
wherein the epoxy resin comprises 50-80% of bisphenol F type epoxy resin and 20-50% of phenolic aldehyde type epoxy resin;
the curing agent comprises 50-80% of imidazole type curing agent and 20-50% of polyamide type curing agent;
the inorganic fiber is carbon fiber, and the content is 20-40 parts by weight.
10. Cured product comprising an environmentally and ageing resistant epoxy resin system according to any one of claims 1 to 9.
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| US5439746A (en) * | 1991-09-09 | 1995-08-08 | Kabushiki Kaisha Toshiba | Epoxy resin-basin composite material |
| CN109370160A (en) * | 2018-10-31 | 2019-02-22 | 科化新材料泰州有限公司 | A kind of epoxy molding plastic and preparation method thereof that powder fiber is modified |
| CN112771123A (en) * | 2018-10-11 | 2021-05-07 | 三菱化学株式会社 | Resin composition, cured resin, and composite molded article |
| CN113861651A (en) * | 2021-08-20 | 2021-12-31 | 天津金发新材料有限公司 | Polycarbonate composition and preparation method and application thereof |
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2022
- 2022-07-06 CN CN202210786289.9A patent/CN115572457A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5439746A (en) * | 1991-09-09 | 1995-08-08 | Kabushiki Kaisha Toshiba | Epoxy resin-basin composite material |
| CN112771123A (en) * | 2018-10-11 | 2021-05-07 | 三菱化学株式会社 | Resin composition, cured resin, and composite molded article |
| CN109370160A (en) * | 2018-10-31 | 2019-02-22 | 科化新材料泰州有限公司 | A kind of epoxy molding plastic and preparation method thereof that powder fiber is modified |
| CN113861651A (en) * | 2021-08-20 | 2021-12-31 | 天津金发新材料有限公司 | Polycarbonate composition and preparation method and application thereof |
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