CN110791053A - Epoxy resin composition containing microcapsule curing agent, and prepreg and composite material thereof - Google Patents
Epoxy resin composition containing microcapsule curing agent, and prepreg and composite material thereof Download PDFInfo
- Publication number
- CN110791053A CN110791053A CN201911118414.3A CN201911118414A CN110791053A CN 110791053 A CN110791053 A CN 110791053A CN 201911118414 A CN201911118414 A CN 201911118414A CN 110791053 A CN110791053 A CN 110791053A
- Authority
- CN
- China
- Prior art keywords
- curing agent
- epoxy resin
- resin composition
- microcapsule
- microcapsule curing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 254
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 211
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 211
- 239000003094 microcapsule Substances 0.000 title claims abstract description 189
- 239000000203 mixture Substances 0.000 title claims abstract description 103
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 239000003085 diluting agent Substances 0.000 claims abstract description 60
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 54
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 54
- 239000002245 particle Substances 0.000 claims abstract description 30
- 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 claims description 17
- 239000002250 absorbent Substances 0.000 claims description 17
- 230000002745 absorbent Effects 0.000 claims description 17
- 239000002216 antistatic agent Substances 0.000 claims description 17
- 239000003063 flame retardant Substances 0.000 claims description 17
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000002657 fibrous material Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 12
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 11
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 150000008064 anhydrides Chemical class 0.000 claims description 10
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 10
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 claims description 9
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 9
- 230000001680 brushing effect Effects 0.000 claims description 9
- -1 polypropylene acrylate Polymers 0.000 claims description 9
- 238000005096 rolling process Methods 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 8
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 7
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical group CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 6
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 6
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- VWYIWOYBERNXLX-KTKRTIGZSA-N Glycidyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC1CO1 VWYIWOYBERNXLX-KTKRTIGZSA-N 0.000 claims description 6
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- 229920000299 Nylon 12 Polymers 0.000 claims description 6
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 229920000388 Polyphosphate Polymers 0.000 claims description 6
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- XRQKARZTFMEBBY-UHFFFAOYSA-N oxiran-2-ylmethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1CO1 XRQKARZTFMEBBY-UHFFFAOYSA-N 0.000 claims description 6
- 239000003973 paint Substances 0.000 claims description 6
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 claims description 6
- 239000001205 polyphosphate Substances 0.000 claims description 6
- 235000011176 polyphosphates Nutrition 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 6
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 claims description 5
- OQZDJLFNMXRJHZ-UHFFFAOYSA-N 1-benzyl-2-ethylimidazole Chemical compound CCC1=NC=CN1CC1=CC=CC=C1 OQZDJLFNMXRJHZ-UHFFFAOYSA-N 0.000 claims description 5
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 claims description 5
- XZKLXPPYISZJCV-UHFFFAOYSA-N 1-benzyl-2-phenylimidazole Chemical compound C1=CN=C(C=2C=CC=CC=2)N1CC1=CC=CC=C1 XZKLXPPYISZJCV-UHFFFAOYSA-N 0.000 claims description 5
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 5
- YMJPBYVLNFBSFE-UHFFFAOYSA-N 2-ethyl-4-methylimidazole-1-carbonitrile Chemical compound CCC1=NC(C)=CN1C#N YMJPBYVLNFBSFE-UHFFFAOYSA-N 0.000 claims description 5
- UCCGHLMDDOUWAF-UHFFFAOYSA-N 2-phenylimidazole-1-carbonitrile Chemical compound N#CN1C=CN=C1C1=CC=CC=C1 UCCGHLMDDOUWAF-UHFFFAOYSA-N 0.000 claims description 5
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 5
- ADAHGVUHKDNLEB-UHFFFAOYSA-N Bis(2,3-epoxycyclopentyl)ether Chemical compound C1CC2OC2C1OC1CCC2OC21 ADAHGVUHKDNLEB-UHFFFAOYSA-N 0.000 claims description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 5
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229920000571 Nylon 11 Polymers 0.000 claims description 5
- 229920002292 Nylon 6 Polymers 0.000 claims description 5
- 229920000572 Nylon 6/12 Polymers 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 5
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 5
- 239000004695 Polyether sulfone Substances 0.000 claims description 5
- 239000004697 Polyetherimide Substances 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 229940064734 aminobenzoate Drugs 0.000 claims description 5
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 claims description 5
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims description 5
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 5
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 claims description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 5
- BQQUFAMSJAKLNB-UHFFFAOYSA-N dicyclopentadiene diepoxide Chemical compound C12C(C3OC33)CC3C2CC2C1O2 BQQUFAMSJAKLNB-UHFFFAOYSA-N 0.000 claims description 5
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 5
- ZMUCVNSKULGPQG-UHFFFAOYSA-N dodecanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCCCC(O)=O ZMUCVNSKULGPQG-UHFFFAOYSA-N 0.000 claims description 5
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 claims description 5
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 5
- 125000002883 imidazolyl group Chemical group 0.000 claims description 5
- OVMJVEMNBCGDGM-UHFFFAOYSA-N iron silver Chemical compound [Fe].[Ag] OVMJVEMNBCGDGM-UHFFFAOYSA-N 0.000 claims description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 5
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 5
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 5
- 229920001652 poly(etherketoneketone) Polymers 0.000 claims description 5
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 claims description 5
- 229920006393 polyether sulfone Polymers 0.000 claims description 5
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- 150000003505 terpenes Chemical class 0.000 claims description 5
- 235000007586 terpenes Nutrition 0.000 claims description 5
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 5
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- 229920002319 Poly(methyl acrylate) Polymers 0.000 claims description 2
- MEMNKNZDROKJHP-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;methyl sulfate Chemical compound COS([O-])(=O)=O.CCCCN1C=C[N+](C)=C1 MEMNKNZDROKJHP-UHFFFAOYSA-M 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 1
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- 239000011257 shell material Substances 0.000 description 54
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- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
- B32B21/10—Next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
- B32B3/12—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by a layer of regularly- arranged cells, e.g. a honeycomb structure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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Abstract
The invention discloses an epoxy resin composition containing a microcapsule curing agent, and a prepreg and a composite material thereof, wherein the epoxy resin composition comprises the microcapsule curing agent, epoxy resin and a diluent, and the weight parts of the components are as follows: the epoxy resin curing agent comprises 80-100 parts of epoxy resin, 15-30 parts of a microcapsule curing agent and 10-20 parts of a diluent, wherein the microcapsule curing agent consists of a thermoplastic shell and the epoxy resin curing agent, the epoxy resin curing agent is wrapped inside the thermoplastic shell, and the particle size of the microcapsule curing agent is 3-20 microns.
Description
Technical Field
The invention belongs to the technical field of toughening modification of epoxy resin, and particularly relates to an epoxy resin composition containing a microcapsule curing agent, and a prepreg and a composite material thereof.
Background
The fiber reinforced composite material is widely applied to structural members, aerospace products, automobile outer plates, display shells and the like due to light weight, high strength and attractive appearance, and the prepreg can be used in the manufacturing method. The prepreg is a sheet-shaped intermediate material obtained by infiltrating uncured matrix resin into reinforcing fibers, and a fiber-reinforced composite material is obtained by layering a plurality of prepregs and heating and pressurizing the layers.
Epoxy resin is an epoxy oligomer, can form three-dimensional reticular thermosetting plastic when reacting with a curing agent, has the characteristics of small shrinkage rate in the curing reaction process, and excellent cohesiveness, heat resistance, chemical resistance, mechanical property and electrical property of a cured product, is a variety with larger application amount in thermosetting resin, has the defect of poor toughness, and therefore, the toughness of the cured product needs to be improved by a certain method.
The toughening modification of the epoxy resin is an important research content of basic research and application development in the field of polymer science, and the epoxy resin is toughened by only adopting rubber, an elastomer or rigid particles, which has some defects. For example, the toughening effect can be achieved only by adopting rubber or elastomer to toughen the epoxy resin and usually by adding 20 percent of the epoxy resin; the inorganic rigid particles are adopted for toughening, the rigid particles are strict in size requirement, and are not beneficial to toughening when being too large, and in addition, the rigid particles need to have proper elastic modulus and good interface compatibility with an epoxy resin matrix, so that the rigid particles are required to be modified, the manufacturability is reduced, and the cost is increased.
At present, the service life of a large amount of supplied prepreg is generally 30 days at normal temperature, the prepreg is generally required to be stored in a freezing mode, the freezing storage temperature is-18 ℃, and a prepreg user needs to be equipped with a refrigeration house or freezing equipment, so that the use cost is increased.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides an epoxy resin composition containing a microcapsule curing agent, and a prepreg and a composite material thereof, and overcomes the defects of 1: the toughening epoxy resin is toughened by only adopting rubber or elastomer, and the toughening effect can be achieved only by the addition of 20 percent of the epoxy resin; 2: the inorganic rigid particles are adopted for toughening, the rigid particles have strict requirements on the size, and are not beneficial to toughening when being too large, and in addition, the rigid particles need to have proper elastic modulus and good interface compatibility with an epoxy resin matrix, so that the rigid particles are required to be modified, the manufacturability is reduced, and the cost is increased; 3: the working life of the existing prepreg at normal temperature is generally 30 days, the prepreg is generally required to be frozen and stored at the temperature of-18 ℃, and a prepreg user needs to be equipped with a refrigeration house or refrigeration equipment, so that the use cost is increased, and the like.
In order to solve the technical problem, the technical scheme of the invention is as follows: the epoxy resin composition containing the microcapsule curing agent comprises the microcapsule curing agent, epoxy resin and a diluent, wherein the weight parts of the components are as follows: the epoxy resin curing agent comprises 80-100 parts of epoxy resin, 15-30 parts of a microcapsule curing agent and 10-20 parts of a diluent, wherein the microcapsule curing agent consists of a thermoplastic shell and the epoxy resin curing agent, the epoxy resin curing agent is wrapped inside the thermoplastic shell, and the particle size of the microcapsule curing agent is 3-20 microns.
Preferably, the paint also comprises one or more of a flame retardant, a UV absorbent, an antistatic agent and an electromagnetic shielding agent, wherein the weight parts of each component are as follows: 100 parts of epoxy resin, 15-20 parts of microcapsule curing agent, 10-15 parts of diluent, 0-15 parts of flame retardant, 0-15 parts of UV absorbent, 0-15 parts of antistatic agent and 0-15 parts of electromagnetic shielding agent.
Preferably, the thermoplastic shell is selected from the group consisting of polymethylmethacrylate, polyethylmethacrylate, polymethylmethacrylate, polybutylacrylate, polypropylpropyl acrylate, nylon 6, nylon 12, nylon 6/12 copolymer, nylon 11, polyethersulfone, polyetherethersulfone, polyetherimide, PEEK, PEK, or PEKK.
Preferably, the epoxy resin curing agent is selected from imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-phenylimidazole, 1-cyano-2-ethyl-4-methylimidazole, 1-cyano-2-phenylimidazole, dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, aminobenzoate, methylhexahydrophthalic anhydride, phthalic anhydride, pyromellitic dianhydride, trimellitic anhydride, eleostearic anhydride, nadic anhydride, glutaric anhydride, or terpene-based anhydride.
Preferably, the epoxy resin is selected from liquid bisphenol A epoxy resin, liquid bisphenol F epoxy resin, E-51, E-44, E-42 or YDF-1020.
Preferably, the diluent is a reactive diluent or a non-reactive diluent, wherein the reactive diluent is selected from butyl glycidyl ether, benzyl glycidyl ether, glycidyl oleate, glycidyl benzoate, phenyl glycidyl ether, bis (2, 3-epoxycyclopentyl) ether or dicyclopentadiene dioxide, and wherein the non-reactive diluent is selected from acetone, absolute ethanol, toluene, xylene, styrene, ethyl acetate, butyl acetate, dimethylformamide, a polyol or benzyl alcohol.
Preferably, the flame retardant is selected from melamine polyphosphate, coated red phosphorus, methyl dimethyl phosphate, DOPO, aluminum hydroxide, magnesium hydroxide, triphenyl phosphate, chlorohydrocarbon 50, decabromodiphenyl oxide or antimony trioxide, the UV absorbent is selected from UV531, UV326, UV327, UV234, UV329, UV-P, UV328, UV360, UV622, UV770 and UV284, the antistatic agent is selected from Hostapur 93, Hostastat HS-1, Mersolat H95, Irgastat P18, PELECTRON PVL, ionics LQ01, CHEMISTAT 3033, CHEMISTAT 3500 or PESTAT LE1251, and the electromagnetic shielding agent is selected from silver-nickel-glass bead powder, copper powder, SAS, carbon black, graphene, carbon nanotube or iron-silver composite powder.
Preferably, the prepreg prepared by using the epoxy resin composition containing the microcapsule curing agent as described in any one of the above is prepared by adding the epoxy resin composition containing the microcapsule curing agent into a dip tank of a prepreg device, fully soaking the epoxy resin composition containing the microcapsule curing agent in a fiber material after the device is operated, and rolling to obtain the prepreg, wherein the fiber material is a unidirectional fiber bundle, plain cloth or twill cloth.
Preferably, the composite material prepared by using the epoxy resin composition containing the microcapsule curing agent as described in any one of the above comprises the epoxy resin composition containing the microcapsule curing agent, a sandwich structure and a prepreg, and the preparation process comprises the following steps:
step 1) brushing an epoxy resin composition containing a microcapsule curing agent on two surfaces of a sandwich structure;
step 2) respectively paving and sticking a plurality of layers of prepreg on two surfaces of the sandwich structure coated with the epoxy resin composition containing the microcapsule curing agent;
and 3) vacuumizing, heating and curing for 2 hours in an oven at the temperature of 90-130 ℃, and demolding to obtain the composite material of the epoxy resin composition containing the microcapsule curing agent.
Preferably, in the step 2), 2-10 layers of prepreg are respectively paved on two surfaces of the sandwich structure coated with the epoxy resin composition containing the microcapsule curing agent.
Compared with the prior art, the invention has the advantages that:
(1) the epoxy resin composition containing the microcapsule curing agent comprises the microcapsule curing agent, epoxy resin and a diluent, wherein the microcapsule curing agent consists of a thermoplastic shell and the epoxy resin curing agent, the epoxy resin curing agent is wrapped in the thermoplastic shell, and the particle size of the microcapsule curing agent is 3-20 mu m; because the epoxy resin curing agent is wrapped by the thermoplastic shell, the epoxy resin curing agent and the epoxy resin can be fully isolated, so that the quality guarantee period of the prepreg obtained by soaking the epoxy resin composition of the microcapsule curing agent is longer, can reach 180 days at normal temperature, and the quality guarantee period of the prepreg is greatly prolonged because the common prepreg is only 30 days;
(2) the microcapsule curing agent of the epoxy resin composition containing the microcapsule curing agent consists of a thermoplastic shell and the epoxy resin curing agent, wherein the thermoplastic microcapsule gradually collapses under the action of heating and a diluent, the epoxy resin curing agent flows out of the thermoplastic shell or the epoxy resin permeates into the thermoplastic shell to participate in reaction, and a three-dimensional network structure penetrating through the thermoplastic shell, namely a semi-interpenetrating network structure (semi-IPN) is gradually formed, and the domain size of a composite material system obtained by infiltrating the epoxy resin composition of the microcapsule curing agent after curing of a prepreg is about 2 microns, so that the toughness of the composite material is obviously improved;
(3) the prepreg prepared by the epoxy resin composition containing the microcapsule curing agent does not need to be stored in a freezing way, and only needs to be placed in a normal-temperature drying and sealing environment, so that the cost is greatly reduced, the storage stability is high, and the epoxy resin composition containing the microcapsule curing agent has a simple preparation method and reasonable compatibility of components.
Drawings
FIG. 1 is a particle size diagram of a microcapsule curing agent of the present invention;
FIG. 2 is a schematic diagram showing the coating rate of the microcapsule curing agent of the present invention;
FIG. 3 is a schematic view of a fracture surface of an epoxy resin composition containing a microcapsule curing agent according to the present invention;
FIG. 4 is a schematic diagram showing the glass transition temperature of the epoxy resin composition containing a microcapsule curing agent of the present invention.
Detailed Description
The following describes embodiments of the present invention with reference to examples:
it should be noted that the structures, proportions, sizes, and other elements shown in the specification are included for the purpose of understanding and reading only, and are not intended to limit the scope of the invention, which is defined by the claims, and any modifications of the structures, changes in the proportions and adjustments of the sizes, without affecting the efficacy and attainment of the same.
In addition, the terms "upper", "lower", "left", "right", "middle" and "one" used in the present specification are for clarity of description, and are not intended to limit the scope of the present invention, and the relative relationship between the terms and the terms is not to be construed as a scope of the present invention.
Example 1
The invention discloses an epoxy resin composition containing a microcapsule curing agent, which is characterized in that: the microcapsule curing agent comprises a microcapsule curing agent, epoxy resin and a diluent, wherein the microcapsule curing agent comprises the following components in parts by weight: the epoxy resin curing agent comprises 80-100 parts of epoxy resin, 15-30 parts of a microcapsule curing agent and 10-20 parts of a diluent, wherein the microcapsule curing agent consists of a thermoplastic shell and the epoxy resin curing agent, the epoxy resin curing agent is wrapped inside the thermoplastic shell, and the particle size of the microcapsule curing agent is 3-20 microns.
Example 2
The invention discloses an epoxy resin composition containing a microcapsule curing agent, which is characterized in that: the microcapsule curing agent comprises a microcapsule curing agent, epoxy resin and a diluent, wherein the microcapsule curing agent comprises the following components in parts by weight: the epoxy resin curing agent comprises 80-100 parts of epoxy resin, 15-30 parts of a microcapsule curing agent and 10-20 parts of a diluent, wherein the microcapsule curing agent consists of a thermoplastic shell and the epoxy resin curing agent, the epoxy resin curing agent is wrapped inside the thermoplastic shell, and the particle size of the microcapsule curing agent is 3-20 microns.
Preferably, the paint also comprises one or more of a flame retardant, a UV absorbent, an antistatic agent and an electromagnetic shielding agent, wherein the weight parts of each component are as follows: 100 parts of epoxy resin, 15-20 parts of microcapsule curing agent, 10-15 parts of diluent, 0-15 parts of flame retardant, 0-15 parts of UV absorbent, 0-15 parts of antistatic agent and 0-15 parts of electromagnetic shielding agent.
Example 3
The invention discloses an epoxy resin composition containing a microcapsule curing agent, which is characterized in that: the microcapsule curing agent comprises a microcapsule curing agent, epoxy resin and a diluent, wherein the microcapsule curing agent comprises the following components in parts by weight: the epoxy resin curing agent comprises 80-100 parts of epoxy resin, 15-30 parts of a microcapsule curing agent and 10-20 parts of a diluent, wherein the microcapsule curing agent consists of a thermoplastic shell and the epoxy resin curing agent, the epoxy resin curing agent is wrapped inside the thermoplastic shell, and the particle size of the microcapsule curing agent is 3-20 microns.
Preferably, the paint also comprises one or more of a flame retardant, a UV absorbent, an antistatic agent and an electromagnetic shielding agent, wherein the weight parts of each component are as follows: 100 parts of epoxy resin, 15-20 parts of microcapsule curing agent, 10-15 parts of diluent, 0-15 parts of flame retardant, 0-15 parts of UV absorbent, 0-15 parts of antistatic agent and 0-15 parts of electromagnetic shielding agent.
Preferably, the thermoplastic shell is selected from the group consisting of polymethylmethacrylate, polyethylmethacrylate, polymethylmethacrylate, polybutylacrylate, polypropylpropyl acrylate, nylon 6, nylon 12, nylon 6/12 copolymer, nylon 11, polyethersulfone, polyetherethersulfone, polyetherimide, PEEK, PEK, or PEKK.
Preferably, the epoxy resin curing agent is selected from imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-phenylimidazole, 1-cyano-2-ethyl-4-methylimidazole, 1-cyano-2-phenylimidazole, dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, aminobenzoate, methylhexahydrophthalic anhydride, phthalic anhydride, pyromellitic dianhydride, trimellitic anhydride, eleostearic anhydride, nadic anhydride, glutaric anhydride, or terpene-based anhydride.
Preferably, the epoxy resin is selected from liquid bisphenol A epoxy resin, liquid bisphenol F epoxy resin, E-51, E-44, E-42 or YDF-1020.
Preferably, the diluent is a reactive diluent or a non-reactive diluent, wherein the reactive diluent is selected from butyl glycidyl ether, benzyl glycidyl ether, glycidyl oleate, glycidyl benzoate, phenyl glycidyl ether, bis (2, 3-epoxycyclopentyl) ether or dicyclopentadiene dioxide, and wherein the non-reactive diluent is selected from acetone, absolute ethanol, toluene, xylene, styrene, ethyl acetate, butyl acetate, dimethylformamide, a polyol or benzyl alcohol.
Preferably, the flame retardant is selected from melamine polyphosphate, coated red phosphorus, methyl dimethyl phosphate, DOPO, aluminum hydroxide, magnesium hydroxide, triphenyl phosphate, chlorohydrocarbon 50, decabromodiphenyl oxide or antimony trioxide, the UV absorbent is selected from UV531, UV326, UV327, UV234, UV329, UV-P, UV328, UV360, UV622, UV770 and UV284, the antistatic agent is selected from Hostapur 93, Hostastat HS-1, Mersolat H95, Irgastat P18, PELECTRON PVL, ionics LQ01, CHEMISTAT 3033, CHEMISTAT 3500 or PESTAT LE1251, and the electromagnetic shielding agent is selected from silver-nickel-glass bead powder, copper powder, SAS, carbon black, graphene, carbon nanotube or iron-silver composite powder.
Example 4
The invention discloses an epoxy resin composition containing a microcapsule curing agent, which is characterized in that: the microcapsule curing agent comprises a microcapsule curing agent, epoxy resin and a diluent, wherein the microcapsule curing agent comprises the following components in parts by weight: the epoxy resin curing agent comprises 80-100 parts of epoxy resin, 15-30 parts of a microcapsule curing agent and 10-20 parts of a diluent, wherein the microcapsule curing agent consists of a thermoplastic shell and the epoxy resin curing agent, the epoxy resin curing agent is wrapped inside the thermoplastic shell, and the particle size of the microcapsule curing agent is 3-20 microns.
Preferably, the paint also comprises one or more of a flame retardant, a UV absorbent, an antistatic agent and an electromagnetic shielding agent, wherein the weight parts of each component are as follows: 100 parts of epoxy resin, 15-20 parts of microcapsule curing agent, 10-15 parts of diluent, 0-15 parts of flame retardant, 0-15 parts of UV absorbent, 0-15 parts of antistatic agent and 0-15 parts of electromagnetic shielding agent.
Preferably, the thermoplastic shell is selected from the group consisting of polymethylmethacrylate, polyethylmethacrylate, polymethylmethacrylate, polybutylacrylate, polypropylpropyl acrylate, nylon 6, nylon 12, nylon 6/12 copolymer, nylon 11, polyethersulfone, polyetherethersulfone, polyetherimide, PEEK, PEK, or PEKK.
Preferably, the epoxy resin curing agent is selected from imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-phenylimidazole, 1-cyano-2-ethyl-4-methylimidazole, 1-cyano-2-phenylimidazole, dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, aminobenzoate, methylhexahydrophthalic anhydride, phthalic anhydride, pyromellitic dianhydride, trimellitic anhydride, eleostearic anhydride, nadic anhydride, glutaric anhydride, or terpene-based anhydride.
Preferably, the epoxy resin is selected from liquid bisphenol A epoxy resin, liquid bisphenol F epoxy resin, E-51, E-44, E-42 or YDF-1020.
Preferably, the diluent is a reactive diluent or a non-reactive diluent, wherein the reactive diluent is selected from butyl glycidyl ether, benzyl glycidyl ether, glycidyl oleate, glycidyl benzoate, phenyl glycidyl ether, bis (2, 3-epoxycyclopentyl) ether or dicyclopentadiene dioxide, and wherein the non-reactive diluent is selected from acetone, absolute ethanol, toluene, xylene, styrene, ethyl acetate, butyl acetate, dimethylformamide, a polyol or benzyl alcohol.
Preferably, the flame retardant is selected from melamine polyphosphate, coated red phosphorus, methyl dimethyl phosphate, DOPO, aluminum hydroxide, magnesium hydroxide, triphenyl phosphate, chlorohydrocarbon 50, decabromodiphenyl oxide or antimony trioxide, the UV absorbent is selected from UV531, UV326, UV327, UV234, UV329, UV-P, UV328, UV360, UV622, UV770 and UV284, the antistatic agent is selected from Hostapur 93, Hostastat HS-1, Mersolat H95, Irgastat P18, PELECTRON PVL, ionics LQ01, CHEMISTAT 3033, CHEMISTAT 3500 or PESTAT LE1251, and the electromagnetic shielding agent is selected from silver-nickel-glass bead powder, copper powder, SAS, carbon black, graphene, carbon nanotube or iron-silver composite powder.
Preferably, the prepreg prepared by using the epoxy resin composition containing the microcapsule curing agent as described in any one of the above is prepared by adding the epoxy resin composition containing the microcapsule curing agent into a dip tank of a prepreg device, fully soaking the epoxy resin composition containing the microcapsule curing agent in a fiber material after the device is operated, and rolling to obtain the prepreg.
Example 5
The invention discloses an epoxy resin composition containing a microcapsule curing agent, which is characterized in that: the microcapsule curing agent comprises a microcapsule curing agent, epoxy resin and a diluent, wherein the microcapsule curing agent comprises the following components in parts by weight: the epoxy resin curing agent comprises 80-100 parts of epoxy resin, 15-30 parts of a microcapsule curing agent and 10-20 parts of a diluent, wherein the microcapsule curing agent consists of a thermoplastic shell and the epoxy resin curing agent, the epoxy resin curing agent is wrapped inside the thermoplastic shell, and the particle size of the microcapsule curing agent is 3-20 microns.
Preferably, the paint also comprises one or more of a flame retardant, a UV absorbent, an antistatic agent and an electromagnetic shielding agent, wherein the weight parts of each component are as follows: 100 parts of epoxy resin, 15-20 parts of microcapsule curing agent, 10-15 parts of diluent, 0-15 parts of flame retardant, 0-15 parts of UV absorbent, 0-15 parts of antistatic agent and 0-15 parts of electromagnetic shielding agent.
Preferably, the thermoplastic shell is selected from the group consisting of polymethylmethacrylate, polyethylmethacrylate, polymethylmethacrylate, polybutylacrylate, polypropylpropyl acrylate, nylon 6, nylon 12, nylon 6/12 copolymer, nylon 11, polyethersulfone, polyetherethersulfone, polyetherimide, PEEK, PEK, or PEKK.
Preferably, the epoxy resin curing agent is selected from imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-phenylimidazole, 1-cyano-2-ethyl-4-methylimidazole, 1-cyano-2-phenylimidazole, dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, aminobenzoate, methylhexahydrophthalic anhydride, phthalic anhydride, pyromellitic dianhydride, trimellitic anhydride, eleostearic anhydride, nadic anhydride, glutaric anhydride, or terpene-based anhydride.
Preferably, the epoxy resin is selected from liquid bisphenol A epoxy resin, liquid bisphenol F epoxy resin, E-51, E-44, E-42 or YDF-1020.
Preferably, the diluent is a reactive diluent or a non-reactive diluent, wherein the reactive diluent is selected from butyl glycidyl ether, benzyl glycidyl ether, glycidyl oleate, glycidyl benzoate, phenyl glycidyl ether, bis (2, 3-epoxycyclopentyl) ether or dicyclopentadiene dioxide, and wherein the non-reactive diluent is selected from acetone, absolute ethanol, toluene, xylene, styrene, ethyl acetate, butyl acetate, dimethylformamide, a polyol or benzyl alcohol.
Preferably, the flame retardant is selected from melamine polyphosphate, coated red phosphorus, methyl dimethyl phosphate, DOPO, aluminum hydroxide, magnesium hydroxide, triphenyl phosphate, chlorohydrocarbon 50, decabromodiphenyl oxide or antimony trioxide, the UV absorbent is selected from UV531, UV326, UV327, UV234, UV329, UV-P, UV328, UV360, UV622, UV770 and UV284, the antistatic agent is selected from Hostapur 93, Hostastat HS-1, Mersolat H95, Irgastat P18, PELECTRON PVL, ionics LQ01, CHEMISTAT 3033, CHEMISTAT 3500 or PESTAT LE1251, and the electromagnetic shielding agent is selected from silver-nickel-glass bead powder, copper powder, SAS, carbon black, graphene, carbon nanotube or iron-silver composite powder.
Preferably, the prepreg prepared by using the epoxy resin composition containing the microcapsule curing agent as described in any one of the above is prepared by adding the epoxy resin composition containing the microcapsule curing agent into a dip tank of a prepreg device, fully soaking the epoxy resin composition containing the microcapsule curing agent in a fiber material after the device is operated, and rolling to obtain the prepreg, wherein the fiber material is a unidirectional fiber bundle, plain cloth or twill cloth.
Preferably, the composite material prepared by using the epoxy resin composition containing the microcapsule curing agent as described in any one of the above comprises the epoxy resin composition containing the microcapsule curing agent, a sandwich structure and a prepreg, and the preparation process comprises the following steps:
step 1) brushing an epoxy resin composition containing a microcapsule curing agent on two surfaces of a sandwich structure;
step 2) respectively paving and sticking a plurality of layers of prepreg on two surfaces of the sandwich structure coated with the epoxy resin composition containing the microcapsule curing agent;
and 3) vacuumizing, heating and curing for 2 hours in an oven at the temperature of 90-130 ℃, and demolding to obtain the composite material of the epoxy resin composition containing the microcapsule curing agent.
Preferably, in the step 2), 2-10 layers of prepreg are respectively paved on two surfaces of the sandwich structure coated with the epoxy resin composition containing the microcapsule curing agent.
The microcapsule shell used in the prior art is a reaction product of any 2 or more than 2 of isocyanate compound, active hydrogen compound, curing agent for epoxy resin, epoxy resin and low molecular amine compound, the microcapsule shell has the functions of isolating the curing agent and resin and increasing solvent resistance and moisture resistance, and the microcapsule shell is an epoxy resin curing system and is different from the thermoplastic shell.
The epoxy resin is preferably a low-viscosity liquid bisphenol A epoxy resin or liquid bisphenol F epoxy resin, and examples thereof include domestic E-51, E-44 and E-42, 6004, 6005, 6010, 6020 and 6030 available from GIba-Gelgy, EPON826, EPON828 and EPON830 available from Shell, and domestic YDF-1020 available from Shell.
The fiber material plays a bearing role in the composite material, and is selected from glass fiber, carbon fiber, silicon carbide fiber, high silica fiber, boron carbide fiber, quartz fiber and the like. The fibrous material may be unidirectional fiber bundles, plain or twill.
The sandwich structure in the composite material mainly bears the transverse shear stress transmitted by the panels, stabilizes the upper and lower panels and prevents local yielding. The sandwich structure is Nomex honeycomb, PVC foam, PMI foam, polyurethane foam, balsa wood and the like.
The thermoplastic shell is made of a material with good compatibility with epoxy resin, and the molecular weight of the thermoplastic shell is 10000-1000000. The microcapsule curing agent is prepared by any one of a solvent volatilization method, a spray freezing method, a spray drying method or an interfacial polymerization method.
The prepregs of the present invention may be prepared on prepreg equipment in a manner which is conventional to those skilled in the art.
The composite material is prepared in a drying room or an autoclave, wherein the preparation method is vacuum bag pressing method or autoclave forming method. The various materials described herein are commercially available.
Example 6
Fully mixing 100g of epoxy resin E-51, 20g of a microcapsule curing agent (the particle diameter is 3-20 mu m) of polymethyl methacrylate wrapping 2-phenylimidazole and 15g of a diluent benzyl glycidyl ether by using a mixing device to obtain an epoxy resin composition containing the microcapsule curing agent;
adding the prepared epoxy resin composition containing the microcapsule curing agent into a glue dipping tank of prepreg equipment, fully soaking the epoxy resin composition containing the microcapsule curing agent into a fiber material after the equipment runs, and rolling to obtain a prepreg;
brushing the epoxy resin composition containing the microcapsule curing agent on two surfaces of a sandwich structure, paving two layers of prepreg on the two surfaces of the sandwich structure respectively, vacuumizing, heating and curing for 2 hours in an oven at 90-130 ℃, demolding to obtain the composite material of the epoxy resin composition containing the microcapsule curing agent, and cutting the demolded sample into sample strips with the thickness of 75 x 10 x 5 mm.
Example 7
By utilizing a mixing device, fully mixing 80g of epoxy resin E-44, 15g of imidazole-coated polyethylene methacrylate microcapsule curing agent (the particle size is 3-20 mu m) and 10g of diluent butyl glycidyl ether to obtain an epoxy resin composition containing the microcapsule curing agent;
adding the prepared epoxy resin composition containing the microcapsule curing agent into a glue dipping tank of prepreg equipment, fully soaking the epoxy resin composition containing the microcapsule curing agent into a fiber material after the equipment runs, and rolling to obtain a prepreg;
brushing the epoxy resin composition containing the microcapsule curing agent on two surfaces of a sandwich structure, paving two layers of prepreg on the two surfaces of the sandwich structure respectively, vacuumizing, heating and curing for 2 hours in an oven at 90-130 ℃, demolding to obtain the composite material of the epoxy resin composition containing the microcapsule curing agent, and cutting the demolded sample into sample strips with the thickness of 75 x 10 x 5 mm.
Example 8
By utilizing a mixing device, fully mixing 90g of epoxy resin E-42, 18g of microcapsule curing agent (the particle size is 3-20 mu m) of polymethyl acrylate wrapping 2-methylimidazole, 15g of diluent glycidyl oleate, 15g of melamine polyphosphate, 10gUV531, 5g of Hostapur SAS93 and 5g of silver-nickel-glass bead powder to obtain an epoxy resin composition containing the microcapsule curing agent;
adding the prepared epoxy resin composition containing the microcapsule curing agent into a glue dipping tank of prepreg equipment, fully soaking the epoxy resin composition containing the microcapsule curing agent into a fiber material after the equipment runs, and rolling to obtain a prepreg;
brushing the epoxy resin composition containing the microcapsule curing agent on two surfaces of a sandwich structure, paving two layers of prepreg on the two surfaces of the sandwich structure respectively, vacuumizing, heating and curing for 2 hours in an oven at 90-130 ℃, demolding to obtain the composite material of the epoxy resin composition containing the microcapsule curing agent, and cutting the demolded sample into sample strips with the thickness of 75 x 10 x 5 mm.
Example 9
Fully mixing 100g of epoxy resin YDF-1020, 30g of a microcapsule curing agent (the particle diameter is 3-20 mu m) of polybutyl acrylate wrapping 2-ethylimidazole, 20g of diluent glycidyl benzoate, 10g of coated red phosphorus, 15gUV326, 15g of Hostastat HS-1 and 10g of copper powder by using a mixing device to obtain an epoxy resin composition containing the microcapsule curing agent;
adding the prepared epoxy resin composition containing the microcapsule curing agent into a glue dipping tank of prepreg equipment, fully soaking the epoxy resin composition containing the microcapsule curing agent into a fiber material after the equipment runs, and rolling to obtain a prepreg;
brushing the epoxy resin composition containing the microcapsule curing agent on two surfaces of a sandwich structure, paving two layers of prepreg on the two surfaces of the sandwich structure respectively, vacuumizing, heating and curing for 2 hours in an oven at 90-130 ℃, demolding to obtain the composite material of the epoxy resin composition containing the microcapsule curing agent, and cutting the demolded sample into sample strips with the thickness of 75 x 10 x 5 mm.
Example 10
An epoxy resin composition containing a microcapsule curing agent was obtained by thoroughly mixing 100g of a liquid bisphenol A epoxy resin, 20g of a microcapsule curing agent (particle diameter: 3 to 20 μm) of 2-ethyl-4-methylimidazole-coated nylon 12, 15g of a diluent, phenyl glycidyl ether, 5g of dimethyl methyl phosphate, 5gUV234, 10g of Irgastat P18 and 15g of carbon black in a mixing apparatus;
adding the prepared epoxy resin composition containing the microcapsule curing agent into a glue dipping tank of prepreg equipment, fully soaking the epoxy resin composition containing the microcapsule curing agent into a fiber material after the equipment runs, and rolling to obtain a prepreg;
brushing the epoxy resin composition containing the microcapsule curing agent on two surfaces of a sandwich structure, paving two layers of prepreg on the two surfaces of the sandwich structure respectively, vacuumizing, heating and curing for 2 hours in an oven at 90-130 ℃, demolding to obtain the composite material of the epoxy resin composition containing the microcapsule curing agent, and cutting the demolded sample into sample strips with the thickness of 75 x 10 x 5 mm.
Comparative example 1
100g of epoxy resin E-51, 2g of 2-phenylimidazole curing agent and 15g of benzyl glycidyl ether as a diluent were thoroughly mixed by a mixing device to obtain an epoxy resin composition, and a prepreg and a composite material were prepared from the epoxy resin composition.
Comparative example 2
100g of epoxy resin E-51, 2g of 2-phenylimidazole curing agent, 18g of polymethyl methacrylate powder (particle size: about 10 μm), and 15g of benzyl glycidyl ether as a diluent were thoroughly mixed by a mixing device to obtain an epoxy resin composition, and a prepreg and a composite material were prepared from the epoxy resin composition.
Comparative example 3
100g of epoxy resin E-51, 2g of 2-phenylimidazole, 28g of polymethyl methacrylate microcapsule curing agent and 15g of diluent benzyl glycidyl ether are fully mixed by a mixing device to obtain an epoxy resin composition, and the epoxy resin composition is used for preparing prepregs and composite materials.
Measurement of Room temperature storage period of prepreg obtained by impregnating epoxy resin composition containing microcapsule curing agent
The prepreg obtained in the embodiment 6-10 is placed in a normal-temperature dry closed environment, the prepreg state is checked after 40 days, and the prepreg has consistent touch feeling compared with a fresh prepreg and is not hardened; the prepreg state was checked after 180 days and was consistent with a fresh prepreg to the touch and not stiff.
And (3) placing the prepreg obtained in the comparative examples 1-3 in a normal-temperature dry closed environment, and checking the state of the prepreg after 40 days to make the prepreg hard.
Impact power and impact toughness detection of composite material prepared from prepreg soaked by epoxy resin composition containing microcapsule curing agent
Brushing the epoxy resin composition on two surfaces of a sandwich structure, respectively laying two layers of epoxy prepregs containing the microcapsule curing agent on the two surfaces of the sandwich structure, vacuumizing, heating and curing in an oven at 90-130 ℃ for 2 hours, demolding, cutting a demolded sample into sample strips of 75 x 10 x 5mm, testing impact energy and impact toughness according to the standard ISO 179-1:2000, and testing the results as shown in Table 1:
TABLE 1 impact work and impact toughness of the composites
As can be seen from Table 1, the composite material prepared from the prepreg impregnated with the epoxy resin composition containing the microcapsule curing agent has impact energy and impact toughness both significantly higher than those of the comparative examples, and has impact toughness higher than that of the comparative examples, and the toughness is improved by 95.8% at most.
As can be seen from the comparison between example 6 and comparative example 2, the toughening mechanism of the epoxy cured product of the present invention is no longer the conventional blending toughening, but a new structure semi-interpenetrating network structure semi-IPN is formed, and the semi-IPN can effectively prevent crack propagation and improve the toughness of the composite material.
The invention has the following characteristics on the particle size of the microcapsule curing agent: the particle size of the microcapsule curing agent can be characterized by a polarizing microscope, as shown in fig. 1, and the characterization result is as follows: the microcapsule curing agent has a particle size of about 3 to 20 μm.
The invention has the characteristics of the coating rate of the microcapsule curing agent: the invention adopts a thermogravimetric analyzer to represent the coating rate of the microcapsule curing agent, as shown in figure 2:
as can be seen from FIG. 2, the temperature at which the thermoplastic shell (shell) starts to decompose is about 380 ℃ and the temperature at which the epoxy resin curing agent (core) starts to decompose is about 180 ℃. The epoxy resin curing agent is wrapped in the thermoplastic shell to form the microcapsule curing agent (microcapsule), the decomposition temperature starts to move towards the high temperature direction, as can be seen from fig. 2, the decomposition temperature of the microcapsule curing agent is about 250 ℃, a step appears at about 350 ℃, the decomposition temperature curve after the step is consistent with the decomposition temperature trend and the inclination of the thermoplastic shell, which shows that the thermoplastic shell is decomposed after the step, and the epoxy resin curing agent (core) is decomposed at the step. By comparing the left coordinates, the coating rate of the epoxy resin curing agent was about 10%.
The invention is characterized in that the fracture surface of the epoxy resin composition containing the microcapsule curing agent is as follows: the fracture surface of the epoxy resin composition containing the microcapsule curing agent can be characterized by a scanning electron microscope, as shown in fig. 3, the microcapsule curing agent already participates in the reaction, the fracture surface after the reaction is not a smooth section, but is a stacked spherical particle, the particle size is about 2 μm and is less than 3-20 μm of the microcapsule size, the microcapsule curing agent is a multi-core structure, each core is a reaction center, and each reaction center forms a micron-sized semi-interpenetrating network structure semi-IPN with the epoxy resin.
The invention is characterized by the glass transition temperature of the epoxy resin composition containing the microcapsule curing agent: the glass transition temperature of the epoxy resin composition containing the microcapsule curing agent can be characterized by DMA, as shown in fig. 4:
FIG. 4 is a DMA curve of curing agent and epoxy resin (EP/curing agent), curing agent and epoxy system with the addition of pure shell microspheres (EP/curing agent + thermoplastic shell), and epoxy resin with the addition of microcapsule curing agent (EP/microcapsule curing agent). The temperature corresponding to the peak value of the curve is the glass transition temperature of the system, and compared with the three curves, the EP/microcapsule curing agent system has the lowest glass transition temperature, the EP/curing agent + thermoplastic shell is the second order, and the highest EP/curing agent system. Therefore, the thermoplastic shell material has a toughening effect on an epoxy resin system, the glass transition temperature can be reduced to a certain extent by simply mixing, and the toughness of the system is improved, but the effects of reducing the glass transition temperature and improving the toughness of the microcapsule curing agent are better.
The reaction principle of the invention is as follows:
the microcapsule curing agent of the invention is composed of a thermoplastic shell and an epoxy resin curing agent, after the microcapsule curing agent is added into epoxy resin, under the action of heating and a diluent, the thermoplastic shell gradually collapses, the epoxy resin curing agent flows out of the thermoplastic shell or the epoxy resin permeates into the thermoplastic shell to participate in reaction, and a three-dimensional network structure penetrating through the thermoplastic microcapsule shell is gradually formed, namely a semi-interpenetrating network structure (semi-IPN), because the microsphere phase size of a cured material system is smaller than the microcapsule size, as can be seen from the comparison of figure 1 and figure 3, the microcapsule is a multi-core structure. Each microcapsule curing agent forms a plurality of micron-sized semi-IPN structures (as shown in figure 3), and when cracks expand to the surface of a micro semi-IPN spherical structure, the crack expansion can be effectively blocked, namely the toughness of a cured product is effectively improved. The thermoplastic shell material has good compatibility with the epoxy matrix, and the thermoplastic shell material has softer segments than the epoxy matrix, and can act as a plasticizer for the epoxy matrix, as evidenced by the decrease in glass transition temperature (as shown in fig. 4).
The epoxy resin composition containing the microcapsule curing agent comprises the microcapsule curing agent, epoxy resin and a diluent, wherein the microcapsule curing agent consists of a thermoplastic shell and the epoxy resin curing agent, the epoxy resin curing agent is wrapped in the thermoplastic shell, and the particle size of the microcapsule curing agent is 3-20 mu m; because the epoxy resin curing agent is wrapped by the thermoplastic shell, the epoxy resin curing agent and the epoxy resin can be fully isolated, so that the shelf life of the prepreg obtained by soaking the epoxy resin composition of the microcapsule curing agent is longer, can reach 180 days at normal temperature, and the shelf life of the prepreg is greatly prolonged because the common prepreg is only 30 days.
The microcapsule curing agent of the epoxy resin composition containing the microcapsule curing agent comprises a thermoplastic shell and the epoxy resin curing agent, wherein the thermoplastic microcapsule gradually collapses under the action of heating and a diluent, the epoxy resin curing agent flows out of the thermoplastic shell or the epoxy resin permeates into the thermoplastic shell to participate in reaction, and a three-dimensional network structure penetrating through the thermoplastic shell, namely a semi-interpenetrating network structure (semi-IPN) is gradually formed, and the domain size of a composite material system obtained by impregnating the epoxy resin composition of the microcapsule curing agent after curing of a prepreg is about 2 microns, so that the toughness of the composite material is obviously improved.
The prepreg prepared by the epoxy resin composition containing the microcapsule curing agent does not need to be stored in a freezing way, and only needs to be placed in a normal-temperature drying and sealing environment, so that the cost is greatly reduced, the storage stability is high, and the epoxy resin composition containing the microcapsule curing agent has a simple preparation method and reasonable compatibility of components.
While the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Many other changes and modifications can be made without departing from the spirit and scope of the invention. It is to be understood that the invention is not to be limited to the specific embodiments, but only by the scope of the appended claims.
Claims (10)
1. An epoxy resin composition containing a microcapsule curing agent, characterized in that: the microcapsule curing agent comprises a microcapsule curing agent, epoxy resin and a diluent, wherein the microcapsule curing agent comprises the following components in parts by weight: the epoxy resin curing agent comprises 80-100 parts of epoxy resin, 15-30 parts of a microcapsule curing agent and 10-20 parts of a diluent, wherein the microcapsule curing agent consists of a thermoplastic shell and the epoxy resin curing agent, the epoxy resin curing agent is wrapped inside the thermoplastic shell, and the particle size of the microcapsule curing agent is 3-20 microns.
2. The microcapsule curing agent-containing epoxy resin composition according to claim 1, characterized in that: the paint also comprises one or more of a flame retardant, a UV absorbent, an antistatic agent and an electromagnetic shielding agent, wherein the weight parts of the components are as follows: 100 parts of epoxy resin, 15-20 parts of microcapsule curing agent, 10-15 parts of diluent, 0-15 parts of flame retardant, 0-15 parts of UV absorbent, 0-15 parts of antistatic agent and 0-15 parts of electromagnetic shielding agent.
3. The microcapsule curing agent-containing epoxy resin composition according to claim 2, characterized in that: the thermoplastic shell is selected from the group consisting of polymethyl methacrylate, polyethyl methacrylate, polymethyl acrylate, polybutyl acrylate, polypropylene acrylate, nylon 6, nylon 12, nylon 6/12 copolymer, nylon 11, polyethersulfone, polyether ether sulfone, polyetherimide, PEEK, PEK, or PEKK.
4. The microcapsule curing agent-containing epoxy resin composition according to claim 2, characterized in that: the epoxy resin curing agent is selected from imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-phenylimidazole, 1-cyano-2-ethyl-4-methylimidazole, 1-cyano-2-phenylimidazole, dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, aminobenzoate, methylhexahydrophthalic anhydride, phthalic anhydride, pyromellitic dianhydride, trimellitic anhydride, elaeostearic anhydride, nadic anhydride, glutaric anhydride or terpene-based anhydride.
5. The microcapsule curing agent-containing epoxy resin composition according to claim 2, characterized in that: the epoxy resin is selected from liquid bisphenol A epoxy resin, liquid bisphenol F epoxy resin, E-51, E-44, E-42 or YDF-1020.
6. The microcapsule curing agent-containing epoxy resin composition according to claim 2, characterized in that: the diluent is a reactive diluent or a non-reactive diluent, wherein the reactive diluent is selected from butyl glycidyl ether, benzyl glycidyl ether, glycidyl oleate, glycidyl benzoate, phenyl glycidyl ether, bis (2, 3-epoxycyclopentyl) ether or dicyclopentadiene dioxide, and the non-reactive diluent is selected from acetone, absolute ethyl alcohol, toluene, xylene, styrene, ethyl acetate, butyl acetate, dimethylformamide, polyhydric alcohol or benzyl alcohol.
7. The microcapsule curing agent-containing epoxy resin composition according to claim 2, characterized in that: the flame retardant is selected from melamine polyphosphate, coated red phosphorus, methyl dimethyl phosphate, DOPO, aluminum hydroxide, magnesium hydroxide, triphenyl phosphate, chlorocarbon 50, decabromodiphenyl oxide or antimony trioxide, the UV absorbent is selected from UV531, UV326, UV327, UV234, UV329, UV-P, UV328, UV360, UV622, UV770 and UV284, the antistatic agent is selected from Hostapu SAS93, Hostastat HS-1, Mersolat H95, Irgastat P18, PELECTRON PVL, Basionics LQ01, CHEMISTAT 3033, CHEMISTAT 3500 or PELESTAT 1251, and the electromagnetic shielding agent is selected from silver-nickel-glass powder, copper powder, iron powder, carbon black, graphene, carbon nano tube or iron-silver composite powder.
8. A prepreg produced using the microcapsule curing agent-containing epoxy resin composition according to any one of claims 1 to 7, characterized in that: adding the epoxy resin composition containing the microcapsule curing agent into a glue dipping tank of prepreg equipment, fully soaking the epoxy resin composition containing the microcapsule curing agent into a fiber material after the equipment runs, and rolling to obtain the prepreg, wherein the fiber material is a unidirectional fiber bundle, plain cloth or twill cloth.
9. A composite material prepared by using the epoxy resin composition containing the microcapsule curing agent as described in any one of claims 1 to 8, which comprises the epoxy resin composition containing the microcapsule curing agent, a sandwich structure and a prepreg, and the preparation process comprises the following steps:
step 1) brushing an epoxy resin composition containing a microcapsule curing agent on two surfaces of a sandwich structure;
step 2) respectively paving and sticking a plurality of layers of prepreg on two surfaces of the sandwich structure coated with the epoxy resin composition containing the microcapsule curing agent;
and 3) vacuumizing, heating and curing for 2 hours in an oven at the temperature of 90-130 ℃, and demolding to obtain the composite material of the epoxy resin composition containing the microcapsule curing agent.
10. The composite material prepared from the epoxy resin composition containing the microcapsule curing agent according to claim 9, wherein 2-10 layers of prepreg are respectively laid on two surfaces of the sandwich structure coated with the epoxy resin composition containing the microcapsule curing agent in the step 2).
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CN201911118414.3A CN110791053A (en) | 2019-11-15 | 2019-11-15 | Epoxy resin composition containing microcapsule curing agent, and prepreg and composite material thereof |
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Cited By (2)
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CN113817426A (en) * | 2021-08-25 | 2021-12-21 | 苏州锐朗新材料有限公司 | Conductive adhesive applied to bonding of large-size chips and preparation method thereof |
CN113908782A (en) * | 2021-08-13 | 2022-01-11 | 深圳市深赛尔股份有限公司 | Environment-friendly epoxy resin self-repairing microcapsule and preparation process thereof |
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CN1112142A (en) * | 1994-03-15 | 1995-11-22 | 东丽株式会社 | Microcapsule-type curing agent, method for producing the same, thermosetting resin composition, prepreg and fiber reinforced composite material |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113908782A (en) * | 2021-08-13 | 2022-01-11 | 深圳市深赛尔股份有限公司 | Environment-friendly epoxy resin self-repairing microcapsule and preparation process thereof |
CN113908782B (en) * | 2021-08-13 | 2024-05-24 | 深圳市深赛尔股份有限公司 | Environment-friendly epoxy resin self-repairing microcapsule and preparation process thereof |
CN113817426A (en) * | 2021-08-25 | 2021-12-21 | 苏州锐朗新材料有限公司 | Conductive adhesive applied to bonding of large-size chips and preparation method thereof |
CN113817426B (en) * | 2021-08-25 | 2023-06-30 | 上海锐朗光电材料有限公司 | Conductive adhesive applied to large-size chip bonding and preparation method thereof |
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