CN104403268A - Ultraviolet-curable resin composition and fiber reinforced resin-based composite material thereof - Google Patents
Ultraviolet-curable resin composition and fiber reinforced resin-based composite material thereof Download PDFInfo
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- CN104403268A CN104403268A CN201410617499.0A CN201410617499A CN104403268A CN 104403268 A CN104403268 A CN 104403268A CN 201410617499 A CN201410617499 A CN 201410617499A CN 104403268 A CN104403268 A CN 104403268A
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- curable resin
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- 239000011342 resin composition Substances 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 29
- 239000000835 fiber Substances 0.000 title claims abstract description 20
- 239000000805 composite resin Substances 0.000 title abstract description 5
- 239000011159 matrix material Substances 0.000 claims abstract description 32
- 239000003822 epoxy resin Substances 0.000 claims abstract description 22
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 22
- 239000003999 initiator Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims description 40
- 239000011347 resin Substances 0.000 claims description 40
- -1 glycidyl ester Chemical class 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 150000001768 cations Chemical class 0.000 claims description 9
- 239000004744 fabric Substances 0.000 claims description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 8
- 229920013657 polymer matrix composite Polymers 0.000 claims description 8
- 239000011160 polymer matrix composite Substances 0.000 claims description 8
- 230000002787 reinforcement Effects 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000049 pigment Substances 0.000 claims description 6
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- QXONIHMUSQFKJU-UHFFFAOYSA-N 2-(prop-1-enoxymethyl)oxirane Chemical compound CC=COCC1CO1 QXONIHMUSQFKJU-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 4
- 125000001743 benzylic group Chemical group 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 4
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 claims description 2
- 244000028419 Styrax benzoin Species 0.000 claims description 2
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 2
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 claims description 2
- 229960002130 benzoin Drugs 0.000 claims description 2
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004845 glycidylamine epoxy resin Substances 0.000 claims description 2
- 235000019382 gum benzoic Nutrition 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 8
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 238000010538 cationic polymerization reaction Methods 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 239000012952 cationic photoinitiator Substances 0.000 abstract 2
- 239000003085 diluting agent Substances 0.000 abstract 1
- 230000001902 propagating effect Effects 0.000 abstract 1
- 230000003014 reinforcing effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 15
- 238000007711 solidification Methods 0.000 description 15
- 230000008023 solidification Effects 0.000 description 15
- 238000003756 stirring Methods 0.000 description 9
- 239000005864 Sulphur Substances 0.000 description 6
- 238000003848 UV Light-Curing Methods 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
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Landscapes
- Reinforced Plastic Materials (AREA)
Abstract
The invention relates to an ultraviolet-curable resin composition and a fiber reinforced resin-based composite material thereof, and belongs to the technical field of light curing technologies and resin-based composite materials. The ultraviolet-curable resin composition comprises, by weight, 90-110 parts of epoxy resin, 0.1-0.7 parts of a cationic photoinitiator, 0.1-0.5 parts of a thermal initiator, 0-1 part of a photosensitizer, 0-35 parts of an active diluent and 0-30 parts of an additive. The ultraviolet-curable resin composition initiates a cationic polymerization reaction under the irradiation of ultraviolet light; and heat release of the polymerization reaction and the decomposition of the cationic photoinitiator commonly urges the thermal initiator to decompose in order to initiate a self propagating wave polymerization reaction. The ultraviolet-curable resin composition has the advantages of fast curing speed, high curing thickness, and realization of one-stage rapid deep curing. The fiber reinforced resin-based composite material with the composition as a matrix phase has good tensile strength, and curing is not affected by the laying layer number of fibers or the light transmission of a reinforcing phase.
Description
(1) technical field
The present invention relates to photocuring technology, polymer matrix composites technical field, specifically a kind of Ultraviolet curable resin composition and fiber-reinforced resin matrix compound material thereof with quick self-propagating solidification feature.
(2) background technology
Ultraviolet light polymerization reaction belongs to a modal class in radiation curing, needed for this reaction, activation energy is low, and reaction can be carried out in wide temperature range, is particularly easy to carry out low-temperature curing, effectively can eliminate the thermal stresses because hot setting causes, be the material preparation technology of a kind of green, environmental protection.
Polymer matrix composites are generally made up of wild phase and matrix phase, and conventional wild phase mostly is inorganic fibre, as glass fibre, carbon fiber; Matrix phase is organic polymer material.Existing polymer matrix composites are adopt traditional thermofixation mode to manufacture substantially, and the method energy consumption is large, set time is long, and production cost is high.Because ultraviolet light polymerization then can realize fast setting at room temperature, even lower temperature.Therefore, if be incorporated in the preparation of matrix material by UV-curing technology, for reduction production cost, enhancing productivity has important theory and realistic meaning.
UV-curing technology mainly divides radical UV curing and cation photocuring two kinds of mechanism.Relative to radical UV curing, cation photocuring has the advantages that chain carrier does not go out, and can continue to be cured reaction after stopping illumination, be particularly useful for the solidification of three-dimensional part, once becoming the focus of research in recent years.But be limited by limited and light tight wild phase the blocking or attenuation UV-light of UV-light penetrativity, ultraviolet light polymerization is applicable to usually can the preparation of galss fiber reinforced resin based composites of printing opacity, and need successively lay glass fibre, successively solidify during preparation, the solidification of disposable rapid deep zone cannot be realized.Meanwhile, in order to improve the performance after resin solidification, need add functional filler or pigment, this can affect solidification effect, even causes solidifying.For containing light tight wild phase system, as the ultraviolet light polymerization of carbon fibre reinforced composite, then have no relevant report.The application of above weak point extreme influence UV-curing technology in technical field of composite materials.
Self-propagating FP is a kind of is the reaction pattern of polymkeric substance to unreacted region continuous moving by conversion of monomer by local reaction region, and self-propagating curing technology is that the solution of this technical problem provides a valuable reference scheme.The resin system that can carry out self-propagating solidification of current report is mostly the radically curing system of thermal initiation, there is not yet the report that can be used for carbon fiber enhancement resin base composite material.
(3) summary of the invention
Technical assignment of the present invention is for the deficiencies in the prior art, though provide a kind of can rapid deep zone solidification stop illumination also can carrying out voluntarily self-propagating solidification and to the unconfined Ultraviolet curable resin composition of polymer matrix composites wild phase light transmission and carbon fiber enhancement resin base composite material thereof.
Ultraviolet curable resin composition of the present invention and fiber-reinforced resin matrix compound material reaction model thereof or theoretical foundation as follows: under ultraviolet light irradiation, cation light initiator decomposes and produces super strong proton acid, thus causes cationic polymerization; The heat release of polyreaction and cation light initiator decomposition impel thermal initiator to decompose generation free radical jointly, the free radical produced can bring out the decomposition of the luminous initiator of positively charged ion further, cause cationic polymerization, simultaneously free radical can the polyreaction of initiating methacrylates monomer; So, reaction is once after causing, and under the driving of polyreaction heat release, system can self-propagating solidification voluntarily.Like this, irradiation or cannot the deep layer resin area of direct irradiation is stopped in UV-light, no matter shallow table or bottom difficulty are shown in that light region all can fast setting, and by fiber reinforcement phase light transmission and the restriction of laying the number of plies, whole resin system shows the feature of self-propagating solidification.
The technical solution adopted for the present invention to solve the technical problems is:
The invention provides a kind of Ultraviolet curable resin composition, its formula Raw composition and each ingredients weight parts as follows: epoxy resin 90-110 part, cation light initiator 0.1-0.7 part, thermal initiator 0.1-0.5 part.
Described epoxy resin is one or more in glycidyl ether type epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, cycloaliphatic epoxy resin, as E44 epoxy resin, E51 epoxy resin, 3,4-epoxycyclohexyl-methyl-3, one or more in 4-epoxycyclohexyl manthanoate, two ((3,4-epoxycyclohexyl) methyl) adipic acid ester, epoxy modified silicone resin.
Described cation light initiator is one or more in salt compounded of iodine, sulfosalt, as one or more in 4,4-dimethyl diphenyl iodine father-in-law hexafluorophosphate, diphenyl iodine hexafluorophosphate, triphenyl sulfosalt, phenylbenzene-(4-phenyl sulphur) phenyl sulfonium hexafluorophosphate.
Described thermal initiator is one or more in peroxide type initiators, azo-initiator, as one or more in benzoyl peroxide, azo-bis-isobutyl cyanide.
Ultraviolet curable resin composition of the present invention, except in formula, the raw material of regulation forms and except each ingredients weight parts, can also coordinate photosensitizers 0-1 weight part, reactive thinner 0-35 weight part, additive 0-30 weight part or acrylate 5-40 weight part.
Described photosensitizers is α, alpha, alpha-dimethyl oxygen base-α-phenyl acetophenone, benzophenone, benzoin methyl ether, benzoin isobutyl propyl group ether, benzoin isobutyl ether, benzil, Michler's keton, one or more in thioxanthone.The introducing of photosensitizers, is conducive to shortening cure times, improves Light-Curing Efficiency.
Described reactive thinner is one or more in propylene oxide benzylic ether, propylene oxide phenyl ether, C12 ~ C14 alkyl glycidyl ether, propenyl glycidyl ether, bisglycidyl ether, ethylene glycol bis glycidyl ether.The introducing of reactive thinner, can be used for the viscosity of regulating ring epoxy resins, improves the operability of operating procedure system.
Described additive is one or more in the filler of powder or particle form, pigment, Nano filling, as filler or the pigment such as carbon black or titanium white of the powder such as talcum powder, aluminum oxide, pure aluminium silicate, glass, pottery, quartz, barium aluminosilicate, borate, aerosil or particle form, Nano filling can also be added, such as nanometer hydroxyapatite, nano silicon, nano-nylon fiber etc.The introducing of filler, can improve the intensity of formed cured article on the one hand, reduces the volumetric shrinkage of solidification, and the viscosity of adjustable ring epoxy resins, improves operative weldability on the other hand.
Described acrylate is one or more in butyl acrylate, butyl methacrylate, methyl acrylate, methyl methacrylate.Wherein, have and can also play epoxy resin toughened effect compared with the acrylate of long-chain.
Ultraviolet curable resin composition of the present invention, its preparation method comprises the steps:
1) each component is taken by each ingredients weight parts of regulation in formula;
2) epoxy resin, cation light initiator, thermal initiator, photosensitizers, reactive thinner, additive, acrylate are added in reaction vessel and mixed, stir to obtain Ultraviolet curable resin composition.
UV-cured resin cured article of the present invention, obtains by carrying out UV-irradiation to above-mentioned Ultraviolet curable resin composition.
Described ultraviolet source can be the light source of various generation UV-light, can according to the type selecting of light trigger, such as conventional high voltage mercury lamp.
The invention provides a kind of fiber-reinforced resin matrix compound material, prepare by after above-mentioned Ultraviolet curable resin composition matrix phase blend fiber wild phase, described fiber reinforcement comprises carbon cloth or glasscloth mutually, and wherein every 100 percent by weight fiber strengthen the Ultraviolet curable resin composition containing 40-75 weight part in polymer matrix composites.
Fiber-reinforced resin matrix compound material of the present invention, its preparation method comprises the steps:
Above-mentioned Ultraviolet curable resin composition matrix phase is coated on the substrate (as tetrafluoroethylene or polyethylene film) of easily stripping, then fiber reinforcement phase is laid, diameter is utilized to roll or other instruments, Ultraviolet curable resin composition is made to soak into fiber reinforcement phase, coated UV curable resin combination again, lay the 2nd layer of fiber reinforcement phase subsequently, so successively replace, each laying will ensure that Ultraviolet curable resin composition soaks into fiber reinforcement phase, compacting is irradiated under being placed on UV-light, it is laid the number of plies and can determine as required, unrestricted.After fiber reinforcement also can first all be soaked into by the preparation method of fiber-reinforced resin matrix compound material mutually, more successively lay, compacting is irradiated under being placed on UV-light.
Compared with prior art, Ultraviolet curable resin composition of the present invention and fiber-reinforced resin matrix compound material beneficial effect thereof are:
1) Ultraviolet curable resin composition of the present invention has quick self-propagating solidification feature, and its curing speed is fast, cured thickness large, and it can complete curing reaction in 9-10 minute after tested.
2) the present invention is that the fiber-reinforced resin matrix compound material tensile strength of matrix phase is good with said composition, and solidification is by the impact of the fleece-laying number of plies and polymer matrix composites wild phase light transmission.The polymer matrix composites laying 3 layers of fibre reinforced phase can complete the solidification of disposable rapid deep zone in 30 ~ 40 minutes.
(4) embodiment
Below in conjunction with embodiment, Ultraviolet curable resin composition of the present invention and fiber-reinforced resin matrix compound material thereof are described in detail below.
Ultraviolet source of the present invention can be the light source of various generation UV-light, can according to the type selecting of light trigger, as conventional high voltage mercury lamp.
Embodiment 1
Take E44 epoxy resin 90g, 4,4-dimethyl diphenyl iodine father-in-law hexafluorophosphate 0.5g, benzoyl peroxide 0.5g add in reaction vessel and mix, stir, obtain Ultraviolet curable resin composition.
The UV-cured resin cured article of the present embodiment, by carrying out above-mentioned Ultraviolet curable resin composition obtaining for UV-irradiation 9-10 minute.
The fiber-reinforced resin matrix compound material preparation method of the present embodiment comprises the steps:
Above-mentioned Ultraviolet curable resin composition matrix phase is coated on the substrate (as tetrafluoroethylene or polyethylene film) of easily stripping, then carbon cloth is laid, diameter is utilized to roll or other instruments, Ultraviolet curable resin composition is made to soak into carbon cloth, coated UV curable resin combination again, lay the 2nd layer of carbon cloth subsequently, so successively replace, each laying will ensure that Ultraviolet curable resin composition soaks into carbon cloth, and compacting is irradiated 30 minutes under being placed on UV-light.Ultraviolet curable resin composition wherein containing 40g in every 100g fiber-reinforced resin matrix compound material.
In the present embodiment, the carbon cloth laying number of plies can be determined as required, unrestricted.
Carbon cloth also available glass fiber cloth replacement in the present embodiment.
Embodiment 2
Take E51 epoxy resin 100g, triphenyl sulfosalt 0.1g, benzoyl peroxide 0.2g, azo-bis-isobutyl cyanide 0.2g add in reaction vessel and mix, stir, obtain Ultraviolet curable resin composition.
The present embodiment UV-cured resin cured article and fiber-reinforced resin matrix compound material preparation method are with embodiment 1, and difference is the Ultraviolet curable resin composition containing 60g in every 100g fiber-reinforced resin matrix compound material.
Embodiment 3
Take 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexyl manthanoate 110g, diphenyl iodine hexafluorophosphate 0.4g, phenylbenzene-(4-phenyl sulphur) phenyl sulfonium hexafluorophosphate 0.3g, azo-bis-isobutyl cyanide 0.1g adds in reaction vessel and mixes, stir, obtain Ultraviolet curable resin composition.
The present embodiment UV-cured resin cured article and fiber-reinforced resin matrix compound material preparation method are with embodiment 1, and difference is the Ultraviolet curable resin composition containing 75g in every 100g fiber-reinforced resin matrix compound material.
Embodiment 4
Take two ((3,4-epoxycyclohexyl) methyl) adipic acid ester 50g, E51 epoxy resin 55g, phenylbenzene-(4-phenyl sulphur) phenyl sulfonium hexafluorophosphate 0.1g, azo-bis-isobutyl cyanide 0.3g, propylene oxide benzylic ether 35g, add in reaction vessel and mix, stir, obtain Ultraviolet curable resin composition.
The present embodiment UV-cured resin cured article and fiber-reinforced resin matrix compound material preparation method are with embodiment 1.
The present embodiment oxypropylene benzylic ether also can use one or more replacements in C12 ~ C14 alkyl glycidyl ether, propenyl glycidyl ether, bisglycidyl ether, ethylene glycol bis glycidyl ether.
Embodiment 5
Take E51 epoxy resin 55g, epoxy modified silicone resin epoxy resin ES-0640g, triphenyl sulfosalt 0.5g, benzoyl peroxide 0.4g, butyl acrylate 5g add in reaction vessel and mix, stir, obtain Ultraviolet curable resin composition.
The present embodiment UV-cured resin cured article and fiber-reinforced resin matrix compound material preparation method are with embodiment 2.
In the present embodiment, butyl acrylate also can use one or more replacements in butyl methacrylate, methyl acrylate, methyl methacrylate.
Embodiment 6
Take epoxy resin 100g, phenylbenzene-(4-phenyl sulphur) phenyl sulfonium hexafluorophosphate 0.2g, azo-bis-isobutyl cyanide 0.4g, α, alpha, alpha-dimethyl oxygen base-α-phenyl acetophenone 1g, propenyl glycidyl ether 20g, butyl methacrylate 40g, add in reaction vessel and mix, stir, obtain Ultraviolet curable resin composition.
The present embodiment UV-cured resin cured article and fiber-reinforced resin matrix compound material preparation method are with embodiment 3.
Embodiment 7
Take two ((3,4-epoxycyclohexyl) methyl) adipic acid ester 95g, triphenyl sulfosalt 0.1g, phenylbenzene-(4-phenyl sulphur) phenyl sulfonium hexafluorophosphate 0.2g, azo-bis-isobutyl cyanide 0.2g, benzophenone 0.2g, benzoin methyl ether 0.3g, C12 ~ C14 alkyl glycidyl ether 10g, bisglycidyl ether 5g, ethylene glycol bis glycidyl ether 10g, butyl methacrylate 40g, add in reaction vessel and mix, stir, obtain Ultraviolet curable resin composition.
The present embodiment UV-cured resin cured article and fiber-reinforced resin matrix compound material preparation method are with embodiment 1.
Embodiment 8
Take two ((3,4-epoxycyclohexyl) methyl) adipic acid ester 20g, epoxy modified silicone resin epoxy resin ES-0680g, 4,4-dimethyl diphenyl iodine father-in-law hexafluorophosphate 0.2g, phenylbenzene-(4-phenyl sulphur) phenyl sulfonium hexafluorophosphate 0.2g, azo-bis-isobutyl cyanide 0.2g, bisglycidyl ether 15g, ethylene glycol bis glycidyl ether 10g, butyl methacrylate 10g, methyl acrylate 10g, methyl methacrylate 10g, filler 15g add in reaction vessel and mix, stir, obtain Ultraviolet curable resin composition.
The present embodiment UV-cured resin cured article and fiber-reinforced resin matrix compound material preparation method are with embodiment 2.
Additive described in the present embodiment is one or more in the filler of powder or particle form, pigment, Nano filling, as filler or the pigment such as carbon black or titanium white of the powder such as talcum powder, aluminum oxide, pure aluminium silicate, glass, pottery, quartz, barium aluminosilicate, borate, aerosil or particle form, Nano filling can also be added, such as nanometer hydroxyapatite, nano silicon, nano-nylon fiber etc.
Embodiment 9
With embodiment 8, difference is filler is 30g.
Embodiment 10
In embodiment 1 to 9, arbitrary fiber-reinforced resin matrix compound material lays the number of plies 3 layers, UV-irradiation 30 minutes, after solidification on material universal testing machine its tensile property of tstr, its tensile strength reaches more than 500MPa to 600MPa.
Claims (10)
1. a Ultraviolet curable resin composition, is characterized in that, its formula Raw composition and each ingredients weight parts as follows: epoxy resin 90-110 part, cation light initiator 0.1-0.7 part, thermal initiator 0.1-0.5 part, photosensitizers 0-1 part, reactive thinner 0-35 part, additive 0-30 part.
2. Ultraviolet curable resin composition according to claim 1, is characterized in that, also comprises acrylate 5-40 weight part.
3. Ultraviolet curable resin composition according to claim 1, it is characterized in that, described epoxy resin is one or more in glycidyl ether type epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, cycloaliphatic epoxy resin.
4. Ultraviolet curable resin composition according to claim 1, is characterized in that, described cation light initiator is one or more in salt compounded of iodine, sulfosalt.
5. Ultraviolet curable resin composition according to claim 1, is characterized in that, described thermal initiator is one or more in peroxide type initiators, azo-initiator.
6. Ultraviolet curable resin composition according to claim 1, is characterized in that, described photosensitizers is α, alpha, alpha-dimethyl oxygen base-α-phenyl acetophenone, benzophenone, benzoin methyl ether, benzoin isobutyl propyl group ether, benzoin isobutyl ether, benzil, Michler's keton, one or more in thioxanthone.
7. Ultraviolet curable resin composition according to claim 1, it is characterized in that, described reactive thinner is one or more in propylene oxide benzylic ether, propylene oxide phenyl ether, C12 ~ C14 alkyl glycidyl ether, propenyl glycidyl ether, bisglycidyl ether, ethylene glycol bis glycidyl ether.
8. Ultraviolet curable resin composition according to claim 1, is characterized in that, described additive is one or more in the filler of powder or particle form, pigment, Nano filling.
9. Ultraviolet curable resin composition according to claim 2, is characterized in that, described acrylate is one or more in butyl acrylate, butyl methacrylate, methyl acrylate, methyl methacrylate.
10. a fiber-reinforced resin matrix compound material, it is characterized in that, described fiber-reinforced resin matrix compound material prepares after the Ultraviolet curable resin composition matrix phase blend fiber wild phase according to any one of claim 1 ~ 9, described fiber reinforcement comprises carbon cloth or glasscloth mutually, and wherein every 100 percent by weight fiber strengthen the Ultraviolet curable resin composition containing 40-75 weight part in polymer matrix composites.
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| CN109135152A (en) * | 2017-06-16 | 2019-01-04 | 合肥杰事杰新材料股份有限公司 | A kind of carbon fiber ball modified light-sensitive resin composite materials and preparation method thereof |
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| CN112912449A (en) * | 2018-10-23 | 2021-06-04 | 株式会社东进世美肯 | Composition for forming hard coat layer, hard coat layer using same, and laminate comprising same |
| CN112912449B (en) * | 2018-10-23 | 2023-06-30 | 株式会社东进世美肯 | Composition for forming hard coat layer, hard coat layer using same, and laminate comprising same |
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