CN103965582A - Carbon nano dual-cured resin matrix for pultrusion process and composite of carbon nano dual-cured resin matrix - Google Patents
Carbon nano dual-cured resin matrix for pultrusion process and composite of carbon nano dual-cured resin matrix Download PDFInfo
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- CN103965582A CN103965582A CN201410168070.8A CN201410168070A CN103965582A CN 103965582 A CN103965582 A CN 103965582A CN 201410168070 A CN201410168070 A CN 201410168070A CN 103965582 A CN103965582 A CN 103965582A
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- 229920005989 resin Polymers 0.000 title claims abstract description 154
- 239000011347 resin Substances 0.000 title claims abstract description 154
- 239000011159 matrix material Substances 0.000 title claims abstract description 149
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 52
- 230000008569 process Effects 0.000 title claims abstract description 47
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 239000003822 epoxy resin Substances 0.000 claims abstract description 77
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 77
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 67
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 58
- 239000000835 fiber Substances 0.000 claims abstract description 53
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 34
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 34
- 239000003999 initiator Substances 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000000465 moulding Methods 0.000 claims description 34
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 32
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 28
- 239000004917 carbon fiber Substances 0.000 claims description 28
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 26
- -1 glycidyl ester Chemical class 0.000 claims description 18
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000004593 Epoxy Substances 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229930185605 Bisphenol Natural products 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 7
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims description 6
- 239000003365 glass fiber Substances 0.000 claims description 6
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920002994 synthetic fiber Polymers 0.000 claims description 6
- 239000012209 synthetic fiber Substances 0.000 claims description 6
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 6
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims description 5
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 claims description 5
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 5
- 229920002748 Basalt fiber Polymers 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 4
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 229920006241 epoxy vinyl ester resin Polymers 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- 229960004418 trolamine Drugs 0.000 claims description 4
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 claims description 3
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 3
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 claims description 3
- OFMBSIAKTAZWIE-UHFFFAOYSA-N 2-oxo-3-phenylpropanal Chemical compound O=CC(=O)CC1=CC=CC=C1 OFMBSIAKTAZWIE-UHFFFAOYSA-N 0.000 claims description 3
- UCNCZASVJWGNBZ-UHFFFAOYSA-N 3-(2-ethyl-5-methyl-1h-imidazol-4-yl)propanenitrile Chemical compound CCC1=NC(CCC#N)=C(C)N1 UCNCZASVJWGNBZ-UHFFFAOYSA-N 0.000 claims description 3
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004844 aliphatic epoxy resin Substances 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- 229940015043 glyoxal Drugs 0.000 claims description 3
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 3
- 229920003986 novolac Polymers 0.000 claims description 3
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 238000007142 ring opening reaction Methods 0.000 claims description 3
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
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- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 6
- 239000002048 multi walled nanotube Substances 0.000 description 6
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- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
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- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- 241001112258 Moca Species 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
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- Reinforced Plastic Materials (AREA)
Abstract
The invention relates to a carbon nano dual-cured resin matrix for a pultrusion process and a composite of the carbon nano dual-cured resin matrix. The resin matrix is made from the following raw materials in parts by weight: 50-90 parts of epoxy resin and a curing agent thereof, 10-50 parts of vinyl ester resin and an initiator thereof, 1-2 parts of carbon nanotubes, and an appropriate amount of optional additives; the resin matrix is a dual-cured homogeneous system formed by the epoxy resin and the curing agent thereof, the vinyl ester resin and the initiator thereof, and the carbon nanotubes uniformly dispersed in the resin matrix. The resin system has the characteristics of low viscosity, high invasion with fibers, high curing speed and uniform heat and mass transfer; the resin matrix is high in stability and continuity in the pultrusion process. The composite prepared through pultrusion is high in flexibility, higher in interlaminar shear strength, high in heat resistance, and excellent in surface smoothness and rigidity.
Description
(1) technical field
The present invention relates to fiber-reinforced resin matrix compound material and manufacture field, especially relate to a kind of carbon nano double cured resin matrix and matrix material thereof for pultrusion molding process.
(2) background technology
Resin base pultrusion composite materials, is to be prepared from through pultrusion molding process by continuous fortifying fibre and various resin, is widely used in space flight and aviation, building, electric, and the field such as industrial, agriculture.Along with the progress in epoch, performance requriements to resin base pultrusion composite materials is more and more higher, wherein taking performance requriementss such as the intensity of matrix material, snappiness, thermotolerances as main, and require this matrix material to there is good processing characteristics in improving physicals.
The fortifying fibre of pultrusion composite materials mainly contains glass fibre, carbon fiber, the contour performance fibers of aramid fiber, and resin matrix is taking thermosetting resin as main, such as unsaturated polyester resin, vinyl ester resin, epoxy resin etc.Conventional moulding process is continuous fortifying fibre solvent impregnated resin matrix, solidifies through mold heated, forms the matrix material of constant cross-section shape.But by the restriction of the performance of resin own, the performance of existing matrix material is single, cannot reaches properties simultaneously and all satisfy the demand.As: Chinese patent CN02117884.4A discloses a kind of fiber reinforcing drawing-extruding matrix material for coiled rod, employing carbon fiber is fortifying fibre, taking vinyl ester resin as matrix, pultrusion speed is 0.2-2m/min, but in production technique, must adopt fiber surface to process stove to burn the upper glue layer of carbon fiber surface, improve the interface performance of fiber and resin matrix, but its prepared matrix material heat-drawn wire only reaches 131 DEG C-147 DEG C.
Chinese patent ZL200410039473, disclose a kind of resin matrix and carbon fiber pultruded composite thereof being mixed by phenol aldehyde type vinyl ester resin and bisphenol A-type vinyl ester resin, this matrix material second-order transition temperature can reach 153 DEG C-162 DEG C, but in production technique, need to burn equally carbon fiber surface upper glue layer, partial loss the intensity of carbon fiber.
Simultaneously, epoxy resin is because its adhesiveproperties is good, composite material interface excellent property, mechanical property and resistance toheat all greatly improve than unsaturated resinoid matrix, are also often used in the preparation of pultrusion composite materials, but resin base pultrusion molding process requires, resin activity is high, curing speed is fast, curing molding in 1～3 minute, but the feature of epoxy resin cure is progressively polymerization of open loop, and speed of response is slow, mold temperature is high, production efficiency is lower, is difficult to meet the requirement of fast pultrusion moulding.
Thermosetting resin by some excellent performances of modification in prior art or by adding some functional aids, to reach the various aspects of performance that improves resin base pultrusion composite materials simultaneously, but its result is all undesirable, some poor effect, some complex process, is difficult to realize the high performance resin base pultrusion composite materials of production in enormous quantities.
In order to overcome the deficiencies in the prior art, now simple in the urgent need to a kind of technique, and various performance all can meet the resin base pultrusion composite materials of service requirements.
(3) summary of the invention
The object of the invention is for the deficiencies in the prior art, a kind of carbon nano double cured resin matrix and matrix material for pultrusion molding process is provided, wherein for the carbon nano double cured resin matrix of pultrusion molding process, its have viscosity low, with the feature that wetting property is good, curing speed is fast, solidification value is low of fiber, matrix material, it has, and processing characteristics is good, snappiness good, intensity is high, resistant to elevated temperatures feature.
The present invention is achieved through the following technical solutions:
For a carbon nano double cured resin matrix for pultrusion molding process, its special character is: the raw material by following parts by weight is made:
50-90 part epoxy resin and solidifying agent thereof, 10-50 part vinyl ester resin and initiator thereof, 1-2 part carbon nanotube and optional appropriate amount of addition agent, this matrix is the two curing homogeneous system being made up of epoxy resin and solidifying agent thereof and vinyl ester resin and initiator thereof, dispersed carbon nanotube wherein.
Carbon nano double cured resin matrix for pultrusion molding process of the present invention, the weight part of auxiliary agent is 1-8, epoxy resin and solidifying agent weight proportion are 100: 25-100, vinyl ester resin and initiator weight proportion are 100:0.5-2.
Carbon nano double cured resin matrix for pultrusion molding process of the present invention, epoxy resin is glycidyl ether type, glycidic amine type, glycidyl ester type, aliphatic epoxy resin, a kind of or its mixture in novolac epoxy, solidifying agent comprises acid anhydride type curing agent, amine curing agent, a kind of or its mixture of imidazole curing agent, vinyl ester resin is to carry out by epoxy resin and unsaturated organic monocarboxylic acid the molecule two ends that esterification by ring opening reacts and obtain to contain vinyl ester group, the class unsaturated polyester resin that middle skeleton is epoxy resin, initiator is that heating can be decomposed the organo-peroxide that produces free radical, auxiliary agent is one or more in releasing agent and reactive thinner.
Carbon nano double cured resin matrix for pultrusion molding process of the present invention, Racemic glycidol ether type epoxy is a kind of or its mixture in bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, and available acid anhydride type curing agent comprises: methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl carbic anhydride, dodecenylsuccinic anhydride etc.; Amine curing agent comprises 4,4-, bis-amido ditanes, mphenylenediamine, m-xylene diamine, diethyl toluene diamine, isophorone diamine, 3,3'-dimethyl-4,4'-diamino-dicyclohexyl methyl hydride etc., and corresponding modified multicomponent amine; Imidazole curing agent is included as 2-ethyl-4-methylimidazole, benzyl-glyoxal ethyline, cyanoethyl-2-ethyl-4-methylimidazole, glyoxal ethyline, vinyl ester resin is bisphenol A-type vinyl ester resin and/or phenol aldehyde type vinyl ester resin, initiator comprises: methylethyl ketone peroxide, benzoyl peroxide, cyclohexanone peroxide, dicumyl peroxide, tert-butyl peroxide, t-butylperoxyl benzoate, and available releasing agent comprises modified phosphate, organic fluorinated silicone compound, trolamine oil; Available reactive thinner includes but not limited to that glycidyl allyl ether, ethylene glycol diglycidylether, butanediol diglycidyl ether etc. have the multi-functional compound of low viscosity.
A kind of preparation method of the carbon nano double cured resin matrix for pultrusion molding process, comprise the following steps: the common curing reaction of epoxy resin and vinyl ester resin, even carbon nanotube disperses wherein to form two curing homogeneous system-carbon nano double cured resin matrixes.
A kind of matrix material of preparing for the carbon nano double cured resin matrix of pultrusion molding process, solidify to form by continuous fortifying fibre and above-mentioned carbon nano double cured resin matrix composite heating, wherein resin matrix is cross-linked to form the multidimensional crossover network structure taking carbon nanotube as contact.
Matrix material of the present invention, fortifying fibre accounts for the 53%-74% of matrix material volume total content continuously.
Matrix material of the present invention, fortifying fibre is a kind of or its mixture of carbon fiber, glass fibre, basalt fibre, organic synthetic fibers, steel fiber continuously.
A preparation method for matrix material, comprises the following steps: continuous fortifying fibre and the compound post-heating of above-mentioned carbon nano double cured resin matrix are solidified and formed, and wherein, in matrix material, resin matrix is cross-linked to form multidimensional crossover network structure.
The preparation method of matrix material of the present invention, comprises the following steps: solidifying agent, nanotube are added in effective dispersing machine and disperseed successively; Then add successively epoxy resin, vinyl ester resin to disperse; Add successively again initiator, releasing agent, by after above component mixing and stirring, inject the steeping vat of extruding equipment, with after continuous fortifying fibre impregnated carbon nano double cured resin matrix, by the matrix material that is heating and curing and forms.
The invention has the beneficial effects as follows: form homogeneous double cured resin system by epoxy resin and solidifying agent thereof and vinyl ester resin and initiator thereof, carbon nanotube, two kinds of resins are cross-linked to form the multidimensional crossover network taking carbon nanotube as contact by curing mechanism separately.This resin system has that viscosity is low, good with the wetting property of fiber, curing speed is fast, the uniform feature of heat and mass, and pultrusion molding process is had to satisfactory stability and continuity.The matrix material of preparing by pultrusion has good snappiness, higher interlaminar shear strength and good resistance toheat, good surface smoothness and rigidity.
(4) embodiment
Be noted that following detailed description is all exemplary, is intended to the invention provides further instruction.Unless otherwise, all technology used herein and scientific terminology have the identical meanings of conventionally understanding with general technical staff of the technical field of the invention.
Contriver proposes the present invention based on such imagination, select the common curing reaction of epoxy resin and vinyl ester resin, select multi-walled carbon nano-tubes as Anchor Agent and all thermit powder, fiber filament are as toughener, crosslinking reaction and carbon nanotube form the multidimensional crossover network structure taking carbon nanotube as contact jointly simultaneously according to different separately curing mechanisms for two kinds of resins.Multi-walled carbon nano-tubes has powerful specific surface area, resin chain can be coupled together with different dimensions, as the rivet by fiber filament with intersect together with the resin chain of IPN is anchored at.
In a kind of exemplary embodiment of the present invention, this carbon nano double cured resin matrix comprises by weight: 50-90 part epoxy resin and solidifying agent thereof, 10-50 part vinyl ester resin and initiator thereof, 1-2 part multi-walled carbon nano-tubes, and appropriate auxiliary agent.
The multidimensional crossover network cured article taking carbon nanotube as contact that carbon nano double cured resin matrix of the present invention forms, the cross-linking density of homogeneous while having changed single resin solidification, cross-linking density distribution range is broadened, in the time that material is subject to complicated external impacts, external force is transmitted along the resin chain of different directions by carbon nanotube, play the effect of impact-absorbing energy, reduce the stress defect point in pitch state structure, not only can improve the fragility of single resin matrix, can also suitably improve the intensity of material.Due in the multidimensional crossover network taking carbon nanotube as contact taking the rigid chain segment of epoxy resin as main, material thermal resistance still shows as the good resistance toheat of epoxy resin.
Preferably, in the present invention, spendable epoxy resin is a kind of or its mixture in glycidyl ether type, glycidic amine type, glycidyl ester type, aliphatic epoxy resin, novolac epoxy.
Wherein, Racemic glycidol ether type epoxy is preferably a kind of or its mixture in bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin.
It is good that epoxy resin has adhesiveproperties, good heat resistance, and physical strength is high, water-fast, radiotolerant feature, the composite material interface excellent property that uses epoxy resin to prepare, mechanical property and resistance toheat are all better.
Preferably, in a kind of embodiment of the present invention, epoxy resin used is bisphenol A type epoxy resin.
Can comprise for solidifying agent of the present invention a kind of or its mixture of acid anhydride type curing agent, amine curing agent, imidazole curing agent.Wherein, available acid anhydride type curing agent comprises: methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl carbic anhydride, dodecenylsuccinic anhydride etc.; Amine curing agent comprises 4,4-, bis-amido ditanes, mphenylenediamine, m-xylene diamine, diethyl toluene diamine, isophorone diamine, 3,3'-dimethyl-4,4'-diamino-dicyclohexyl methyl hydride etc., and corresponding modified multicomponent amine; Imidazole curing agent is included as 2-ethyl-4-methylimidazole, benzyl-glyoxal ethyline, cyanoethyl-2-ethyl-4-methylimidazole, glyoxal ethyline.
Select different solidifying agent according to the different moulding process of epoxy resin and performance requriements, these selections are well known in the prior art.Make epoxy resin and solidifying agent be related to complete reaction by chemically reactive functional group equivalent, epoxy resin and solidifying agent weight proportion are 100: 25-100; Be preferably 100:35-85.Epoxy resin after solidifying has good mechanical property, thermotolerance and resistant to chemical media.
In the present invention, the vinyl ester resin of use is preferably bisphenol A-type vinyl ester resin and/or phenol aldehyde type vinyl ester resin.
Vinyl ester resin be by epoxy resin and unsaturated organic monocarboxylic acid carry out that esterification by ring opening reacts and molecule two ends contain the class unsaturated polyester resin that vinyl ester group, middle skeleton are epoxy resin, there is the premium properties of epoxy resin and vinylformic acid unsaturated polyester resin, chemical structure is similar to epoxy resin, processing performance and unsaturated polyester resin are close, have the advantages that curing speed is fast, cross-linking density is large, chemical resistance is good.
Preferably, the initiator using in the present invention can decompose for heating the organo-peroxide that produces free radical.Comprise: methylethyl ketone peroxide, benzoyl peroxide, cyclohexanone peroxide, dicumyl peroxide, tert-butyl peroxide, t-butylperoxyl benzoate etc.
Select different initiators according to the different moulding process of vinyl ester resin and performance requriements, this selection is well known in the prior art.Vinyl ester resin can be solidified fully, and cross-linking density is suitable, and vinyl ester resin and initiator weight proportion are 100:0.5-2; Be preferably 100: 0.8-1.6.Vinyl ester resin after solidifying has good mechanical properties, toughness is moderate, chemical resistance is good feature.
Preferably, the selected decomposition temperature of initiator of the present invention is suitable with the solidification value of epoxy resin, to improve the utilization ratio of curing speed and superoxide of epoxy resin.
Carbon nano double curing system of the present invention is in solidify reaction process, the crosslinking curing of vinyl ester resin is by radical initiation reaction, and speed of response is fast, first forms gel structure and discharges a large amount of reaction heat, promote the curing reaction of epoxy resin, accelerated the curing speed of epoxy resin.Add carbon nanotube, improve system thermal conduction effect, make heat distribution equilibrium in system, prevent local superheating, reduce material property, interrupt pultrusion process, improve stability and the persistence of pultrusion process.
Alternatively, in one embodiment of the invention, auxiliary agent is one or more in releasing agent and reactive thinner, wherein two kinds of situations about all comprising most preferably.Available releasing agent comprises modified phosphate, organic fluorinated silicone compound, trolamine wet goods, and consumption is preferably 1-3 weight part; Available reactive thinner includes but not limited to that glycidyl allyl ether, ethylene glycol diglycidylether, butanediol diglycidyl ether etc. have the multi-functional compound of low viscosity, and consumption can be between 1-5 weight part.This reactive thinner is in order to improve pultrude process, to reduce resin viscosity.
The invention still further relates to a kind of continuous composite material, it solidifies and forms with continuous fortifying fibre and the compound post-heating of above-mentioned carbon nano double cured resin matrix.This matrix material can be prepreg, form material etc.In matrix material, resin matrix is cross-linked to form multidimensional crossover network structure.
The multidimensional crossover network that resin matrix forms by the crosslinking net polymkeric substance of epoxy resin and vinyl ester resin mutually run through taking carbon nanotube as contact, entanglement, anchoring form, to be gone by random the extending through in another kind of material of a kind of material, play a part " forcing mutual appearance " and " synergistic effect ", thermotolerance, mechanical property, composite material interface performance that can make polymkeric substance etc. can increase simultaneously, the slow shortcoming of curing speed while having improved independent use epoxy resin, has improved again the shortcoming of the poor processability of independent use vinyl ester resin.
In the present invention, continuous fortifying fibre accounts for the 53%-74% of matrix material total content.Be preferably 55%-65%, more preferably 60%.
In the present invention, continuous fortifying fibre is preferably a kind of or its mixture of carbon fiber, glass fibre, basalt fibre, organic synthetic fibers, steel fiber.
The preparation method of matrix material of the present invention is simple, because product carbon fiber surface cementing agent is mainly epoxy resin, carbon fiber and epoxy resin-base have good interface compatibility energy, carbon nanotube has powerful specific surface area and micropore, itself and epoxy resin also have good interface compatibility energy, more there is similar micro interface to carbon fiber, the matrix material micro interface inconsistent problem of having avoided the unsaturated resinoid matrixes such as simple employing vinyl ester resin to produce, and without adopting fiber surface to process stove to burn the upper glue layer of carbon fiber surface, both saved the time, shorten again production stage, reduce energy consumption.
Embodiment 1
Constitutive material for the carbon nano double cured resin matrix of pultrusion molding process is as follows:
Bisphenol A type epoxy resin CYD-128 3kg; Methyl carbic anhydride 3kg; Dihydroxyphenyl propane vinyl ester resin Hetron922 4kg; Initiator peroxidation-2-ethyl acetic acid tert-butyl ester 0.04kg; Releasing agent INT-PS125 0.15kg; Carbon nanotube 0.1kg.
The preparation method of matrix material: 3kg methyl carbic anhydride, 0.1kg carbon nanotube are added successively in effective dispersing machine and disperseed 10 minutes; Add successively above component epoxide resin, vinyl ester resin to disperse 15 minutes; Add successively again initiator, releasing agent, by after above component mixing and stirring, inject the steeping vat of extruding equipment.With after continuous fortifying fibre impregnated carbon nano double cured resin matrix, by the matrix material that is heating and curing and forms.Fiber reinforced material is T300-12K carbon fiber, and goods are the flat bar of cross section 32mm × 4.6mm, and carbon fiber is 60% of matrix material volume content.
Embodiment 2
Constitutive material for the carbon nano double cured resin matrix of pultrusion molding process is as follows:
Bisphenol A type epoxy resin CYD-128 6kg; Solidifying agent: 3,3'-dimethyl-4,4'-diamino-dicyclohexyl methyl hydride 1 kg, 4,4-, bis-amido ditane 0.6 kg, mphenylenediamine 0.2 kg; Dihydroxyphenyl propane vinyl ester resin DOW411-350 2.2 kg; Dibenzoyl peroxide 25 g; Releasing agent INT-1890M 0.12 kg; Carbon nanotube 0.1 kg.
The preparation method of matrix material: the solidifying agent of above component, carbon nanotube are added in effective dispersing machine successively, disperse 10 minutes; Add successively again epoxy resin, the vinyl ester resin of above component, disperse 15 minutes; Add successively again dibenzoyl peroxide, releasing agent by after above component mixing and stirring, inject the steeping vat of extruding equipment.With after continuous fortifying fibre impregnated carbon nano double cured resin matrix, by the matrix material that is heating and curing and forms, fiber reinforced material is 40K large-tow carbon fiber, and goods are the banded bar of the flat of cross section 32mm × 4.6mm, and carbon fiber is 60% of matrix material volume content.
Embodiment 3
Constitutive material for the carbon nano double cured resin matrix of pultrusion molding process is as follows:
Bisphenol f type epoxy resin NPEF-170 7.2kg; 2-ethyl-4-methylimidazole 1.8kg; Phenolic aldehyde epoxy vingl ester resin 4.975kg; Initiator methylethyl ketone peroxide 25g; INT-1846N 0.15kg; Carbon nanotube 0.2kg.
The preparation method of matrix material: 1.8kg2-ethyl-4-methylimidazole, 0.2kg carbon nanotube are added successively in effective dispersing machine and disperseed 10 minutes; Add successively above component epoxide resin, vinyl ester resin to disperse 15 minutes; Add successively again initiator, releasing agent, by after above component mixing and stirring, inject the steeping vat of extruding equipment.With after continuous fortifying fibre impregnated carbon nano double cured resin matrix, by the matrix material that is heating and curing and forms.Fiber reinforced material is glass fibre, and goods are the flat bar of cross section 32mm × 4.5mm, and glass fibre is 74% of matrix material volume content.
Embodiment 4
Constitutive material for the carbon nano double cured resin matrix of pultrusion molding process is as follows:
Bisphenol-s epoxy resin 185S 1kg; Bisphenol f type epoxy resin NPEF-170 2kg; Methyl tetrahydrophthalic anhydride 0.5kg, isophorone diamine 0.5kg; Dihydroxyphenyl propane vinyl ester resin Hetron922 0.5kg, phenolic aldehyde epoxy vingl ester resin 0.5kg; Initiator cyclohexanone peroxide 14g, dicumyl peroxide 0.06kg; Releasing agent trolamine oil 0.2kg; Glycidyl allyl ether 0.4kg; Carbon nanotube 0.15kg.
The preparation method of matrix material: methyl tetrahydrophthalic anhydride 0.5kg, isophorone diamine 0.5kg, 0.15kg carbon nanotube are added successively in effective dispersing machine and disperseed 10 minutes; Add successively above component glycidyl allyl ether, epoxy resin, vinyl ester resin to disperse 15 minutes; Add successively again initiator, releasing agent, by after above component mixing and stirring, inject the steeping vat of extruding equipment.With after continuous fortifying fibre impregnated carbon nano double cured resin matrix, by the matrix material that is heating and curing and forms.Fiber reinforced material is basalt fibre, and goods are the flat bar of cross section 31mm × 4.6mm, and basalt fibre is 53% of matrix material volume content.
Embodiment 5
Constitutive material for the carbon nano double cured resin matrix of pultrusion molding process is as follows:
Bisphenol A type epoxy resin CYD-128 1kg, bisphenol-s epoxy resin 185S 1kg, bisphenol f type epoxy resin NPEF-170 2kg; 3,3 ' one two chloro-4,4 ': diphenylmethanediamiand (MOCA) 1kg; Dihydroxyphenyl propane vinyl ester resin Hetron922 3kg; Cyclohexanone peroxide 0.03kg; Polyether-modified Polysiloxane Phosphate 0.1kg, ethylene glycol diglycidylether 0.5kg; Carbon nanotube 0.18kg.
The preparation method of matrix material: fiber reinforced material is organic synthetic fibers, steel fiber, goods are the flat bar of cross section 31mm × 4.6mm, organic synthetic fibers, steel fiber total amount are 65% of matrix material volume content, and organic synthetic fibers is 30% of matrix material volume content.
Other are identical with embodiment 1.
In above-described embodiment, epoxy resin, solidifying agent, vinyl ester resin, initiator, auxiliary agent can convert specifically and select materials, and its performance test results is similar, describe as example taking following.
The carbon nano double cured resin matrix viscosity in 0-6 hour for pultrusion molding process of preparing in embodiment of the present invention 1-2 changes as table 1.
Table 1,0-6 hour double cured resin base viscosity change viscosity unit: mPa.s
Conclusion: as shown in table 1, change littlely according to the prepared carbon nano double cured resin matrix for pultrusion molding process of embodiment of the present invention 1-2 viscosity at 25 DEG C of normal temperature, there is longer working life, meet pultrude process requirement.
Comparative example 1
Epoxy resin cure matrix material: bisphenol A type epoxy resin CYD-128 10kg; Solidifying agent: methyl tetrahydrophthalic anhydride 8 kg; Releasing agent INT-1846N 0.15 kg.
Composite material preparation process: by after above component mixing and stirring, inject the steeping vat of extruding equipment, with after continuous fortifying fibre epoxy resin-impregnated matrix, by the matrix material that is heating and curing and forms.Fiber reinforced material is T300-12K carbon fiber, and goods cross section is the banded bar of 32mm × 4.6mm flat, and the volume content of fiber is 60%.
Comparative example 2
Vinyl ester resin cured matrix raw material: dihydroxyphenyl propane vinyl ester resin Hetron922 10 kg; Organic peroxide evocating agent: two (4-tertiary butyl cyclohexyl ester) 0.02 kg of peroxy dicarbonate, dibenzoyl peroxide 0.03 kg, peroxidized t-butyl perbenzoate 0.05 kg; Releasing agent INT-PS125 0.12 kg.
Composite material preparation process: by after above component mixing and stirring, inject the steeping vat of extruding equipment, with after continuous fortifying fibre dipping vinyl ester resin matrix, by the matrix material that is heating and curing and forms, and adopt fiber surface to process stove to burn the upper glue layer of carbon fiber surface.Fiber reinforced material is T300-12K carbon fiber, disposes surperficial epoxy sizing agent through 350 DEG C of processing stoves.Goods are the flat bar of cross section 32mm × 4.6mm, and the volume content of fiber is 60%.
Comparative example 3
Vinyl ester resin cured matrix raw material: dihydroxyphenyl propane vinyl ester resin Hetron922 6 kg; Phenol aldehyde type vinyl ester resin 4kg; Organic peroxide evocating agent: two (4-tertiary butyl cyclohexyl ester) 0.02 kg of peroxy dicarbonate, dibenzoyl peroxide 0.03 kg, peroxidized t-butyl perbenzoate 0.05 kg; Releasing agent INT-PS125 0.12 kg.
Composite material preparation process: with comparative example 2
Performance test:
1, to carrying out tensile strength and toughness test according to the prepared resin matrix of embodiments of the invention 1-2 and comparative example 1-3.Wherein the toughness of resin matrix represents by the relative value of flexural strength and modulus in flexure, and flexural strength is higher, and modulus in flexure is lower, and the toughness of resin matrix is better.
2, to carry out thermotolerance and the test of matrix material interlayer shearing resistance according to the prepared matrix material of embodiments of the invention 1-2 and comparative example 1-3.Wherein the data of comparative example 2 and 3 prepared matrix materials are for the composite material test of processing stove and burn the upper glue layer of carbon fiber surface with fiber surface.For the prepared matrix material of comparative example 2 and comparative example 3, the interlaminar shear strength of surface treated matrix material is not far below surface treated matrix material.
3, to testing according to the pultrusion speed in the prepared composite material of embodiments of the invention 1-2 and comparative example 1-3.The pultrusion speed of surveying all needs to meet the completely crued condition of resin matrix, and the pultrusion speed of equipment need to coordinate the curing speed of resin, and the curing speed of resin matrix is slow, and its pultrusion speed also needs slowly, and curing speed is fast, and its pultrusion speed also can correspondingly be accelerated.
4, to being composite continuous moulding length according to embodiments of the invention 1-2 and the prepared composite material drawing and extruding stability assessment of production process index of comparative example 1-3, the more stable moulding length of technique is longer; Unsettled process system is in pultrusion process, its technic index needs change continuously, changes, be easy to break or interrupt process, cause the different interface performance discretenesses of product large, cause composite property cannot meet homogeneity requirement, limit the Application Areas of matrix material, had the product of requirement cannot continue to produce for length especially, caused a large amount of waste products.
5, to testing according to the torsional property of embodiment of the present invention 1-2 and the prepared matrix material of comparative example 1-3.Continuous composite material in the time using as hawser owing in use often can being distorted; for example, when carbon-fibre composite uses as oil pumping in oil fields bar; can be twisted into fried dough twist type in down-hole, under stressing conditions, easily crack or splitting, the body of rod was lost efficacy.
The ordinary method that testing method is used for those skilled in the art, test result is listed in table 2, table 3.
The performance test of table 2 resin matrix
The test of table 3 composite property
By result shown in table 2, table 3, be analyzed as follows:
According to the tensile strength of the prepared resin matrix of embodiments of the invention 1-2, toughness obviously promotes with respect to comparative example 1-3.According to the resistance toheat of the prepared matrix material of embodiments of the invention 1-2, matrix material interlayer shearing resistance is apparently higher than comparative example 1-3.
Speed while obviously preparing matrix material faster than comparative example 1 according to the pultrusion speed of the prepared matrix material of embodiment of the present invention 1-2, and continuously shaped length is much larger than comparative example 1, pultrusion speed and moulding same length when its pultrusion speed, continuously shaped length and this comparative example 2-3 prepare matrix material, the pultrusion speed while even preparing matrix material faster than this documents 2-3.
Much larger than comparative example 1-3, turn round three-sixth turn angle at 1m carbon beam according to the torsional property of the prepared matrix material of embodiment of the present invention 1-2, two ends apply under 15t stress condition, 1,000 ten thousand fatigue tests, surperficial flawless.
Conclusion: the present invention is used for the carbon nano double cured resin matrix of pultrusion molding process because the double cured resin system that it forms taking multi-walled carbon nano-tubes as contact has been improved resin crosslinks density, multi-walled carbon nano-tubes is as the rivet, resin chain is anchored at together, resin-cast body tensile strength is improved than single resin system, bending strength ratio vinyl ester resin obviously improves, and modulus in flexure declines, and indicates that the tough property improvement of resin is obvious.
Simultaneously, because vinyl ester resin curing reaction speed is fast, first form gel structure and discharge a large amount of reaction heat, due to the good heat conductivility of carbon nanotube, it is evenly distributed in resin system, be conducive to the thermal conduction equilibrium in system, promote the curing reaction of epoxy resin, solve the slow problem of epoxy resin cure, prevent medium local superheating in mould, make reaction process steady, conduct heat evenly, promote the curing speed of two cured matrix, thereby promoted pultrusion speed time prepared by matrix material.Due to the synergy of carbon nanotube and double cured resin matrix, system is conducted heat, mass transfer is even, reacting balance, thereby improved the performance of matrix material.
The matrix material that the present invention is prepared, because product carbon fiber surface cementing agent is mainly epoxy resin, carbon fiber and epoxy resin-base have good interface compatibility energy, carbon nanotube has powerful specific surface area and micropore, and surface is through amination processing, itself and epoxy resin have good interface compatibility energy, also there is good interface compatibility energy with vinyl ester resin, more there is similar micro interface to carbon fiber, multi-walled carbon nano-tubes has played and has connected the role as a bridge and a link between three, the matrix material micro interface inconsistent problem of having avoided the unsaturated resinoid matrixes such as simple employing vinyl ester resin to produce, and without adopting fiber surface to process stove to burn the upper glue layer of carbon fiber surface, also can there is good matrix material interlayer shearing resistance, both saved the time, shorten again production stage, reduce energy consumption.
Carbon nano double cured resin matrix for pultrude process of the present invention has good resistance to elevated temperatures, shock resistance and torsional property, meanwhile, its have viscosity low, with the feature that wetting property is good, curing speed is fast, solidification value is low of fiber.By its prepared matrix material, have that processing characteristics is good, snappiness good, intensity is high, resistant to elevated temperatures feature.
Simultaneously, the preparation method of matrix material of the present invention is simple, because product carbon fiber surface cementing agent is mainly epoxy resin, carbon fiber and epoxy resin-base have good interface compatibility energy, epoxy resin is same with carbon nanotube has good interface compatibility energy, carbon nanotube and Vinylite also have good interface compatibility energy, the matrix material micro interface inconsistent problem of having avoided the unsaturated resinoid matrixes such as simple employing vinyl ester resin to produce, and without adopting fiber surface to process stove to burn the upper glue layer of carbon fiber surface, both saved the time, shorten again production stage, reduce energy consumption.
More than explanation is only the preferred embodiment of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. for a carbon nano double cured resin matrix for pultrusion molding process, it is characterized in that: the raw material by following parts by weight is made:
50-90 part epoxy resin and solidifying agent thereof, 10-50 part vinyl ester resin and initiator thereof, 1-2 part carbon nanotube and optional appropriate amount of addition agent, this matrix is the two curing homogeneous system being made up of epoxy resin and solidifying agent thereof and vinyl ester resin and initiator thereof, dispersed carbon nanotube wherein.
2. the carbon nano double cured resin matrix for pultrusion molding process according to claim 1, it is characterized in that: the weight part of auxiliary agent is 1-8, epoxy resin and solidifying agent weight proportion are 100: 25-100, vinyl ester resin and initiator weight proportion are 100:0.5-2.
3. the carbon nano double cured resin matrix for pultrusion molding process according to claim 1 and 2, it is characterized in that: epoxy resin is glycidyl ether type, glycidic amine type, glycidyl ester type, aliphatic epoxy resin, a kind of or its mixture in novolac epoxy, solidifying agent comprises acid anhydride type curing agent, amine curing agent, a kind of or its mixture of imidazole curing agent, vinyl ester resin is to carry out by epoxy resin and unsaturated organic monocarboxylic acid the molecule two ends that esterification by ring opening reacts and obtain to contain vinyl ester group, the class unsaturated polyester resin that middle skeleton is epoxy resin, initiator is that heating can be decomposed the organo-peroxide that produces free radical, auxiliary agent is one or more in releasing agent and reactive thinner.
4. the carbon nano double cured resin matrix for pultrusion molding process according to claim 1 and 2, it is characterized in that: Racemic glycidol ether type epoxy is a kind of or its mixture in bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, and available acid anhydride type curing agent comprises: methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl carbic anhydride, dodecenylsuccinic anhydride etc.; Amine curing agent comprises 4,4-, bis-amido ditanes, mphenylenediamine, m-xylene diamine, diethyl toluene diamine, isophorone diamine, 3,3'-dimethyl-4,4'-diamino-dicyclohexyl methyl hydride etc., and corresponding modified multicomponent amine; Imidazole curing agent is included as 2-ethyl-4-methylimidazole, benzyl-glyoxal ethyline, cyanoethyl-2-ethyl-4-methylimidazole, glyoxal ethyline, vinyl ester resin is bisphenol A-type vinyl ester resin and/or phenol aldehyde type vinyl ester resin, initiator comprises: methylethyl ketone peroxide, benzoyl peroxide, cyclohexanone peroxide, dicumyl peroxide, tert-butyl peroxide, t-butylperoxyl benzoate, and available releasing agent comprises modified phosphate, organic fluorinated silicone compound, trolamine oil; Available reactive thinner includes but not limited to that glycidyl allyl ether, ethylene glycol diglycidylether, butanediol diglycidyl ether etc. have the multi-functional compound of low viscosity.
5. the preparation method of the carbon nano double cured resin matrix for pultrusion molding process according to claim 1 and 2, it is characterized in that: comprise the following steps: the common curing reaction of epoxy resin and vinyl ester resin, even carbon nanotube disperses wherein to form two curing homogeneous system-carbon nano double cured resin matrixes.
6. a matrix material of preparing for the carbon nano double cured resin matrix of pultrusion molding process according to claim 1 and 2, it is characterized in that: solidify to form by continuous fortifying fibre and above-mentioned carbon nano double cured resin matrix composite heating, wherein resin matrix is cross-linked to form the multidimensional crossover network structure taking carbon nanotube as contact.
7. matrix material according to claim 6, is characterized in that: fortifying fibre accounts for the 53%-74% of matrix material volume total content continuously.
8. matrix material according to claim 7, is characterized in that: fortifying fibre is a kind of or its mixture of carbon fiber, glass fibre, basalt fibre, organic synthetic fibers, steel fiber continuously.
9. the preparation method of a matrix material according to claim 6, it is characterized in that: comprise the following steps: continuous fortifying fibre and the compound post-heating of above-mentioned carbon nano double cured resin matrix are solidified and formed, wherein, in matrix material, resin matrix is cross-linked to form multidimensional crossover network structure.
10. according to the preparation method of claim matrix material according to claim 9, it is characterized in that: comprise the following steps: solidifying agent, carbon nanotube are added in effective dispersing machine and disperseed successively; Then add successively epoxy resin, vinyl ester resin to disperse; Add successively again initiator, releasing agent, by after above component mixing and stirring, inject the steeping vat of extruding equipment, with after continuous fortifying fibre impregnated carbon nano double cured resin matrix, by the matrix material that is heating and curing and forms.
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| 张铭: ""互穿网络型乙烯基酯树脂/环氧树脂及其在碳纤维拉挤复合材料的制备研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, 15 March 2005 (2005-03-15), pages 020 - 26 * |
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