CN103214792B - A kind of carbon fiber/epoxy resin composite material and preparation method thereof - Google Patents
A kind of carbon fiber/epoxy resin composite material and preparation method thereof Download PDFInfo
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- CN103214792B CN103214792B CN201310125726.3A CN201310125726A CN103214792B CN 103214792 B CN103214792 B CN 103214792B CN 201310125726 A CN201310125726 A CN 201310125726A CN 103214792 B CN103214792 B CN 103214792B
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 177
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 177
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 92
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 92
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000002131 composite material Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000003063 flame retardant Substances 0.000 claims abstract description 65
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 238000004132 cross linking Methods 0.000 claims abstract description 26
- 239000007787 solid Substances 0.000 claims abstract description 18
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 12
- 235000021317 phosphate Nutrition 0.000 claims abstract description 12
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 15
- 239000000835 fiber Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 238000001721 transfer moulding Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 2
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 8
- 231100001010 corrosive Toxicity 0.000 abstract description 7
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 239000003518 caustics Substances 0.000 abstract description 6
- 238000002485 combustion reaction Methods 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 230000000979 retarding effect Effects 0.000 abstract description 6
- 231100000331 toxic Toxicity 0.000 abstract description 6
- 230000002588 toxic effect Effects 0.000 abstract description 6
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 abstract description 2
- 235000010290 biphenyl Nutrition 0.000 description 13
- 239000004305 biphenyl Substances 0.000 description 13
- 125000006267 biphenyl group Chemical group 0.000 description 13
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 13
- 239000005341 toughened glass Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 5
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 3
- YASRHLDAFCMIPB-UHFFFAOYSA-N (1-oxo-2,6,7-trioxa-1$l^{5}-phosphabicyclo[2.2.2]octan-4-yl)methanol Chemical compound C1OP2(=O)OCC1(CO)CO2 YASRHLDAFCMIPB-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 description 1
- 101710130081 Aspergillopepsin-1 Proteins 0.000 description 1
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- -1 hydrogen halides Chemical class 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
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Abstract
The invention discloses a kind of carbon fiber/epoxy resin composite material, comprising: by the solid epoxy resin formed after liquid-state epoxy resin crosslinking curing, the solidifying agent making liquid-state epoxy resin crosslinking curing, organic phosphates fire retardant, carbon fiber.This carbon fiber/epoxy resin composite material adopts organic phosphates fire retardant as fire retardant, and corrosives in the degradation production of this fire retardant and the products of combustion of fire retarding epoxide resin, Toxic are less, greatly reduce the secondary pollution for environment.Organic phosphonate system fire retardant solubility is strong, is scattered in epoxy resin than being easier to.In carbon fiber/epoxy resin composite material, organic phosphates fire retardant is few as the consumption of fire retardant, good flame retardation effect.The preparation method of this carbon fiber/epoxy resin composite material is simple, is easy to a large amount of production.
Description
Technical field
The invention belongs to field of compound material, particularly a kind of carbon fiber/epoxy resin composite material and preparation method thereof.
Background technology
Fibre reinforced composites have specific tenacity and specific modulus is high, performance can design and be easy to many excellent specific properties such as global formation, make it obtain increasingly extensive application, particularly field of aerospace in dual-use field.At present, fibre reinforced composites also result in very large concern, particularly carbon fiber/epoxy resin composite material in the application of automotive field.Carbon fiber/epoxy resin composite material is a kind of high strength composite, carbon fiber mainly as strongthener and the epoxy resin as body material form, in numerous lightweighting materials, there is higher specific tenacity, specific modulus, the advantage that light weight effect is fairly obvious.
Along with the raising of people's security against fire consciousness, the requirement for the fire-retardant performance of matrix material is also more and more higher.Main ingredient in a lot of matrix material is epoxy resin, but for epoxy resin, incendive characteristic limits its application in a lot of field.Therefore, develop high-performance refractory carbon-fibre reinforced epoxy resin composite material to have great importance.But the fire retardant in carbon fiber/epoxy resin composite material is in the past halogen containing flame-retardant, when after carbon fiber/epoxy resin composite material burning, a large amount of smog and poisonous corrosive hydrogen halides gas can be produced, thus cause secondary to endanger to environment.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in prior art, a kind of carbon fiber/epoxy resin composite material and preparation method thereof is provided, corrosives in the degradation production of the fire retardant in this matrix material and the products of combustion of fire retarding epoxide resin, Toxic are less, greatly reduce the secondary pollution for environment, and good flame retardation effect.
The technical scheme that solution the technology of the present invention problem adopts is to provide a kind of carbon fiber/epoxy resin composite material, and it comprises: by the solid epoxy resin formed after liquid-state epoxy resin crosslinking curing, the solidifying agent making liquid-state epoxy resin crosslinking curing, organic phosphates fire retardant, carbon fiber.
Preferably, the viscosity of described liquid-state epoxy resin 25 DEG C time is 100cps ~ 5000cps.
Preferably, described organic phosphates fire retardant comprises one or several mixtures in phosphoric acid ester, condensed phosphoric esters, phosphine oxide and phosphorous heterocylic compound.
Preferably, described carbon fiber comprises any one in the plain weave of 3K, 6K, 12K, 24K, 48K or twill carbon cloth or Unidirectional fiber laid fabric.
Preferably, described carbon fiber/epoxy resin composite material comprises: 100 mass parts by the solidifying agent making liquid-state epoxy resin crosslinking curing of the solid epoxy resin formed after liquid-state epoxy resin crosslinking curing, 10 ~ 40 mass parts.
Preferably, the quality of described organic phosphates fire retardant be by the solid epoxy resin formed after liquid-state epoxy resin crosslinking curing and make 5% ~ 25% of the quality sum of the solidifying agent of liquid-state epoxy resin crosslinking curing, the quality of described carbon fiber is by 60% ~ 70% of the solid epoxy resin quality formed after liquid-state epoxy resin crosslinking curing.
The present invention also provides the preparation method of above-mentioned carbon fiber/epoxy resin composite material, comprises the following steps:
(1) organic phosphates fire retardant is mixed with liquid-state epoxy resin;
(2) solidifying agent making liquid-state epoxy resin crosslinking curing is added;
(3) adopting composite material process planning, by using carbon fiber and said mixture, after liquid-state epoxy resin crosslinking curing forms solid epoxy resin, preparing carbon fiber/epoxy resin composite material.
Preferably, the mixture in described step (1) stirs 0.5 ~ 2 hour, then places 1 ~ 3 hour at the temperature of 40 DEG C ~ 60 DEG C;
And/or the mixture in described step (2) stirs 10 ~ 30 minutes.
Preferably, when the viscosity when described liquid-state epoxy resin is at 25 DEG C is not less than 500cps, in described step (1), also need to add thinner, wherein, described liquid-state epoxy resin is 100 mass parts, described solidifying agent is 10 ~ 40 mass parts, and described thinner is 0 ~ 15 mass parts.
Preferably, described thinner is any one or a few in acetone, ethanol, vinyl acetic monomer, dimethyl formamide.
Preferably, described composite material process planning is any one in manual pasting forming process, the molded technique of vacuum bag, Resin transfer molding moulding process.
Carbon fiber/epoxy resin composite material in the present invention adopts organic phosphates fire retardant as fire retardant, corrosives in the degradation production of this fire retardant and the products of combustion of fire retarding epoxide resin, Toxic are less, greatly reduce the secondary pollution for environment.Organic phosphonate system fire retardant solubility is strong, is scattered in epoxy resin than being easier to.In carbon fiber/epoxy resin composite material, organic phosphates fire retardant is few as the consumption of fire retardant, good flame retardation effect.The preparation method of this carbon fiber/epoxy resin composite material is simple, is easy to a large amount of production.
Accompanying drawing explanation
Fig. 1 is the total heat release graphic representation of the carbon fiber/epoxy resin composite material of preparation in embodiment 1 ~ 3 in the present invention, comparative example 1.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
In following embodiment, when preparing carbon fiber/epoxy resin composite material, in employing composite material process planning, use toughened glass as rigidity one-side mould, the treating processes of this toughened glass is: after being cleaned out by toughened glass surface sanitising agent, apply three times with releasing agent again, each coating midfeather is 20 minutes, obtains stand-by toughened glass.Treating processes due to toughened glass is known, therefore is no longer described in greater detail in an embodiment.Certainly, when preparing carbon fiber/epoxy resin composite material, also can use other mould, repeating no longer one by one here.
Embodiment 1
The present embodiment provides a kind of preparation method preparing carbon fiber/epoxy resin composite material, comprises the following steps:
(1) the fire retardant Resorcino of 6.5 mass parts two (diphenyl phosphoester) (being called for short RDP) is joined in the liquid-state epoxy resin (DOWVoraforceTF301EpoxyResin) of 100 mass parts, then add in the diluent ethanol of 12 mass parts, stir after 1 hour, then in the baking oven being positioned over 40 DEG C 1 hour.Wherein, the viscosity of liquid-state epoxy resin (DOWVoraforceTF301EpoxyResin) 25 DEG C time is 1100cps.
(2) from baking oven, take out the mixture of fire retardant Resorcino two (diphenyl phosphoester) and liquid-state epoxy resin (DOWVoraforceTF301EpoxyResin), add the solidifying agent (DOWVoraforceTF350Hardener) of 30 mass parts more wherein, stir 5 minutes.Wherein, the quality of the fire retardant Resorcino in step (1) two (diphenyl phosphoester) be liquid-state epoxy resin (DOWVoraforceTF301EpoxyResin) and solidifying agent (DOWVoraforceTF350Hardener) quality and 5%.The epoxy resin formed after the quality of liquid-state epoxy resin and its crosslinking curing in the present embodiment identical in quality.
(3) at the above-mentioned stand-by toughened glass handled well as rigidity one-side mould, adopt manual pasting forming process preparation containing the composite material laminated board of the plain weave carbon fiber of 8 layers of 12K, length and the width of described plate are respectively 60cm and 40cm, at room temperature solidify 24 hours, obtain carbon fiber/epoxy resin composite material, wherein, the quality of the plain weave carbon fiber of 8 layers of 12K is 60% of the quality of solid epoxy resin.Carbon fiber greatly strengthen the intensity of matrix material in this carbon fiber/epoxy resin composite material.
Carbon fiber/epoxy resin composite material in the present embodiment adopts Resorcino two (diphenyl phosphoester) as fire retardant, corrosives in the degradation production of this fire retardant and the products of combustion of fire retarding epoxide resin, Toxic are less, greatly reduce the secondary pollution for environment.Two (diphenyl phosphoester) solubility of Resorcino is strong, is scattered in epoxy resin than being easier to.In carbon fiber/epoxy resin composite material, Resorcino two (diphenyl phosphoester) is few as the consumption of fire retardant, good flame retardation effect.The preparation method of this carbon fiber/epoxy resin composite material is simple, is easy to a large amount of production.
Comparative example 1
This comparative example provides a kind of preparation method preparing carbon fiber/epoxy resin composite material, comprises the following steps:
(1) liquid-state epoxy resin (DOWVoraforceTF301EpoxyResin) of 100 mass parts is added in the diluent ethanol of 12 mass parts, stir after 1 hour, then in the baking oven being positioned over 40 DEG C 1 hour.Wherein, the viscosity of liquid-state epoxy resin (DOWVoraforceTF301EpoxyResin) 25 DEG C time is 1100cps.
(2) from baking oven, take out the mixture of liquid-state epoxy resin (DOWVoraforceTF301EpoxyResin), then add the solidifying agent (DOWVoraforceTF350Hardener) of 30 mass parts wherein, stir 5 minutes.The epoxy resin formed after the quality of liquid-state epoxy resin and its crosslinking curing in the present embodiment identical in quality.
(3) at the above-mentioned stand-by toughened glass handled well as rigidity one-side mould, adopt manual pasting forming process preparation containing the composite material laminated board of the plain weave carbon fiber of 8 layers of 12K, length and the width of described plate are respectively 60cm and 40cm, at room temperature solidify 24 hours, obtain carbon fiber/epoxy resin composite material, wherein, the quality of the plain weave carbon fiber of 8 layers of 12K is 60% of the quality of solid epoxy resin.Not containing fire retardant in carbon fiber/epoxy resin composite material obtained in the present embodiment.
Embodiment 2
The present embodiment provides a kind of preparation method preparing carbon fiber/epoxy resin composite material, comprises the following steps:
(1) the fire retardant Resorcino of 19.5 mass parts two (diphenyl phosphoester) (being called for short RDP) is joined in the liquid-state epoxy resin (DOWVoraforceTF301EpoxyResin) of 100 mass parts, then add in the diluent ethanol of 15 mass parts and the mixed solvent of acetone, stir after 1 hour, then in the baking oven being positioned over 40 DEG C 1 hour.Wherein, the viscosity of liquid-state epoxy resin (DOWVoraforceTF301EpoxyResin) 25 DEG C time is 1100cps.
(2) from baking oven, take out the mixture of fire retardant Resorcino two (diphenyl phosphoester) and liquid-state epoxy resin (DOWVoraforceTF301EpoxyResin), add the solidifying agent (DOWVoraforceTF350Hardener) of 30 mass parts more wherein, stir 5 minutes.Wherein, the quality of the fire retardant Resorcino in step (1) two (diphenyl phosphoester) be liquid-state epoxy resin (DOWVoraforceTF301EpoxyResin) and solidifying agent (DOWVoraforceTF350Hardener) quality and 15%.The epoxy resin formed after the quality of liquid-state epoxy resin and its crosslinking curing in the present embodiment identical in quality.
(3) at the above-mentioned stand-by toughened glass handled well as rigidity one-side mould, adopt manual pasting forming process preparation containing the composite material laminated board of Unidirectional fiber laid fabric, length and the width of described plate are respectively 60cm and 40cm, at room temperature solidify 24 hours, obtain carbon fiber/epoxy resin composite material, wherein, the quality of Unidirectional fiber laid fabric is 68% of the quality of solid epoxy resin.
Embodiment 3
The present embodiment provides a kind of preparation method preparing carbon fiber/epoxy resin composite material, comprises the following steps:
(1) the fire retardant Resorcino of 32.5 mass parts two (diphenyl phosphoester) (being called for short RDP) is joined in the liquid-state epoxy resin (DOWVoraforceTF301EpoxyResin) of 100 mass parts, then add in the thinner vinyl acetic monomer of 10 mass parts, stir after 1 hour, then in the baking oven being positioned over 40 DEG C 1 hour.Wherein, the viscosity of liquid-state epoxy resin (DOWVoraforceTF301EpoxyResin) 25 DEG C time is 1100cps.
(2) from baking oven, take out the mixture of fire retardant Resorcino two (diphenyl phosphoester) and liquid-state epoxy resin (DOWVoraforceTF301EpoxyResin), add the solidifying agent (DOWVoraforceTF350Hardener) of 30 mass parts more wherein, stir 5 minutes.Wherein, the quality of the fire retardant Resorcino in step (1) two (diphenyl phosphoester) be liquid-state epoxy resin (DOWVoraforceTF301EpoxyResin) and solidifying agent (DOWVoraforceTF350Hardener) quality and 25%.The epoxy resin formed after the quality of liquid-state epoxy resin and its crosslinking curing in the present embodiment identical in quality.
(3) at the above-mentioned stand-by toughened glass handled well as rigidity one-side mould, adopt the preparation of Resin transfer molding moulding process containing the composite material laminated board of the twill carbon fiber of 8 layers of 24K, length and the width of described plate are respectively 60cm and 40cm, at room temperature solidify 24 hours, obtain carbon fiber/epoxy resin composite material, wherein, the quality of the twill carbon fiber of 8 layers of 24K is 62% of the quality of solid epoxy resin.
Embodiment 4
The present embodiment provides a kind of preparation method preparing carbon fiber/epoxy resin composite material, comprises the following steps:
(1) mixture of the fire retardant triphenylphosphine oxide of 27.5 mass parts and tributylphosphine oxide (mass ratio 1: 1) is joined in the liquid-state epoxy resin (HuntsmanLY1564) of 100 mass parts, then add in the thinner acetone of 2 mass parts, stir after 0.5 hour, then in the baking oven being positioned over 50 DEG C 2 hours.Wherein, the viscosity of liquid-state epoxy resin (HuntsmanLY1564) 25 DEG C time is 1200 ~ 1400cps.
(2) from baking oven, take out the mixture of fire retardant triphenylphosphine oxide, tributylphosphine oxide and liquid-state epoxy resin (HuntsmanLY1564), then add the solidifying agent (HuntsmanAradur5003-1) of 10 mass parts wherein, stir 10 minutes.Wherein, the fire retardant triphenylphosphine oxide in step (1) and the quality of tributylphosphine oxide and be liquid-state epoxy resin (HuntsmanLY1564) and solidifying agent (HuntsmanAradur5003-1) quality and 25%.The epoxy resin formed after the quality of liquid-state epoxy resin and its crosslinking curing in the present embodiment identical in quality.
(3) at the above-mentioned stand-by toughened glass handled well as rigidity one-side mould, adopt the molded technique preparation of vacuum bag containing the composite material laminated board of the twill carbon fiber of 8 layers of 6K, length and the width of described plate are respectively 60cm and 40cm, at room temperature solidify 24 hours, obtain carbon fiber/epoxy resin composite material, wherein, the quality of the twill carbon fiber of 8 layers of 6K is 64% of the quality of solid epoxy resin.
Carbon fiber/epoxy resin composite material in the present embodiment adopts triphenylphosphine oxide and tributylphosphine oxide as fire retardant, corrosives in the degradation production of this fire retardant and the products of combustion of fire retarding epoxide resin, Toxic are less, greatly reduce the secondary pollution for environment.In carbon fiber/epoxy resin composite material, triphenylphosphine oxide and tributylphosphine oxide few as the consumption of fire retardant, good flame retardation effect.The preparation method of this carbon fiber/epoxy resin composite material is simple, is easy to a large amount of production.
Embodiment 5
The present embodiment provides a kind of preparation method preparing carbon fiber/epoxy resin composite material, comprises the following steps:
(1) by the fire retardant 10-(2 of 25.2 mass parts, 5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound (be called for short DOPO-HQ) joins in the liquid-state epoxy resin Epon862 of 100 mass parts, then add in the diluent dimethylformamide of 7 mass parts, stir after 2 hours, then in the baking oven being positioned over 60 DEG C 3 hours.Wherein, the viscosity of liquid-state epoxy resin Epon862 25 DEG C time is 2500 ~ 4500cps.
(2) from baking oven, fire retardant 10-(2 is taken out, 5-dihydroxy phenyl) mixture of-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound and liquid-state epoxy resin Epon862, add the solidifying agent EPIKURE3271 of 40 mass parts more wherein, stir 20 minutes.Wherein, the fire retardant 10-(2 in step (1), 5-dihydroxy phenyl) quality of-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound be liquid-state epoxy resin Epon862 and solidifying agent EPIKURE3271 quality and 18%.The epoxy resin formed after the quality of liquid-state epoxy resin and its crosslinking curing in the present embodiment identical in quality.
(3) at the above-mentioned stand-by toughened glass handled well as rigidity one-side mould, adopt the molded technique preparation of vacuum bag containing the composite material laminated board of the plain weave carbon fiber of 8 layers of 48K, length and the width of described plate are respectively 60cm and 40cm, at room temperature solidify 24 hours, obtain carbon fiber/epoxy resin composite material, wherein, the quality of the plain weave carbon fiber of 8 layers of 48K is 70% of the quality of solid epoxy resin.
Carbon fiber/epoxy resin composite material in the present embodiment adopts 10-(2,5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound is as fire retardant, corrosives in the degradation production of this fire retardant and the products of combustion of fire retarding epoxide resin, Toxic are less, greatly reduce the secondary pollution for environment.In carbon fiber/epoxy resin composite material, 10-(2,5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound is few as the consumption of fire retardant, good flame retardation effect.The preparation method of this carbon fiber/epoxy resin composite material is simple, is easy to a large amount of production.
Embodiment 6
The present embodiment provides a kind of preparation method preparing carbon fiber/epoxy resin composite material, comprises the following steps:
(1) by the fire retardant 1-oxo-4-methylol-2 of 6 mass parts, 6,7-trioxa-1-phosphabicyclo [2.2.2] octane (be called for short PEPA) joins in the liquid-state epoxy resin SWANCOR2511-A of 100 mass parts, stirs after 1.5 hours, then in the baking oven being positioned over 45 DEG C 2.5 hours.Wherein, the viscosity of liquid-state epoxy resin SWANCOR2511-A 25 DEG C time is 230 ~ 330cps.Because the viscosity of liquid-state epoxy resin SWANCOR2511-A is lower, do not need to use thinner to disperse, just can realize fire retardant 1-oxo-4-methylol-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane to be scattered in equably in liquid-state epoxy resin SWANCOR2511-A.
(2) from baking oven, take out fire retardant 1-oxo-4-methylol-2,6, the mixture of 7-trioxa-1-phosphabicyclo [2.2.2] octane and liquid-state epoxy resin SWANCOR2511-A, then add the solidifying agent SWANCOR2511-BF of 20 mass parts wherein, stir 30 minutes.Wherein, the quality of fire retardant 1-oxo-4-methylol-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane in step (1) be liquid-state epoxy resin SWANCOR2511-A and solidifying agent SWANCOR2511-BF quality and 5%.The epoxy resin formed after the quality of liquid-state epoxy resin and its crosslinking curing in the present embodiment identical in quality.
(3) at the above-mentioned stand-by toughened glass handled well as rigidity one-side mould, adopt the preparation of Resin transfer molding moulding process containing the composite material laminated board of the twill carbon fiber of 8 layers of 12K, length and the width of described plate are respectively 60cm and 40cm, at room temperature solidify 24 hours, obtain carbon fiber/epoxy resin composite material, wherein, the quality of the twill carbon fiber of 8 layers of 12K is 65% of the quality of solid epoxy resin.
Embodiment 7
The present embodiment provides a kind of preparation method preparing carbon fiber/epoxy resin composite material, comprises the following steps:
(1) the fire retardant triphenylphosphate of 13.5 mass parts is joined in the liquid-state epoxy resin SWANCOR2511-A of 100 mass parts, stir after 1.8 hours, then in the baking oven being positioned over 55 DEG C 1.5 hours.Wherein, the viscosity of liquid-state epoxy resin SWANCOR2511-A 25 DEG C time is 230 ~ 330cps.
(2) from baking oven, take out the mixture of fire retardant triphenylphosphate and liquid-state epoxy resin SWANCOR2511-A, then add the solidifying agent SWANCOR2511-BF of 35 mass parts wherein, stir 25 minutes.Wherein, the quality of the fire retardant triphenylphosphate in step (1) be liquid-state epoxy resin SWANCOR2511-A and solidifying agent SWANCOR2511-BF quality and 10%.The epoxy resin formed after the quality of liquid-state epoxy resin and its crosslinking curing in the present embodiment identical in quality.
(3) at the above-mentioned stand-by toughened glass handled well as rigidity one-side mould, adopt manual pasting forming process preparation containing the composite material laminated board of the plain weave carbon fiber of 8 layers of 3K, length and the width of described plate are respectively 60cm and 40cm, at room temperature solidify 24 hours, obtain carbon fiber/epoxy resin composite material, wherein, the quality of the plain weave carbon fiber of 8 layers of 3K is 63% of the quality of solid epoxy resin.
Table 1. different flame retardant content carbon-fibre composite burning data
In Fig. 1, the curve of numbering 1 correspond to the carbon fiber/epoxy resin composite material of the comparative example 1 in table 1, the carbon fiber/epoxy resin composite material of preparation in comparative example 1 not containing fire retardant.In Fig. 1, the curve of numbering 2 correspond to the carbon fiber/epoxy resin composite material of the embodiment 1 in table 1, the quality of the fire retardant of the carbon fiber/epoxy resin composite material prepared in embodiment 1 be liquid-state epoxy resin (DOWVoraforceTF301EpoxyResin) and solidifying agent (DOWVoraforceTF350Hardener) quality and 5%.In Fig. 1, the curve of numbering 3 correspond to the carbon fiber/epoxy resin composite material of the embodiment 2 in table 1, the quality of the fire retardant of the carbon fiber/epoxy resin composite material prepared in example 2 be liquid-state epoxy resin (DOWVoraforceTF301EpoxyResin) and solidifying agent (DOWVoraforceTF350Hardener) quality and 15%.In Fig. 1, the curve of numbering 4 correspond to the carbon fiber/epoxy resin composite material of the embodiment 3 in table 1, the quality of the fire retardant of the carbon fiber/epoxy resin composite material prepared in embodiment 1 be liquid-state epoxy resin (DOWVoraforceTF301EpoxyResin) and solidifying agent (DOWVoraforceTF350Hardener) quality and 25%.As can be seen from the total heat release of carbon fiber/epoxy resin composite material corresponding when 300 seconds, the addition of fire retardant is more, then the maximum heat release efficiency of carbon fiber/epoxy resin composite material is higher.Along with the increase of fire retardant addition, the total heat release of carbon fiber/epoxy resin composite material constantly reduces, 5%, the addition of fire retardant of 15%, 25% makes total heat release reduce by 12.8%, 25.8% and 49.6% respectively, and this also can find out that the interpolation of Resorcino two (diphenyl phosphoester) can play obvious flame retardant effect to carbon-fibre composite.
Embodiment 8
The present embodiment provides a kind of carbon fiber/epoxy resin composite material, and it is prepared by the described preparation method in above-described embodiment.
Be understandable that, the illustrative embodiments that above embodiment is only used to principle of the present invention is described and adopts, but the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement are also considered as protection scope of the present invention.
Claims (6)
1. a preparation method for carbon fiber/epoxy resin composite material, is characterized in that, comprises the following steps:
(1) mixed with liquid-state epoxy resin by organic phosphates fire retardant, stir 0.5 ~ 2 hour, then place 1 ~ 3 hour at the temperature of 40 DEG C ~ 55 DEG C, the viscosity of described liquid-state epoxy resin 25 DEG C time is 100cps ~ 5000cps;
(2) add the solidifying agent making liquid-state epoxy resin crosslinking curing, stir 10 ~ 30 minutes;
(3) composite material process planning is adopted, by using carbon fiber and said mixture, after liquid-state epoxy resin crosslinking curing forms solid epoxy resin, prepare carbon fiber/epoxy resin composite material, described composite material process planning is the molded technique of vacuum bag or Resin transfer molding moulding process.
2. the preparation method of carbon fiber/epoxy resin composite material according to claim 1, it is characterized in that, when viscosity when described liquid-state epoxy resin is at 25 DEG C is not less than 500cps, in described step (1), also need to add thinner, wherein, described liquid-state epoxy resin is 100 mass parts, described solidifying agent is 10 ~ 40 mass parts, and described thinner is 2 ~ 15 mass parts.
3. the preparation method of carbon fiber/epoxy resin composite material according to claim 1, is characterized in that, described organic phosphates fire retardant comprises one or several mixtures in phosphoric acid ester, condensed phosphoric esters, phosphine oxide and phosphorous heterocylic compound.
4. the preparation method of the carbon fiber/epoxy resin composite material according to claim 1 or 3, it is characterized in that, described carbon fiber comprise in the plain weave of 3K, 6K, 12K, 24K, 48K or twill carbon cloth or Unidirectional fiber laid fabric any one.
5. the preparation method of the carbon fiber/epoxy resin composite material according to claim 1 or 3, it is characterized in that, comprising: 100 mass parts by the solidifying agent making liquid-state epoxy resin crosslinking curing of the solid epoxy resin formed after liquid-state epoxy resin crosslinking curing, 10 ~ 40 mass parts.
6. the preparation method of carbon fiber/epoxy resin composite material according to claim 5, it is characterized in that, the quality of described organic phosphates fire retardant be by the solid epoxy resin formed after liquid-state epoxy resin crosslinking curing and make liquid-state epoxy resin crosslinking curing solidifying agent quality sum 5% ~ 25%, the quality of described carbon fiber is by 60% ~ 70% of the solid epoxy resin quality formed after liquid-state epoxy resin crosslinking curing.
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| CN104479296B (en) * | 2014-12-24 | 2017-01-11 | 芜湖市汽车产业技术研究院有限公司 | Method for improving impact strength of epoxy resin/carbon fiber composite material |
| CN104403279B (en) * | 2014-12-26 | 2017-09-12 | 芜湖市汽车产业技术研究院有限公司 | A kind of preparation method of high-toughness epoxy resin carbon fibre composite |
| CN108884211B (en) * | 2016-04-12 | 2021-04-06 | 三菱瓦斯化学株式会社 | Epoxy resin curing agent, epoxy resin composition, and carbon fiber-reinforced composite material |
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