CN103214792A - Carbon fiber/epoxy resin composite material and preparation method thereof - Google Patents
Carbon fiber/epoxy resin composite material and preparation method thereof Download PDFInfo
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- CN103214792A CN103214792A CN2013101257263A CN201310125726A CN103214792A CN 103214792 A CN103214792 A CN 103214792A CN 2013101257263 A CN2013101257263 A CN 2013101257263A CN 201310125726 A CN201310125726 A CN 201310125726A CN 103214792 A CN103214792 A CN 103214792A
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- epoxy resin
- carbon fiber
- composite material
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- fire retardant
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 170
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 170
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 101
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 101
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000002131 composite material Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000003063 flame retardant Substances 0.000 claims abstract description 68
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- 238000004132 cross linking Methods 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims description 35
- 239000011347 resin Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- 235000021317 phosphate Nutrition 0.000 claims description 10
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 6
- 238000005516 engineering process Methods 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
- 230000000694 effects Effects 0.000 abstract description 8
- 239000003518 caustics Substances 0.000 abstract description 6
- 238000002485 combustion reaction Methods 0.000 abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract 4
- 239000011574 phosphorus Substances 0.000 abstract 4
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 abstract 2
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 231100000614 poison Toxicity 0.000 abstract 1
- 239000003440 toxic substance Substances 0.000 abstract 1
- 239000004593 Epoxy Substances 0.000 description 13
- 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
- 238000004519 manufacturing process Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 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
- 231100001010 corrosive Toxicity 0.000 description 6
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000003912 environmental pollution Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- 230000000979 retarding effect Effects 0.000 description 5
- 231100000331 toxic Toxicity 0.000 description 5
- 230000002588 toxic effect Effects 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
- 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 4
- 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
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 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 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
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 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
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 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
- 239000003562 lightweight material Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
The invention discloses a carbon fiber/epoxy resin composite material comprising solid epoxy resin, a curing agent, an organic phosphorus fire retardant and carbon fiber, wherein the solid epoxy resin is formed after liquid epoxy resin is crosslinked and cured, and the curing agent is used for crosslinking and curing the liquid epoxy resin. The carbon fiber/epoxy resin composite material takes the organic phosphorus fire retardant as the fire retardant, and a decomposition product of the fire retardant and a combustion product of fire retardant epoxy resin contain fewer corrosive substances and toxic substances, so that secondary pollution to the environment is greatly reduced. The organic phosphorus fire retardant is strong in solubility and easier to disperse in epoxy resin. The organic phosphorus fire retardant as the fire retardant in the carbon fiber/epoxy resin composite material is low in usage and good in fire retardant effect. The carbon fiber/epoxy resin composite material is simple in preparation method and easy for large-scale 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 height, performance can design and be easy to many excellent specific properties such as global formation, make it obtain increasingly extensive application in dual-use field, particularly field of aerospace.At present, fibre reinforced composites have also caused very big 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, form mainly as the carbon fiber of strongthener with as the Resins, epoxy of body material, in numerous lightweight materials, have higher specific tenacity, specific modulus, the advantage that the lightweight effect is fairly obvious.
Along with the raising of people's security against fire consciousness, also more and more higher for the fire-retardant performance demands of matrix material.Main ingredient in a lot of matrix materials is a Resins, epoxy, but for Resins, epoxy, incendive characteristic limitations its application in a lot of fields.Therefore, development high-performance refractory carbon-fibre reinforced epoxy resin composite material has great importance.But the fire retardant in the carbon fiber/epoxy resin composite material in the past is halogen containing flame-retardant, after the carbon fiber/epoxy resin composite material burning, can produce a large amount of smog and deleterious corrosive hydrogen halides gas, thereby environment is caused secondary harm.
Summary of the invention
Technical problem to be solved by this invention is at above shortcomings in the 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 for second environmental pollution, and good flame retardation effect.
The technical scheme that solution the technology of the present invention problem is adopted provides a kind of carbon fiber/epoxy resin composite material, and it comprises: by the solid epoxy resin that forms behind the liquid-state epoxy resin crosslinking curing, the solidifying agent that makes the liquid-state epoxy resin crosslinking curing, organic phosphates fire retardant, carbon fiber.
Preferably, the viscosity of described liquid-state epoxy resin in the time of 25 ℃ is 100cps～5000cps.
Preferably, described organic phosphates fire retardant comprises one or several mixtures in phosphoric acid ester, condensed phosphoric esters, phosphine oxide and the 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 the no latitude cloth of unidirectional carbon fiber dimension.
Preferably, described carbon fiber/epoxy resin composite material comprises: the solidifying agent that makes the liquid-state epoxy resin crosslinking curing by the solid epoxy resin that forms behind the liquid-state epoxy resin crosslinking curing, 10～40 mass parts of 100 mass parts.
Preferably, the quality of described organic phosphates fire retardant for by the solid epoxy resin that forms behind the liquid-state epoxy resin crosslinking curing and make the liquid-state epoxy resin crosslinking curing solidifying agent the quality sum 5%～25%, the quality of described carbon fiber is for by 60%～70% of the solid epoxy resin quality that forms behind the liquid-state epoxy resin crosslinking curing.
The present invention also provides the preparation method of above-mentioned carbon fiber/epoxy resin composite material, may further comprise the steps:
(1) the organic phosphates fire retardant is mixed with liquid-state epoxy resin;
(2) add the solidifying agent that makes the liquid-state epoxy resin crosslinking curing;
(3) adopt composite material process planning,, after the liquid-state epoxy resin crosslinking curing forms solid epoxy resin, prepare carbon fiber/epoxy resin composite material by using carbon fiber and said mixture.
Preferably, the mixture in the described step (1) stirred 0.5～2 hour, placed 1～3 hour under 40 ℃～60 ℃ temperature again;
And/or the mixture in the described step (2) stirred 10～30 minutes.
Preferably, when the viscosity of described liquid-state epoxy resin during at 25 ℃ 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, the dimethyl formamide.
Preferably, described composite material process planning is any one in manual pasting forming process, the molded technology of vacuum bag, the resin transfer molding process planning.
Carbon fiber/epoxy resin composite material among the present invention adopts the 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 for second environmental pollution.Organic phosphine flame retardant solubility is strong, is scattered in the Resins, epoxy than being easier to.In carbon fiber/epoxy resin composite material, the 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 mass production.
Description of drawings
Fig. 1 is the total heat burst size graphic representation of the carbon fiber/epoxy resin composite material of preparation among the embodiment 1～3, Comparative Examples 1 among the present invention.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, the present invention is described in further detail below in conjunction with the drawings and specific embodiments.
In following each embodiment, when the preparation carbon fiber/epoxy resin composite material, in adopting composite material process planning, use toughened glass as the rigidity one-side mould, the treating processes of this toughened glass is: after the toughened glass surface is cleaned out with sanitising agent, apply three times with releasing agent, apply midfeather is 20 minutes at every turn, obtains stand-by toughened glass again.Because the treating processes of toughened glass is known, so no longer be described in greater detail in an embodiment.Certainly, when the preparation carbon fiber/epoxy resin composite material, also can use other mould, give unnecessary details no longer one by one here.
Embodiment 1
Present embodiment provides a kind of preparation method who prepares carbon fiber/epoxy resin composite material, may further comprise the steps:
(1) the fire retardant Resorcino two (diphenyl phosphoester) (being called for short RDP) with 6.5 mass parts joins in the liquid-state epoxy resin (DOW Voraforce TF301Epoxy Resin) of 100 mass parts, add then in the diluent ethanol of 12 mass parts, stir after 1 hour, be positioned over again in 40 ℃ the baking oven 1 hour.Wherein, the viscosity of liquid-state epoxy resin (DOW Voraforce TF301Epoxy Resin) in the time of 25 ℃ is 1100cps.
(2) mixture of two (diphenyl phosphoester) and liquid-state epoxy resins (DOW Voraforce TF301Epoxy Resin) of taking-up fire retardant Resorcino from baking oven, to the solidifying agent that wherein adds 30 mass parts (DOW Voraforce TF350Hardener), stirred 5 minutes again.Wherein, the quality of the fire retardant Resorcino in the step (1) two (diphenyl phosphoesters) be liquid-state epoxy resin (DOW Voraforce TF301Epoxy Resin) and solidifying agent (DOW Voraforce TF350Hardener) quality and 5%.The Resins, epoxy that forms behind 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 of handling well as the rigidity one-side mould, adopt the manual pasting forming process preparation to contain the composite material laminated board of the plain weave carbon fiber of 8 layers of 12K, the length of described plate and width are respectively 60cm and 40cm, at room temperature solidified 24 hours, obtain carbon fiber/epoxy resin composite material, wherein, the quality of the plain weave carbon fiber of 8 layers of 12K be solid epoxy resin quality 60%.Carbon fiber has strengthened the intensity of matrix material greatly 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 for second environmental pollution.Two (diphenyl phosphoester) solubilities of Resorcino are strong, are scattered in the Resins, epoxy 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 mass production.
Comparative Examples 1
This Comparative Examples provides a kind of preparation method who prepares carbon fiber/epoxy resin composite material, may further comprise the steps:
(1) liquid-state epoxy resin (DOW Voraforce TF301Epoxy Resin) of 100 mass parts is added in the diluent ethanol of 12 mass parts, stir after 1 hour, be positioned over again in 40 ℃ the baking oven 1 hour.Wherein, the viscosity of liquid-state epoxy resin (DOW Voraforce TF301Epoxy Resin) in the time of 25 ℃ is 1100cps.
(2) from baking oven, take out the mixture of liquid-state epoxy resin (DOW Voraforce TF301Epoxy Resin), to the solidifying agent that wherein adds 30 mass parts (DOW Voraforce TF350Hardener), stirred 5 minutes again.The Resins, epoxy that forms behind 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 of handling well as the rigidity one-side mould, adopt the manual pasting forming process preparation to contain the composite material laminated board of the plain weave carbon fiber of 8 layers of 12K, the length of described plate and width are respectively 60cm and 40cm, at room temperature solidified 24 hours, obtain carbon fiber/epoxy resin composite material, wherein, the quality of the plain weave carbon fiber of 8 layers of 12K be solid epoxy resin quality 60%.Do not contain fire retardant in the carbon fiber/epoxy resin composite material that makes in the present embodiment.
Embodiment 2
Present embodiment provides a kind of preparation method who prepares carbon fiber/epoxy resin composite material, may further comprise the steps:
(1) the fire retardant Resorcino two (diphenyl phosphoester) (being called for short RDP) with 19.5 mass parts joins in the liquid-state epoxy resin (DOW Voraforce TF301Epoxy Resin) of 100 mass parts, add then in the mixed solvent of the diluent ethanol of 15 mass parts and acetone, stir after 1 hour, be positioned over again in 40 ℃ the baking oven 1 hour.Wherein, the viscosity of liquid-state epoxy resin (DOW Voraforce TF301Epoxy Resin) in the time of 25 ℃ is 1100cps.
(2) mixture of two (diphenyl phosphoester) and liquid-state epoxy resins (DOW Voraforce TF301Epoxy Resin) of taking-up fire retardant Resorcino from baking oven, to the solidifying agent that wherein adds 30 mass parts (DOW Voraforce TF350Hardener), stirred 5 minutes again.Wherein, the quality of the fire retardant Resorcino in the step (1) two (diphenyl phosphoesters) be liquid-state epoxy resin (DOW Voraforce TF301Epoxy Resin) and solidifying agent (DOW Voraforce TF350Hardener) quality and 15%.The Resins, epoxy that forms behind 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 of handling well as the rigidity one-side mould, adopt the manual pasting forming process preparation to contain the composite material laminated board of the no latitude cloth of unidirectional carbon fiber dimension, the length of described plate and width are respectively 60cm and 40cm, at room temperature solidified 24 hours, obtain carbon fiber/epoxy resin composite material, wherein, the quality of the no latitude cloth of unidirectional carbon fiber dimension be solid epoxy resin quality 68%.
Embodiment 3
Present embodiment provides a kind of preparation method who prepares carbon fiber/epoxy resin composite material, may further comprise the steps:
(1) the fire retardant Resorcino two (diphenyl phosphoester) (being called for short RDP) with 32.5 mass parts joins in the liquid-state epoxy resin (DOW Voraforce TF301Epoxy Resin) of 100 mass parts, add then in the thinner vinyl acetic monomer of 10 mass parts, stir after 1 hour, be positioned over again in 40 ℃ the baking oven 1 hour.Wherein, the viscosity of liquid-state epoxy resin (DOW Voraforce TF301Epoxy Resin) in the time of 25 ℃ is 1100cps.
(2) mixture of two (diphenyl phosphoester) and liquid-state epoxy resins (DOW Voraforce TF301Epoxy Resin) of taking-up fire retardant Resorcino from baking oven, to the solidifying agent that wherein adds 30 mass parts (DOW Voraforce TF350Hardener), stirred 5 minutes again.Wherein, the quality of the fire retardant Resorcino in the step (1) two (diphenyl phosphoesters) be liquid-state epoxy resin (DOW Voraforce TF301Epoxy Resin) and solidifying agent (DOW Voraforce TF350Hardener) quality and 25%.The Resins, epoxy that forms behind 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 of handling well as the rigidity one-side mould, adopt the preparation of resin transfer molding process planning to contain the composite material laminated board of the twill carbon fiber of 8 layers of 24K, the length of described plate and width are respectively 60cm and 40cm, at room temperature solidified 24 hours, obtain carbon fiber/epoxy resin composite material, wherein, the quality of the twill carbon fiber of 8 layers of 24K be solid epoxy resin quality 62%.
Embodiment 4
Present embodiment provides a kind of preparation method who prepares carbon fiber/epoxy resin composite material, may further comprise the steps:
(1) the fire retardant triphenylphosphine oxide of 27.5 mass parts and the mixture of tributylphosphine oxide (mass ratio 1: 1) are joined in the liquid-state epoxy resin (Huntsman LY1564) of 100 mass parts, add then in the thinner acetone of 2 mass parts, stir after 0.5 hour, be positioned over again in 50 ℃ the baking oven 2 hours.Wherein, the viscosity of liquid-state epoxy resin (Huntsman LY1564) in the time of 25 ℃ is 1200～1400cps.
(2) mixture of taking-up fire retardant triphenylphosphine oxide, tributylphosphine oxide and liquid-state epoxy resin (Huntsman LY1564) from baking oven again to the solidifying agent that wherein adds 10 mass parts (Huntsman Aradur5003-1), stirred 10 minutes.Wherein, the quality of fire retardant triphenylphosphine oxide in the step (1) and tributylphosphine oxide and be liquid-state epoxy resin (Huntsman LY1564) and solidifying agent (Huntsman Aradur5003-1) quality and 25%.The Resins, epoxy that forms behind 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 of handling well as the rigidity one-side mould, adopt the molded prepared of vacuum bag to contain the composite material laminated board of the twill carbon fiber of 8 layers of 6K, the length of described plate and width are respectively 60cm and 40cm, at room temperature solidified 24 hours, obtain carbon fiber/epoxy resin composite material, wherein, the quality of the twill carbon fiber of 8 layers of 6K be solid epoxy resin quality 64%.
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 for second environmental pollution.In carbon fiber/epoxy resin composite material, triphenylphosphine oxide and tributylphosphine oxide are 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 mass production.
Embodiment 5
Present embodiment provides a kind of preparation method who prepares carbon fiber/epoxy resin composite material, may further comprise the steps:
(1) with the fire retardant 10-(2 of 25.2 mass parts, the 5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound (be called for short DOPO-HQ) joins among the liquid-state epoxy resin Epon862 of 100 mass parts, add then in the diluent dimethylformamide of 7 mass parts, stir after 2 hours, be positioned over again in 60 ℃ the baking oven 3 hours.Wherein, the viscosity of liquid-state epoxy resin Epon862 in the time of 25 ℃ is 2500～4500cps.
(2) from baking oven, take out fire retardant 10-(2,5-dihydroxy phenyl)-mixture of 10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound and liquid-state epoxy resin Epon862, again to the solidifying agent EPIKURE3271 that wherein adds 40 mass parts, stirred 20 minutes.Wherein, the fire retardant 10-(2 in the 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 Resins, epoxy that forms behind 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 of handling well as the rigidity one-side mould, adopt the molded prepared of vacuum bag to contain the composite material laminated board of the plain weave carbon fiber of 8 layers of 48K, the length of described plate and width are respectively 60cm and 40cm, at room temperature solidified 24 hours, obtain carbon fiber/epoxy resin composite material, wherein, the quality of the plain weave carbon fiber of 8 layers of 48K be solid epoxy resin quality 70%.
Carbon fiber/epoxy resin composite material in the present embodiment adopts 10-(2, the 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 for second environmental pollution.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 mass production.
Embodiment 6
Present embodiment provides a kind of preparation method who prepares carbon fiber/epoxy resin composite material, may further comprise the steps:
(1) with the fire retardant 1-oxo-4-methylol-2 of 6 mass parts, 6,7-trioxa-1-phospha dicyclo [2.2.2] octane (be called for short PEPA) joins among the liquid-state epoxy resin SWANCOR2511-A of 100 mass parts, stirs after 1.5 hours, is positioned in 45 ℃ the baking oven 2.5 hours again.Wherein, the viscosity of liquid-state epoxy resin SWANCOR2511-A in the time of 25 ℃ 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-phospha dicyclo [2.2.2] octane is scattered among the liquid-state epoxy resin SWANCOR2511-A equably.
(2) from baking oven, take out fire retardant 1-oxo-4-methylol-2,6, the mixture of 7-trioxa-1-phospha dicyclo [2.2.2] octane and liquid-state epoxy resin SWANCOR2511-A again to the solidifying agent SWANCOR2511-BF that wherein adds 20 mass parts, stirred 30 minutes.Wherein, the fire retardant 1-oxo-4-methylol-2,6 in the step (1), the quality of 7-trioxa-1-phospha dicyclo [2.2.2] octane be liquid-state epoxy resin SWANCOR2511-A and solidifying agent SWANCOR2511-BF quality and 5%.The Resins, epoxy that forms behind 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 of handling well as the rigidity one-side mould, adopt the preparation of resin transfer molding process planning to contain the composite material laminated board of the twill carbon fiber of 8 layers of 12K, the length of described plate and width are respectively 60cm and 40cm, at room temperature solidified 24 hours, obtain carbon fiber/epoxy resin composite material, wherein, the quality of the twill carbon fiber of 8 layers of 12K be solid epoxy resin quality 65%.
Embodiment 7
Present embodiment provides a kind of preparation method who prepares carbon fiber/epoxy resin composite material, may further comprise the steps:
(1) the fire retardant triphenylphosphate with 13.5 mass parts joins among the liquid-state epoxy resin SWANCOR2511-A of 100 mass parts, stirs after 1.8 hours, is positioned in 55 ℃ the baking oven 1.5 hours again.Wherein, the viscosity of liquid-state epoxy resin SWANCOR2511-A in the time of 25 ℃ is 230～330cps.
(2) mixture of taking-up fire retardant triphenylphosphate and liquid-state epoxy resin SWANCOR2511-A from baking oven again to the solidifying agent SWANCOR2511-BF that wherein adds 35 mass parts, stirred 25 minutes.Wherein, the quality of the fire retardant triphenylphosphate in the step (1) be liquid-state epoxy resin SWANCOR2511-A and solidifying agent SWANCOR2511-BF quality and 10%.The Resins, epoxy that forms behind 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 of handling well as the rigidity one-side mould, adopt the manual pasting forming process preparation to contain the composite material laminated board of the plain weave carbon fiber of 8 layers of 3K, the length of described plate and width are respectively 60cm and 40cm, at room temperature solidified 24 hours, obtain carbon fiber/epoxy resin composite material, wherein, the quality of the plain weave carbon fiber of 8 layers of 3K be solid epoxy resin quality 63%.
Table 1. different flame retardant content carbon-fibre composite burning data
Numbering 1 curve correspondence the carbon fiber/epoxy resin composite material of the Comparative Examples 1 in the table 1 among Fig. 1, and the carbon fiber/epoxy resin composite material of preparation does not contain fire retardant in Comparative Examples 1.Numbering 2 curve correspondence the carbon fiber/epoxy resin composite material of the embodiment 1 in the table 1 among Fig. 1, in embodiment 1 quality of the fire retardant of the carbon fiber/epoxy resin composite material of preparation be liquid-state epoxy resin (DOW Voraforce TF301Epoxy Resin) and solidifying agent (DOW Voraforce TF350Hardener) quality and 5%.Numbering 3 curve correspondence the carbon fiber/epoxy resin composite material of the embodiment 2 in the table 1 among Fig. 1, in embodiment 2 quality of the fire retardant of the carbon fiber/epoxy resin composite material of preparation be liquid-state epoxy resin (DOW Voraforce TF301Epoxy Resin) and solidifying agent (DOW Voraforce TF350Hardener) quality and 15%.Numbering 4 curve correspondence the carbon fiber/epoxy resin composite material of the embodiment 3 in the table 1 among Fig. 1, in embodiment 1 quality of the fire retardant of the carbon fiber/epoxy resin composite material of preparation be liquid-state epoxy resin (DOW Voraforce TF301Epoxy Resin) and solidifying agent (DOW Voraforce TF350Hardener) quality and 25%.During from 300 seconds the total heat burst size of the carbon fiber/epoxy resin composite material of correspondence as can be seen, the addition of fire retardant is many more, then the maximum heat release efficiency of carbon fiber/epoxy resin composite material is high more.Increase along with the fire retardant addition, the total heat burst size of carbon fiber/epoxy resin composite material constantly reduces, 5%, the addition of 15%, 25% fire retardant makes the total heat burst size reduce by 12.8%, 25.8% and 49.6% respectively, this also as can be seen the interpolation of Resorcino two (diphenyl phosphoesters) can play tangible flame retardant effect to carbon-fibre composite.
Embodiment 8
Present embodiment provides a kind of carbon fiber/epoxy resin composite material, and it is prepared by the described preparation method in the foregoing description.
Be understandable that above embodiment only is the illustrative embodiments that adopts for principle of the present invention is described, yet 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 also are considered as protection scope of the present invention.
Claims (10)
1. a carbon fiber/epoxy resin composite material is characterized in that, comprising: by the solid epoxy resin that forms behind the liquid-state epoxy resin crosslinking curing, the solidifying agent that makes the liquid-state epoxy resin crosslinking curing, organic phosphates fire retardant, carbon fiber.
2. 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 the phosphorous heterocylic compound.
3. carbon fiber/epoxy resin composite material according to claim 1 and 2 is characterized in that, the viscosity of described liquid-state epoxy resin in the time of 25 ℃ is 100cps～5000cps.
4. carbon fiber/epoxy resin composite material according to claim 1 and 2 is characterized in that, described carbon fiber comprises any one in the plain weave of 3K, 6K, 12K, 24K, 48K or twill carbon cloth or the no latitude cloth of unidirectional carbon fiber dimension.
5. carbon fiber/epoxy resin composite material according to claim 1 and 2, it is characterized in that, comprising: the solidifying agent that makes the liquid-state epoxy resin crosslinking curing by the solid epoxy resin that forms behind the liquid-state epoxy resin crosslinking curing, 10～40 mass parts of 100 mass parts.
6. carbon fiber/epoxy resin composite material according to claim 5, it is characterized in that, the quality of described organic phosphates fire retardant is that the quality of described carbon fiber is by 60%～70% of the solid epoxy resin quality that forms behind the liquid-state epoxy resin crosslinking curing by 5%～25% of the quality sum of solid epoxy resin that forms behind the liquid-state epoxy resin crosslinking curing and the solidifying agent that makes the liquid-state epoxy resin crosslinking curing.
7. the preparation method of a carbon fiber/epoxy resin composite material is characterized in that, may further comprise the steps:
(1) the organic phosphates fire retardant is mixed with liquid-state epoxy resin;
(2) add the solidifying agent that makes the liquid-state epoxy resin crosslinking curing;
(3) adopt composite material process planning,, after the liquid-state epoxy resin crosslinking curing forms solid epoxy resin, prepare carbon fiber/epoxy resin composite material by using carbon fiber and said mixture.
8. the preparation method of carbon fiber/epoxy resin composite material according to claim 7 is characterized in that, the mixture in the described step (1) stirred 0.5～2 hour, placed 1～3 hour under 40 ℃～60 ℃ temperature again;
And/or the mixture in the described step (2) stirred 10～30 minutes.
9. the preparation method of carbon fiber/epoxy resin composite material according to claim 7, it is characterized in that, when the viscosity of described liquid-state epoxy resin during at 25 ℃ 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.
10. the preparation method of carbon fiber/epoxy resin composite material according to claim 7 is characterized in that, described composite material process planning is any one in manual pasting forming process, the molded technology of vacuum bag, the resin transfer molding process planning.
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| CN104419119A (en) * | 2013-09-11 | 2015-03-18 | 奇瑞汽车股份有限公司 | Modified carbon fiber/epoxy resin composite material and preparation method thereof |
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| CN108884211A (en) * | 2016-04-12 | 2018-11-23 | 三菱瓦斯化学株式会社 | Epoxy curing agent, composition epoxy resin, carbon fibre reinforced 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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| CN113105717A (en) * | 2021-04-15 | 2021-07-13 | 江苏威久科技发展有限公司 | High-temperature-resistant carbon fiber composite material and preparation method thereof |
| CN113105717B (en) * | 2021-04-15 | 2023-12-08 | 欧通(山东)纺织有限公司 | High-temperature-resistant carbon fiber composite material and preparation method thereof |
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