CN104130550A - High toughness 70DEG C curable epoxy resin prepreg and preparation method thereof - Google Patents
High toughness 70DEG C curable epoxy resin prepreg and preparation method thereof Download PDFInfo
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- CN104130550A CN104130550A CN201410228267.6A CN201410228267A CN104130550A CN 104130550 A CN104130550 A CN 104130550A CN 201410228267 A CN201410228267 A CN 201410228267A CN 104130550 A CN104130550 A CN 104130550A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 125
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 125
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 55
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 12
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 4
- 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 18
- 239000004593 Epoxy Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 239000012943 hotmelt Substances 0.000 claims description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- -1 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- 239000004697 Polyetherimide Substances 0.000 claims description 4
- 229920002396 Polyurea Polymers 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- 229920001601 polyetherimide Polymers 0.000 claims description 4
- 239000002966 varnish Substances 0.000 claims description 4
- 229920002748 Basalt fiber Polymers 0.000 claims description 3
- 239000004705 High-molecular-weight polyethylene Substances 0.000 claims description 3
- 239000004760 aramid Substances 0.000 claims description 3
- 229920006231 aramid fiber Polymers 0.000 claims description 3
- 150000004982 aromatic amines Chemical class 0.000 claims description 3
- 229920003235 aromatic polyamide Polymers 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 238000009954 braiding Methods 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 150000004693 imidazolium salts Chemical class 0.000 claims description 2
- 229920003986 novolac Polymers 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 239000012783 reinforcing fiber Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 238000004073 vulcanization Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 10
- 238000003860 storage Methods 0.000 abstract description 7
- 230000006835 compression Effects 0.000 abstract description 2
- 238000007906 compression Methods 0.000 abstract description 2
- 238000002791 soaking Methods 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 6
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 230000003116 impacting effect Effects 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000007666 vacuum forming Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- Reinforced Plastic Materials (AREA)
- Epoxy Resins (AREA)
Abstract
Belonging to the technical field of materials, the invention relates to a high toughness 70DEG C curable epoxy resin prepreg and a preparation method thereof. In order to solve the problems of poor toughness, high curing temperature and short room temperature storage period in existing epoxy resin prepregs, the prepreg is prepared from a high toughness 70DEG C curable epoxy resin system soaking reinforced material, wherein the high toughness 70DEG C curable epoxy resin system is prepared from an epoxy resin mixture and a curing agent system mixture. The epoxy resin mixture is formed by copolymerization of epoxy resin, thermoplastic resin and an addition type curing agent, and the curing agent system mixture is formed by mixing of a catalytic curing agent and an accelerant. The preparation method includes: 1. preparation of the high toughness epoxy resin mixture; 2. preparation of the curing agent system mixture; and 3. preparation of the prepreg. A composite material prepared from the prepreg has high toughness and compression strength after impact greater than 220MPa, can realize complete curing at 70DEG C, and has a room temperature storage period over 30 days.
Description
Technical field
The invention belongs to material technology field, relate to a kind of epoxy resin-matrix prepreg and preparation method thereof, relate in particular to a kind of high tenacity, can 70 ℃ of cured epoxy resin prepregs and preparation method thereof.
Background technology
Epoxy resin-matrix prepreg is the important intermediate materials of preparing Aeronautics and Astronautics composite products.Epoxy resin-base composite material toughness is low at present, as how impacts rear compressive strength (CAI) lower than 220MPa, and goods shock resistance is poor by force, cannot meet the demand of current aerospace composite products.When secondly the solidification value of epoxy prepreg is higher than 120 ℃, resulting product can produce larger internal stress, be unfavorable for controlling dimension precision, current epoxy prepreg normal temperature storage phase shorter (being generally less than 7 days) of low-temperature curable, limited the range of application of prepreg.
Summary of the invention
In order to solve existing epoxy prepreg poor toughness, solidification value is high, the normal temperature storage phase is short problem, the invention provides a kind of high tenacity, can 70 ℃ of curing prepregs and preparation method thereof.
The object of the invention is to be achieved through the following technical solutions:
High tenacity, can 70 ℃ of cured epoxy prepregs, by high tenacity, can 70 ℃ of cured epoxy resin systems soak into strongthener and be prepared from; Wherein high tenacity, can 70 ℃ of cured epoxy resin systems be made by 60～95% epoxy resin composition, 5～40% curative systems mixture by massfraction; Described epoxy resin composition is formed by 50～80% epoxy resin, 15～40% thermoplastic resins, 1～5% add-on type solidifying agent copolymerization by massfraction, and epoxy resin is solid-state or semi-solid state epoxy resin or liquid-state epoxy resin; Described curative systems mixture is mixed by 20～60% catalytic curing agent and 40～80% promotor by massfraction.
High tenacity, a preparation method that can 70 ℃ of cured epoxy prepregs, comprise the steps:
One, epoxy resin is heated to 50～140 ℃ in dry container, constant temperature 0.5～2 hour, obtain the epoxy resin of melting, add wherein the thermoplastic resin with reactive group, rotating speed with 1700～3000 turn/min in container stirs, and at 50～140 ℃ constant temperature 0.1～3 hour, then add forming and fixing agent to obtain epoxy prepolymer; By mass percentage, the epoxy resin adding in epoxy resin composition is 50～80%, and the thermoplastic resin adding is 15～45%, and the add-on type solidifying agent adding is 1～5%.
Two, catalytic curing agent is heated to 50～100 ℃ in dry container, constant temperature 5～20 hours, adds promotor wherein, and the rotating speed with 1700～3000 turn/min in container stirs 0.5～2h, obtains curative systems mixture; By mass percentage, the catalytic curing agent adding in this curative systems mixture is 20～60%, and the promotor adding is 40～80%.
Three, the curative systems mixture in the epoxy resin composition in step 1 and step 2 is joined in dry container, mixes, obtain high tenacity, can 70 ℃ of cured epoxy resin systems; By mass percentage, the epoxy resin composition adding in this system is 60～95%, and the curative systems mixture adding is 5～40%.
Four, by the high tenacity obtaining in step 3, can 70 ℃ of cured epoxy resin systems at 50～140 ℃, constant temperature polymerization 10～200 minutes; The epoxy-resin systems of polymerization of take is prepared prepreg by hot melt process as body material and strongthener.
Tool of the present invention has the following advantages: matrix material prepared by this prepreg has higher toughness, its impact after compressive strength can be greater than 220MPa, 70 ℃ can realize completely curing, and the shelf lives under normal temperature be greater than 30 days.The application of this prepreg can reduce the manufacturing cost of composite products, improves product size stability; This prepreg is applicable to autoclave molding, vacuum forming, compression molding and matched-mold forming; Matrix material prepared by this prepreg has excellent mechanical property.The present invention can be used for preparing national defence and the civil areas such as aircraft, spacecraft, yacht, bike.
Embodiment
Below provide the specific embodiment of the present invention and be further described, yet technical solution of the present invention is but not limited to following cited embodiment.Every technical solution of the present invention is modified or is equal to replacement, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
Embodiment one: the high tenacity in present embodiment, can 70 ℃ cured epoxy prepreg by high tenacity, can 70 ℃ of epoxy-resin systems soak into strongthener and be prepared from; Wherein high tenacity, can 70 ℃ of cured epoxy resin systems be made by 60～95% epoxy resin composition, 5～40% curative systems mixture by massfraction; Described epoxy resin composition is formed by 50～80% epoxy resin, 15～40% thermoplastic resins, 1～5% forming and fixing agent copolymerization by massfraction, and epoxy resin is solid-state or semi-solid state epoxy resin or liquid-state epoxy resin; Described curative systems mixture is mixed by 20～60% solidifying agent and 40～80% promotor by massfraction.
The high tenacity of present embodiment design, minimum solidification value that can 70 ℃ of cured epoxy prepregs are 70 ℃, and lower solidification value can reduce the manufacturing cost of composite products, improves product size stability; This prepreg is applicable to autoclave molding, vacuum forming, compression molding and matched-mold forming; Matrix material prepared by this type of prepreg has excellent mechanical property, and this type of prepreg has the storage period that is greater than 30 days at normal temperatures, is conducive to storage, transportation and the production of prepreg.
Embodiment two: the difference of present embodiment and embodiment one is: described epoxy resin is solid-state or semi-solid state epoxy resin or liquid-state epoxy resin, described solid-state or semi-solid state epoxy resin is one or more the combination in bisphenol A type epoxy resin, bisphenol-s epoxy resin and novolac epoxy; Liquid-state epoxy resin is one or more the combination in bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, trifunctional epoxy resin, four-functional group epoxy resin, phenolic resin varnish type epoxy resin and formaldehyde varnish type epoxy resin, and other is identical with embodiment one.
Embodiment three: present embodiment and embodiment one or twos' difference is: described thermoplastic resin be in polyolefine, fluoro-resin, polymeric amide, polyester, polycarbonate, polyether-ether-ketone, polyetherimide, polyethylene terephthalate, polyethersulfone one or more, and in molecular skeleton, contain in hydroxyl, carboxyl, amino, vinyl isoreactivity group one or more.
Embodiment four: the difference of present embodiment and embodiment one to three is: described add-on type solidifying agent is a kind of in arylamine, polyether monoamine, acid anhydrides, a kind of in catalytic curing agent Dyhard RU 100, imidazolium compounds; Described promotor is one or several the combination of polyureas compound, polyether monoamine compound, sulphur and vulcanization accelerator.Other is identical with one of embodiment one to three.
Embodiment five: the difference of present embodiment and embodiment one to four is: described strongthener is one or more the combination in carbon fiber, glass fibre, aramid fiber, aromatic polyamide fibre, high molecular weight polyethylene fiber and basalt fibre.Other is identical with one of embodiment one to four.
Embodiment six: present embodiment provides the preparation method of the prepreg that a kind of intermediate temperature setting epoxy resin is body material, specifically completes according to the following steps:
One, epoxy resin is heated to 50～140 ℃ in dry container, constant temperature 0.5～2 hour, obtain the epoxy resin of melting, add wherein the thermoplastic resin with reactive group, rotating speed with 1700～3000 turn/min in container stirs, and at 50～140 ℃ constant temperature 0.1～3 hour, then add forming and fixing agent to obtain epoxy prepolymer; By mass percentage, the epoxy resin adding in epoxy resin composition is 50～80%, and the thermoplastic resin adding is 15～45%, and the add-on type solidifying agent adding is 1～5%.
Two, catalytic curing agent is heated to 50～100 ℃ in dry container, constant temperature 5～20 hours, adds promotor wherein, and the rotating speed with 1700～3000 turn/min in container stirs 0.5～2h, obtains curative systems mixture; By mass percentage, the catalytic curing agent adding in this curative systems mixture is 20～60%, and the promotor adding is 40～80%.
Three, the curative systems mixture in the epoxy resin composition in step 1 and step 2 is joined in dry container, mixes, obtain high tenacity, can 70 ℃ of cured epoxy resin systems; By mass percentage, the epoxy resin composition adding in this system is 60～95%, and the curative systems mixture adding is 5～40%.
Four, by the high tenacity obtaining in step 3, can 70 ℃ of cured epoxy resin systems at 50～140 ℃, constant temperature polymerization 10～200 minutes; The epoxy-resin systems of polymerization of take is prepared prepreg by hot melt process as body material and strongthener.
Embodiment seven: present embodiment and embodiment six differences are: the hot melt process in described step 4 is prepared prepreg method and is: first under film temperature is the condition of 50～140 ℃, the intermediate temperature setting epoxy resin of polymerization is prepared into glued membrane, then is to carry out hot melt preimpregnation under the condition of 50～140 ℃ in preimpregnation temperature by the glued membrane preparing and strongthener.Other is identical with embodiment six.
Embodiment eight: present embodiment and embodiment six to seven differences are: the strongthener in described step 4 is one or more the combination in carbon fiber, glass fibre, aramid fiber, aromatic polyamide fibre, high molecular weight polyethylene fiber and basalt fibre.Other is identical with one of embodiment six to seven.
Embodiment nine: present embodiment and embodiment six to eight differences are: described strongthener is the fibrous braid obtaining by braiding or the fibrous bundle obtaining by unilateral stretching; Wherein, the mass area ratio of fortifying fibre cloth and the ratio of thickness are 300～1700; The unit of mass area ratio is g/m
2, the unit of thickness is mm; The Tex number of reinforcing fiber bundles is 100～10000.Other is identical with one of embodiment six to eight.
Embodiment ten: present embodiment provides the preparation method of the prepreg that a kind of intermediate temperature setting epoxy resin is body material, specifically completes according to the following steps:
One, bisphenol A type epoxy resin CYD012, trifunctional epoxy resin TDE85 are heated to 120 ℃ in dry container, constant temperature 1 hour, obtain the epoxy resin of melting, add wherein the polyetherimide with hydroxyl, the rotating speed with 2000 turn/min in container stirs, and at 120 ℃ constant temperature 1 hour, then add acid anhydrides HK021, rotating speed with 2000 turn/min in container stirs, and at 120 ℃ constant temperature 0.5 hour, obtain epoxy prepolymer; Wherein by mass percentage, the bisphenol A type epoxy resin YD012 adding in epoxy resin composition is 40%, and the trifunctional epoxy resin TDE85 adding is 20%, and polyetherimide is that 35%, HK021 is 5%;
Two, curing agent dicyandiamide is heated to 70 ℃ in dry container, constant temperature 8 hours, adds promotor passivation imidazoles wherein, carries out stirring 1h with the rotating speed of 2000 turn/min in container, obtains curative systems mixture; By mass percentage, the curing agent dicyandiamide adding in this curative systems mixture is 72.7%; The promotor passivation imidazoles adding is 27.3%;
Three, the curative systems mixture in the epoxy resin composition in step 1 and step 2 is joined in dry container, mixes, obtain high tenacity, can 70 ℃ of cured epoxy resin systems; By mass percentage, the epoxy resin composition adding in said composition is 90%, and the curative systems mixture adding is 10%.
Four, by the intermediate temperature setting epoxy resin obtaining in step 3 at 80 ℃, constant temperature polyase 13 0 minute; The intermediate temperature setting epoxy resin of polymerization of take is prepared prepreg by hot melt process as body material and strongthener; Described strongthener is carbon fiber bundle T700, and tex number is 800, and film temperature is 80 ℃, 100 ℃ of preimpregnation temperature.The processing performance of the prepreg of present embodiment gained is as shown in table 1.
Table 1 prepreg processing performance
| Performance | Feature |
| Viscosity under room temperature | Band toughness, can be bonding between prepreg |
| 70 ℃ of gel times | Be less than 180 minutes |
| The lower shelf lives of normal temperature | 60 days |
By prepreg by autoclave legal system for matrix material, its processing parameter is pressure 0.5MPa, solidification value be elder generation 60 ℃ of constant temperature 2 hours, then 70 ℃ of constant temperature 10 hours, measured composite property was as shown in table 2.
Table 2 composite property
| Performance | Test value |
| Fiber volume fraction | 56％ |
| Voidage | 0.36％ |
| Flexural strength | 1589MPa |
| Modulus in flexure | 130GPa |
| Short beam interlaminar shear strength | 78MPa |
| Compressive strength after impacting | 240MPa |
Embodiment 11: present embodiment provides the preparation method of the prepreg that a kind of intermediate temperature setting epoxy resin is body material, specifically completes according to the following steps:
One, phenol aldehyde type epoxy resin F54, bisphenol A type epoxy resin E51 are heated to 100 ℃ in dry container, constant temperature 2 hours, add wherein the polyethersulfone that contains vinyl, rotating speed with 2000 turn/min in container stirs, and at 110 ℃ constant temperature 2 hours, then add acid anhydrides HK021, the rotating speed with 2000 turn/min in container stirs, and at 110 ℃ constant temperature 1 hour, obtain epoxy prepolymer; Wherein by mass percentage, the phenol aldehyde type epoxy resin F54 adding in epoxy resin composition is 30%, and the bisphenol A type epoxy resin E51 adding is 25%; Polyethersulfone is 40%, and aromatic amine curing agent is 5%;
Two, curing agent dicyandiamide is heated to 80 ℃ in dry container, constant temperature 3 hours, add wherein polyether monoamine solidifying agent D2000 and polyureas vulkacit D yhrad UR500, the rotating speed with 2000 turn/min in container stirs 1h, obtains curative systems mixture; By mass percentage, the curing agent dicyandiamide adding in this curative systems mixture is 46.7%, and the polyether monoamine solidifying agent D2000 adding is 33.3%, and the polyureas vulkacit D yhrad UR500 adding is 20%;
Three, the curative systems mixture in the epoxy resin composition in step 1 and step 2 is joined in dry container, mixes, obtain high tenacity, can 70 ℃ of cured epoxy resin systems; By mass percentage, the epoxy resin composition adding in said composition is 93%, and the curative systems mixture adding is 7%;
Four, by the intermediate temperature setting epoxy resin obtaining in step 3 at 60 ℃, constant temperature polyase 13 0 minute; The intermediate temperature setting epoxy resin of polymerization of take is prepared prepreg by hot melt process as body material and strongthener.Described strongthener is carbon fiber bundle T700, and tex number is 800, and film temperature is 80 ℃, 100 ℃ of preimpregnation temperature.
This prepreg is at normal temperatures during 102 days storage times, its viscosity diminishes.The processing performance of the prepreg of present embodiment gained is as shown in table 3.
Table 3 prepreg processing performance
| Performance | Feature |
| Viscosity under room temperature | Band toughness, can be bonding between prepreg |
| 70 ℃ of gel times | Be less than 50 minutes |
| The lower shelf lives of normal temperature | 102 days |
This prepreg is prepared matrix material with vacuum bag molding, and its processing parameter is pressure 0.08MPa, and solidification value is first 60 ℃ of constant temperature 1 hour, then 90 ℃ of constant temperature 5 hours, measured composite property was as shown in table 4.
Table 4 composite property
| Performance | Test value |
| Fiber volume fraction | 62％ |
| Voidage | 0.46％ |
| Flexural strength | 1643MPa |
| Modulus in flexure | 145GPa |
| 0 ° of compressive strength | 1143MPa |
| 0 ° of modulus of compression | 142GPa |
| Short beam interlaminar shear strength | 68MPa |
| Compressive strength after impacting | 240MPa |
Claims (10)
- High tenacity, can 70 ℃ of cured epoxy resin prepregs, by epoxy-resin systems, soak into strongthener and be prepared from; It is characterized in that described epoxy-resin systems be high tenacity, can 70 ℃ of cured epoxy resin systems, high tenacity, can 70 ℃ of cured epoxy resin systems be made by 60～95% epoxy resin composition, 5～40% curative systems mixture by massfraction; Epoxy resin composition is formed by 50～80% epoxy resin, 15～40% thermoplastic resins, 1～5% add-on type solidifying agent copolymerization by massfraction; Curative systems mixture is mixed by 20～60% catalytic curing agent and 40～80% promotor by massfraction.
- High tenacity according to claim 1, can 70 ℃ of cured epoxy resin prepregs, it is characterized in that described epoxy resin is solid-state or semi-solid state epoxy resin or liquid-state epoxy resin; Described solid-state or semi-solid state epoxy resin is one or more the combination in bisphenol A type epoxy resin, bisphenol-s epoxy resin and novolac epoxy; Described liquid-state epoxy resin is one or more the combination in bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, trifunctional epoxy resin, four-functional group epoxy resin, phenolic resin varnish type epoxy resin and formaldehyde varnish type epoxy resin.
- High tenacity according to claim 1, can 70 ℃ of cured epoxy resin prepregs, it is characterized in that described thermoplastic resin be in polyolefine, fluoro-resin, polymeric amide, polyester, polycarbonate, polyether-ether-ketone, polyetherimide, polyethylene terephthalate, polyethersulfone one or more.
- High tenacity according to claim 1, can 70 ℃ of cured epoxy resin prepregs, it is characterized in that described add-on type solidifying agent is a kind of in arylamine, polyether monoamine, acid anhydrides.
- High tenacity according to claim 1, can 70 ℃ of cured epoxy resin prepregs, it is characterized in that a kind of in described catalytic curing agent Dyhard RU 100, imidazolium compounds.
- High tenacity according to claim 1, can 70 ℃ of cured epoxy resin prepregs, it is characterized in that described promotor is one or several the combination of polyureas compound, polyether monoamine compound, sulphur and vulcanization accelerator.
- High tenacity according to claim 1, can 70 ℃ of cured epoxy resin prepregs, it is characterized in that described strongthener is one or more the combination in carbon fiber, glass fibre, aramid fiber, aromatic polyamide fibre, high molecular weight polyethylene fiber and basalt fibre.
- High tenacity described in the arbitrary claim of claim 1-7, can 70 ℃ of cured epoxy resin prepregs a preparation method, it is characterized in that described method steps is as follows:One, epoxy resin is heated to 50～140 ℃ in dry container, constant temperature 0.5～2 hour, obtain the epoxy resin of melting, add wherein the thermoplastic resin with reactive group, rotating speed with 1700～3000 turn/min in container stirs, and at 50～140 ℃ constant temperature 0.1～3 hour, then add forming and fixing agent to obtain epoxy prepolymer; By mass percentage, the epoxy resin adding in epoxy resin composition is 50～80%, and the thermoplastic resin adding is 15～45%, and the add-on type solidifying agent adding is 1～5%;Two, catalytic curing agent is heated to 50～100 ℃ in dry container, constant temperature 5～20 hours, adds promotor wherein, and the rotating speed with 1700～3000 turn/min in container stirs 0.5～2h, obtains curative systems mixture; By mass percentage, the catalytic curing agent adding in this curative systems mixture is 20～60%, and the promotor adding is 40～80%;Three, the curative systems mixture in the epoxy resin composition in step 1 and step 2 is joined in dry container, mixes, obtain high tenacity, can 70 ℃ of cured epoxy resin systems; By mass percentage, the epoxy resin composition adding in this system is 60～95%, and the curative systems mixture adding is 5～40%;Four, by the high tenacity obtaining in step 3, can 70 ℃ of cured epoxy resin systems at 50～140 ℃, constant temperature polymerization 10～200 minutes; The epoxy-resin systems of polymerization of take is prepared prepreg by hot melt process as body material and strongthener.
- High tenacity according to claim 8, can 70 ℃ of cured epoxy resin prepregs preparation method, it is characterized in that hot melt process in described step 4 prepares prepreg method and be: first under film temperature is the condition of 50～140 ℃, the epoxy-resin systems of polymerization is prepared into glued membrane, then by the glued membrane preparing and strongthener, in preimpregnation temperature, is to carry out hot melt preimpregnation under the condition of 50～140 ℃.
- High tenacity according to claim 8, can 70 ℃ of cured epoxy resin prepregs preparation method, it is characterized in that described strongthener is for the fibrous braid obtaining by braiding or the fibrous bundle obtaining by unilateral stretching; Wherein, the mass area ratio of fortifying fibre cloth and the ratio of thickness are 300～1700; The unit of mass area ratio is g/m 2, the unit of thickness is mm; The Tex number of reinforcing fiber bundles is 100～10000.
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910353A (en) * | 2015-06-03 | 2015-09-16 | 东华大学 | Preparation method of high-temperature-resistant epoxy resin adopting polyborosilazane as curing agent |
| CN105566858A (en) * | 2016-03-14 | 2016-05-11 | 江苏欧亚铂瑞碳复合材料有限公司 | Preparation method of moderate-temperature-curing high-temperature-resistant prepreg by chemorheological regulation |
| CN105885357A (en) * | 2016-06-28 | 2016-08-24 | 周易 | Heterogeneous toughened resin, carbon fiber prepreg and carbon fiber composite material |
| CN106398113A (en) * | 2016-06-17 | 2017-02-15 | 句容市百事特复合材料有限公司 | Bicycle completely prepared from basalt-fiber-reinforced resin-based composite and preparation method thereof |
| CN106496941A (en) * | 2016-11-04 | 2017-03-15 | 江苏澳盛复合材料科技有限公司 | One kind can repairing type carbon cloth reinforced epoxy sheet material and its preparation, restorative procedure |
| CN106832752A (en) * | 2017-01-05 | 2017-06-13 | 厦门复晟复合材料有限公司 | A kind of carbon fiber epoxy prepreg |
| CN107987473A (en) * | 2017-11-15 | 2018-05-04 | 中航复合材料有限责任公司 | A kind of vacuum-bag process epoxy resin for prepreg and preparation method thereof |
| CN108264726A (en) * | 2016-12-30 | 2018-07-10 | 比亚迪股份有限公司 | A kind of epoxy resin composite material and product and preparation method thereof |
| CN108546391A (en) * | 2018-04-24 | 2018-09-18 | 国际竹藤中心 | A kind of thin bamboo strips used for weaving braiding high tenacity prepreg and preparation method thereof |
| CN108795305A (en) * | 2018-05-11 | 2018-11-13 | 黑龙江省科学院石油化学研究院 | A kind of areal density functional material surface glued membrane and preparation method with low-temperature setting |
| CN111187438A (en) * | 2020-02-10 | 2020-05-22 | 北京航空航天大学 | Preparation method of carbon fiber/toughened epoxy resin prepreg for vacuum bag forming process |
| CN112549677A (en) * | 2020-12-17 | 2021-03-26 | 江苏集萃复合材料装备研究所有限公司 | High-peel-strength low-temperature-curable panel-core sandwich structure composite material and preparation method thereof |
| CN113480766A (en) * | 2021-06-17 | 2021-10-08 | 牧世复合材料科技(苏州)有限公司 | Preparation method of rapid curing fiber prepreg with incubation period |
| CN114106515A (en) * | 2021-12-31 | 2022-03-01 | 广联航空工业股份有限公司 | Medium-temperature thermosetting resin mixture with high modulus stability and preparation method thereof |
| CN114478427A (en) * | 2022-02-18 | 2022-05-13 | 四川金象赛瑞化工股份有限公司 | High-performance thermosetting resin curing agent/diluent and preparation method thereof |
| CN114702831A (en) * | 2022-03-23 | 2022-07-05 | 株洲中铁电气物资有限公司 | Modified resin composite material, preparation method thereof and cable support |
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| CN102942765A (en) * | 2012-10-24 | 2013-02-27 | 中国航空工业集团公司北京航空材料研究院 | Method for preparing high toughness epoxy resin matrix by using heat fusion method |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910353A (en) * | 2015-06-03 | 2015-09-16 | 东华大学 | Preparation method of high-temperature-resistant epoxy resin adopting polyborosilazane as curing agent |
| CN104910353B (en) * | 2015-06-03 | 2017-01-11 | 东华大学 | Preparation method of high-temperature-resistant epoxy resin adopting polyborosilazane as curing agent |
| CN105566858A (en) * | 2016-03-14 | 2016-05-11 | 江苏欧亚铂瑞碳复合材料有限公司 | Preparation method of moderate-temperature-curing high-temperature-resistant prepreg by chemorheological regulation |
| CN106398113A (en) * | 2016-06-17 | 2017-02-15 | 句容市百事特复合材料有限公司 | Bicycle completely prepared from basalt-fiber-reinforced resin-based composite and preparation method thereof |
| CN105885357A (en) * | 2016-06-28 | 2016-08-24 | 周易 | Heterogeneous toughened resin, carbon fiber prepreg and carbon fiber composite material |
| CN106496941A (en) * | 2016-11-04 | 2017-03-15 | 江苏澳盛复合材料科技有限公司 | One kind can repairing type carbon cloth reinforced epoxy sheet material and its preparation, restorative procedure |
| CN108264726A (en) * | 2016-12-30 | 2018-07-10 | 比亚迪股份有限公司 | A kind of epoxy resin composite material and product and preparation method thereof |
| CN108264726B (en) * | 2016-12-30 | 2019-11-05 | 比亚迪股份有限公司 | A kind of epoxy resin composite material and product and preparation method thereof |
| CN106832752A (en) * | 2017-01-05 | 2017-06-13 | 厦门复晟复合材料有限公司 | A kind of carbon fiber epoxy prepreg |
| CN107987473A (en) * | 2017-11-15 | 2018-05-04 | 中航复合材料有限责任公司 | A kind of vacuum-bag process epoxy resin for prepreg and preparation method thereof |
| CN107987473B (en) * | 2017-11-15 | 2021-05-07 | 中航复合材料有限责任公司 | Epoxy resin for vacuum bag forming prepreg and preparation method thereof |
| CN108546391A (en) * | 2018-04-24 | 2018-09-18 | 国际竹藤中心 | A kind of thin bamboo strips used for weaving braiding high tenacity prepreg and preparation method thereof |
| CN108795305A (en) * | 2018-05-11 | 2018-11-13 | 黑龙江省科学院石油化学研究院 | A kind of areal density functional material surface glued membrane and preparation method with low-temperature setting |
| CN111187438A (en) * | 2020-02-10 | 2020-05-22 | 北京航空航天大学 | Preparation method of carbon fiber/toughened epoxy resin prepreg for vacuum bag forming process |
| CN112549677A (en) * | 2020-12-17 | 2021-03-26 | 江苏集萃复合材料装备研究所有限公司 | High-peel-strength low-temperature-curable panel-core sandwich structure composite material and preparation method thereof |
| CN113480766A (en) * | 2021-06-17 | 2021-10-08 | 牧世复合材料科技(苏州)有限公司 | Preparation method of rapid curing fiber prepreg with incubation period |
| CN114106515A (en) * | 2021-12-31 | 2022-03-01 | 广联航空工业股份有限公司 | Medium-temperature thermosetting resin mixture with high modulus stability and preparation method thereof |
| CN114478427A (en) * | 2022-02-18 | 2022-05-13 | 四川金象赛瑞化工股份有限公司 | High-performance thermosetting resin curing agent/diluent and preparation method thereof |
| CN114702831A (en) * | 2022-03-23 | 2022-07-05 | 株洲中铁电气物资有限公司 | Modified resin composite material, preparation method thereof and cable support |
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