CN102604045A - Epoxy resin composition and method for preparing glue film, prepreg and composite material by using same - Google Patents
Epoxy resin composition and method for preparing glue film, prepreg and composite material by using same Download PDFInfo
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- CN102604045A CN102604045A CN2012100793413A CN201210079341A CN102604045A CN 102604045 A CN102604045 A CN 102604045A CN 2012100793413 A CN2012100793413 A CN 2012100793413A CN 201210079341 A CN201210079341 A CN 201210079341A CN 102604045 A CN102604045 A CN 102604045A
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Abstract
The invention relates to a resin composition, comprising A, B and C components in parts by mass: 20-80 parts of solid epoxy resin A, 20-80 parts of liquid epoxy resin B and 13-35 parts of aromatic amine solidified agent. The invention also provides a preparation method of glue film composed of the resin composition, a preparation method of a uni-directional carbon fiber reinforced epoxy resin prepreg composed of the resin composition and a preparation method of a uni-directional carbon fiber reinforced epoxy resin composite material composed of the resin composition. The preparation methods of the prepreg and the resin composition of the prepreg refer to a glue film method, and the resin composition refers to epoxy resin and an aromatic amine solidified agent. According to the invention, the uni-directional carbon fiber reinforced epoxy resin composite material with excellent flexural strength and interlayer shearing strength can be prepared.
Description
Technical field
The present invention relates to the preparation method of a kind of thomel epoxy prepreg, its matrix material and prepreg, its raw material glued membrane, its matrix material.
Background technology
Thomel/polymer composites only is applied to high leading-edge fields such as aerospace, defence and military at first; Along with the reduction of the production-scale expansion of thomel, cost and the development of thomel utilisation technology, the carbon fiber reinforced polymer matrix material has also obtained development rapidly in the application of civil area.They are widely used in fields such as aerospace, military project, automotive industry, athletic sports appliance (like bike, racket, fishing rod, ski and sailing boat etc.) and material of construction.
The carbon-fibre reinforced epoxy resin prepreg is the intermediate product of carbon-fibre reinforced epoxy resin composite material; The quality of its performance directly influences the performance of composites quality; Therefore, in the prepreg production process, most important to the research of resin formula and prepreg complete processing.
According to the characteristics and the development trend of carbon-fibre reinforced epoxy resin prepreg, be strongthener with the thomel, adopt glued membrane method (dry method a kind of), exploitation unidirectional carbon fiber dimension reinforced epoxy prepreg.Glued membrane manufactured prepreg does not contain solvent, helps processing the high performance composite of low space content; The thickness of glued membrane is controllable, thereby resin content also can be precisely controlled in the prepreg; Technical indicators such as the gel time that paste that reisn base material is mixed with or glued membrane can be checked them at any time, viscosity, thereby quality that can strict control prepreg.
Unidirectional carbon fiber dimension reinforcing epoxy resin composite material flexural strength is mainly born most of load by fiber, and the interlaminar shear strength of matrix material is mainly determined by the intensity of interfacial adhesion strength between fiber and matrix and matrix.Mainly by resin matrix itself and the decision of matrix material complete processing, therefore, under the situation that resin combination is confirmed, it is most important that the matrix material complete processing just seems for interfacial adhesion strength between matrix and the fiber reinforced material.
In addition, the kind of epoxy curing agent and structure are determining curing action, the intensity of resin system to a great extent.The aliphatic amide of linear chain structure type has soft segment, and the segment conformation is many, gives certain snappiness of epoxy resin cured product and shock strength, but can reduce the cured article flexural strength simultaneously; The aromatic amine solidifying agent has the rigidity benzene ring structure, and the mechanical property of epoxy resin cured product is improved greatly.Therefore, in high-intensity carbon-fibre reinforced epoxy resin composite material, the use of aromatic amine is comparatively more desirable than aliphatic amide.But aromatic amine generally all is an xln, uses operation to go up trouble with aliphatic amide, tends to shorten working life if heat to mix with epoxy resin when using.In the preparation prepreg, the too hard and prepreg embrittlement of resin, resin viscosity is too little to influence the preparation of prepreg and the processing of matrix material again.Therefore, resin combination is very important in states of matter control at each temperature.
Summary of the invention
The technical problem that solves:
For fear of the using and reduce the void content in the matrix material of solvent, the invention provides a kind of solidifying agent is the solid resin combination, utilizes the glued membrane legal system to be equipped with unidirectional carbon fiber dimension reinforced epoxy prepreg.But the glued membrane method requires the resin matrix melt temperature lower, and has lower viscosity after the fusion.
In addition, in order to obtain the matrix material of higher mechanical property, the present invention has proposed a kind of preparation method of unidirectional carbon fiber dimension reinforcing epoxy resin composite material through optimizing the matrix material fabrication process condition.
Technical scheme:
A kind of resin combination that is used to form prepreg, prescription and proportioning are: epoxy resin A, 20～80 mass fractions; Epoxy resin B, 20～80 mass fractions; Aromatic amine curing agent: 13～35 mass fractions.In addition, the prepreg composition also comprises thomel.
Described epoxy resin is: E-55, E-51, E-44, E-42, E-33, E-21, E-20, CYD-011, CYD-012, CYD-014, CYD-128.Aromatic amine is: Ursol D, mphenylenediamine, 4,4 '-MDA, 4,4 '-diamino diphenyl sulfone.
Described thomel is a kind of among general thomel: T300, T400H, T700, T800, IM6, IM7, the IM8, and every bundle thomel is 3K, 6K or 12K.
A kind of preparation method of glued membrane of above-mentioned resin combination, the preparation method is following:
A, take by weighing liquid epoxies, solid epoxy, solidifying agent aromatic amine by aforementioned mass ratio; Earlier partially liq epoxy resin and solidifying agent are placed and be warming up to 100～180 ℃ under vessel in heating, the agitation condition; Stir, and be quickly cooled to below 70 ℃;
B, more remaining epoxy resin is joined in the said mixture, under 90 ℃ of conditions, stir, and deaeration in vacuum drying oven;
C, uniform mixture among the above-mentioned b being poured on the release paper, is on 60～90 ℃ the platform in temperature, adopt the knifing legal system be equipped with thickness evenly, smooth surface, tack-free, sticking paper and the random glued membrane of bending.
The thickness of glued membrane changes according to the gel content in the prepreg among the above-mentioned c, and resin matrix (glued membrane) melt temperature is lower, and has lower viscosity after the fusion.
A kind of preparation of above-mentioned unidirectional carbon fiber dimension reinforced epoxy prepreg, its preparation method is following:
A, let resin glued membrane and thomel meet, and be entrenched togather, wherein, the mass fraction of composition epoxy resin glued membrane is: 30～50 parts is 100 parts of calculating with the total mass umber of prepreg;
B, with the block polymer of above-mentioned resin glued membrane and thomel through the hot pressing roller, resin combination and thomel are evenly inlayed, the prepreg thickness of preparation is 0.17～0.18mm;
Prepreg among above-mentioned b volatilization content≤1% and is being put into prepreg～18 ℃ environment preservation down under the sealed state.
A kind of preparation of unidirectional carbon fiber dimension reinforcing epoxy resin composite material, its preparation method is following:
A, qualified prepreg is taken out in room temperature held 2h under-18 ℃ environment, prepreg is carried out cutting according to the physical size of mould and prepreg;
B, above-mentioned prepreg is laid in the mould that scribbles releasing agent, wrong if any the shop, can prepreg be taken off heavily and spread, adopt 0 °, 16 layers shop layer of prepreg, compression molding prepares carbon-fibre reinforced epoxy resin composite material on platen-press.
The pressing process of matrix material is 140 ℃/2h+160 ℃/2h+180 ℃/2h among c, the above-mentioned b, and forming pressure is 0～0.8MPa.
0 ° of flexural strength of the matrix material among the above-mentioned b can reach 1478MPa, and interlaminar shear strength can reach 82MPa.
In order to overcome technologic difficulty, adopted elder generation with the solidifying agent heating and melting among the present invention, add a spot of liquid epoxies addition then, obtain the low curing agent modified thing of molecule, and then cooperate with the epoxy resin of specified amount.Like this, both make things convenient for technological operation, guaranteed the stable of performance again.
The various starting material that adopt of the present invention, chemical reagent all can be bought from commercial sources and obtain.
Because the utilization of technique scheme, the present invention has following advantage: the solidifying agent among (1) the present invention is an aromatic amine, and is higher with the temperature that epoxy reaction needs, longer by the prepreg life-span of its preparation; (2) the aromatic amine solidifying agent has the rigidity benzene ring structure; The mechanical property that makes epoxy resin cured product and unidirectional carbon fiber tie up reinforcing epoxy resin composite material increases, and (0 ° of flexural strength of its matrix material can reach 1478MPa; Interlaminar shear strength can reach 82MPa; And when changing solidifying agent into traditional methyl carbic anhydride, flexural strength is 1025MPa, and interlaminar shear strength is 70MPa); (3) use glued membrane method (dry method is a kind of) preparation unidirectional carbon fiber dimension reinforced epoxy prepreg among the present invention; Do not contain solvent in the glued membrane; Negative impacts such as production cost height that solvent brings, contaminate environment have been avoided; Can not help processing the high performance composite of low space content simultaneously with in the fugitive constituent introducing system; (4) through optimizing unidirectional carbon fiber dimension reinforcing epoxy resin composite material complete processing, can make the matrix material that has improved mechanical property, the interlaminar shear strength of matrix material especially can be significantly; (5) preparation method of the present invention, technology is simple, feasible, is easy to promote.
Embodiment:
Through following preferred embodiment the present invention is done further description at present, but be not to limit the invention.
Embodiment 1
Take by weighing liquid epoxies B (E-51) and solidifying agent aromatic amine C (4 at 1: 1 by mass ratio; 4 '-diamino diphenyl sulfone); With its mixture in 100～180 ℃ oil bath stir about 4～5min to uniform state; It is cooled fast to 70 ℃, in mixed solution, adds remaining epoxy resin B and epoxy resin A (CYD-011) again, at 80 ℃ of stirring in water bath 30～60min; To mix glue and put into vacuum drying oven again and be-0.1MPa held 10min, so that the sloughing of bubble at 80 ℃, vacuum tightness.Above-mentioned even glue is poured on the release paper; Be on 60～90 ℃ the platform in temperature; Adopt the knifing legal system be equipped with thickness evenly, smooth surface, tack-free, sticking paper and the random glued membrane of bending; The control film thickness, the preparation gel content is the prepreg (is 100 parts with the prepreg mass fraction) of 30 (± 2) part.Let the carbon fiber bundle and the resin glued membrane that are arranged in parallel on the preimpregnation machine, meet, in the fibrous bundle embedded resin film, after compressing, cooling off prepreg.Be laid on compression moulding on platen-press in the mould that scribbles releasing agent to prepreg on request.The composite material preparation process condition is: 140 ℃/2h+160 ℃/2h+180 ℃/2h, forming pressure is 0.4MPa, pressurizes during t=0.Obtain the flexural strength 1413MPa of unidirectional shop layer matrix material, interlaminar shear strength is 58MPa.
Embodiment 2
Take by weighing liquid epoxies B (E-51) and solidifying agent aromatic amine C (4 at 1: 1 by mass ratio; 4 '-diamino diphenyl sulfone); With its mixture in 100～180 ℃ oil bath stir about 4～5min to uniform state; It is cooled fast to 70 ℃, in mixed solution, adds remaining epoxy resin B and epoxy resin A (CYD-011) again, at 80 ℃ of stirring in water bath 30～60min; To mix glue and put into vacuum drying oven again and be-0.1MPa held 10min, so that the sloughing of bubble at 80 ℃, vacuum tightness.Above-mentioned even glue is poured on the release paper; Be on 60～90 ℃ the platform in temperature; Adopt the knifing legal system be equipped with thickness evenly, smooth surface, tack-free, sticking paper and the random glued membrane of bending; The control film thickness, the preparation gel content is the prepreg (mass fraction with prepreg is 100 parts) of 40 (± 2) part.Let the carbon fiber bundle and the resin glued membrane that are arranged in parallel on the preimpregnation machine, meet, in the fibrous bundle embedded resin film, after compressing, cooling off prepreg.Be laid on compression moulding on platen-press in the mould that scribbles releasing agent to prepreg on request.The composite material preparation process condition is: 140 ℃/2h+160 ℃/2h+180 ℃/2h, forming pressure is 0.4MPa, pressurizes during t=0.Obtain the flexural strength 1355MPa of unidirectional shop layer matrix material, interlaminar shear strength is 70MPa.With gel content is that 30 parts of unidirectional carbon fiber dimension reinforcing epoxy resin composite material are compared, and the flexural strength of the matrix material of present embodiment has descended 4.10%, and interlaminar shear strength has improved 20.69%.
Embodiment 3
Take by weighing liquid epoxies B (E-51) and solidifying agent aromatic amine C (4 at 1: 1 by mass ratio; 4 '-diamino diphenyl sulfone); With its mixture in 100～180 ℃ oil bath stir about 4～5min to uniform state; It is cooled fast to 70 ℃, in mixed solution, adds remaining epoxy resin B and epoxy resin A (CYD-011) again, at 80 ℃ of stirring in water bath 30～60min; To mix glue and put into vacuum drying oven again and be-0.1MPa held 10min, so that the sloughing of bubble at 80 ℃, vacuum tightness.Above-mentioned even glue is poured on the release paper; Be on 60～90 ℃ the platform in temperature; Adopt the knifing legal system be equipped with thickness evenly, smooth surface, tack-free, sticking paper and the random glued membrane of bending; The control film thickness, the preparation gel content is the prepreg (mass fraction with prepreg is 100 parts) of 50 (± 2) part.Let the carbon fiber bundle and the resin glued membrane that are arranged in parallel on the preimpregnation machine, meet, in the fibrous bundle embedded resin film, after compressing, cooling off prepreg.Be laid on compression moulding on platen-press in the mould that scribbles releasing agent to prepreg on request.The composite material preparation process condition is: 140 ℃/2h+160 ℃/2h+180 ℃/2h, forming pressure is 0.4MPa, pressurizes during t=0.Obtain the flexural strength 1053MPa of unidirectional shop layer matrix material, interlaminar shear strength is 75MPa.With gel content is that 30 parts of unidirectional carbon fiber dimension reinforcing epoxy resin composite material are compared, and the flexural strength of the matrix material of present embodiment has descended 25.48%, and interlaminar shear strength has improved 29.31%.
Embodiment 4
Take by weighing liquid epoxies B (E-51) and solidifying agent aromatic amine C (4 at 1: 1 by mass ratio; 4 '-diamino diphenyl sulfone); With its mixture in 100～180 ℃ oil bath stir about 4～5min to uniform state; It is cooled fast to 70 ℃, in mixed solution, adds remaining epoxy resin B and epoxy resin A (CYD-011) again, at 80 ℃ of stirring in water bath 30～60min; To mix glue and put into vacuum drying oven again and be-0.1MPa held 10min, so that the sloughing of bubble at 80 ℃, vacuum tightness.Above-mentioned even glue is poured on the release paper; Be on 60～90 ℃ the platform in temperature; Adopt the knifing legal system be equipped with thickness evenly, smooth surface, tack-free, sticking paper and the random glued membrane of bending; The control film thickness, the preparation gel content is the prepreg (mass fraction with prepreg is 100 parts) of 40 (± 2) part.Let the carbon fiber bundle and the resin glued membrane that are arranged in parallel on the preimpregnation machine, meet, in the fibrous bundle embedded resin film, after compressing, cooling off prepreg.Be laid on compression moulding on platen-press in the mould that scribbles releasing agent to prepreg on request.The composite material preparation process condition is: 140 ℃/2h+160 ℃/2h+180 ℃/2h, forming pressure is 0MPa, pressurizes during t=0.Obtain the flexural strength 1107MPa of unidirectional shop layer matrix material, interlaminar shear strength is 43MPa.With identical gel content, forming pressure is that the unidirectional carbon fiber dimension reinforcing epoxy resin composite material (being embodiment 2) of 0.4MPa is compared, and the flexural strength of the matrix material of present embodiment has descended 18.30%, and interlaminar shear strength has descended 38.57%.
Embodiment 5
Take by weighing liquid epoxies B (E-51) and solidifying agent aromatic amine C (4 at 1: 1 by mass ratio; 4 '-diamino diphenyl sulfone); With its mixture in 100～180 ℃ oil bath stir about 4～5min to uniform state; It is cooled fast to 70 ℃, in mixed solution, adds remaining epoxy resin B and epoxy resin A (CYD-011) again, at 80 ℃ of stirring in water bath 30～60min; To mix glue and put into vacuum drying oven again and be-0.1MPa held 10min, so that the sloughing of bubble at 80 ℃, vacuum tightness.Above-mentioned even glue is poured on the release paper; Be on 60～90 ℃ the platform in temperature; Adopt the knifing legal system be equipped with thickness evenly, smooth surface, tack-free, sticking paper and the random glued membrane of bending; The control film thickness, the preparation gel content is the prepreg (mass fraction with prepreg is 100 parts) of 40 (± 2) part.Let the carbon fiber bundle and the resin glued membrane that are arranged in parallel on the preimpregnation machine, meet, in the fibrous bundle embedded resin film, after compressing, cooling off prepreg.Be laid on compression moulding on platen-press in the mould that scribbles releasing agent to prepreg on request.The composite material preparation process condition is: 140 ℃/2h+160 ℃/2h+180 ℃/2h, forming pressure is 0.2MPa, pressurizes during t=0.Obtain the flexural strength 1245MPa of unidirectional shop layer matrix material, interlaminar shear strength is 65MPa.With identical gel content, forming pressure is that the unidirectional carbon fiber dimension reinforcing epoxy resin composite material (being embodiment 2) of 0.4MPa is compared, and the flexural strength of the matrix material of present embodiment has descended 8.12%, and interlaminar shear strength has descended 7.14%.
Embodiment 6
Take by weighing liquid epoxies B (E-51) and solidifying agent aromatic amine C (4 at 1: 1 by mass ratio; 4 '-diamino diphenyl sulfone); With its mixture in 100～180 ℃ oil bath stir about 4～5min to uniform state; It is cooled fast to 70 ℃, in mixed solution, adds remaining epoxy resin B and epoxy resin A (CYD-011) again, at 80 ℃ of stirring in water bath 30～60min; To mix glue and put into vacuum drying oven again and be-0.1MPa held 10min, so that the sloughing of bubble at 80 ℃, vacuum tightness.Above-mentioned even glue is poured on the release paper; Be on 60～90 ℃ the platform in temperature; Adopt the knifing legal system be equipped with thickness evenly, smooth surface, tack-free, sticking paper and the random glued membrane of bending; The control film thickness, the preparation gel content is the prepreg (mass fraction with prepreg is 100 parts) of 40 (± 2) %.Let the carbon fiber bundle and the resin glued membrane that are arranged in parallel on the preimpregnation machine, meet, in the fibrous bundle embedded resin film, after compressing, cooling off prepreg.Be laid on compression moulding on platen-press in the mould that scribbles releasing agent to prepreg on request.The composite material preparation process condition is: 140 ℃/2h+160 ℃/2h+180 ℃/2h, forming pressure is 0.6MPa, pressurizes during t=0.Obtain the flexural strength 1379MPa of unidirectional shop layer matrix material, interlaminar shear strength is 69MPa.With identical gel content, forming pressure is that the unidirectional carbon fiber dimension reinforcing epoxy resin composite material (being embodiment 2) of 0.4MPa is compared; The flexural strength of the matrix material of present embodiment has improved 1.78%; Interlaminar shear strength has descended 1.43%; Explained when moulding pressure be 0.4 when the 0.6MPa, composite materials property is more or less the same.
Embodiment 7
Take by weighing liquid epoxies B (E-51) and solidifying agent aromatic amine C (4 at 1: 1 by mass ratio; 4 '-diamino diphenyl sulfone); With its mixture in 100～180 ℃ oil bath stir about 4～5min to uniform state; It is cooled fast to 70 ℃, in mixed solution, adds remaining epoxy resin B and epoxy resin A (CYD-011) again, at 80 ℃ of stirring in water bath 30～60min; To mix glue and put into vacuum drying oven again and be-0.1MPa held 10min, so that the sloughing of bubble at 80 ℃, vacuum tightness.Above-mentioned even glue is poured on the release paper; Be on 60～90 ℃ the platform in temperature; Adopt the knifing legal system be equipped with thickness evenly, smooth surface, tack-free, sticking paper and the random glued membrane of bending; The control film thickness, the preparation gel content is the prepreg (mass fraction with prepreg is 100 parts) of 40 (± 2) %.Let the carbon fiber bundle and the resin glued membrane that are arranged in parallel on the preimpregnation machine, meet, in the fibrous bundle embedded resin film, after compressing, cooling off prepreg.Be laid on compression moulding on platen-press in the mould that scribbles releasing agent to prepreg on request.The composite material preparation process condition is: 140 ℃/2h+160 ℃/2h+180 ℃/2h, forming pressure is 0.8MPa, pressurizes during t=0.Obtain the flexural strength 1491MPa of unidirectional shop layer matrix material, interlaminar shear strength is 61MPa.With identical gel content, forming pressure is that the unidirectional carbon fiber dimension reinforcing epoxy resin composite material (being embodiment 2) of 0.4MPa is compared, and the flexural strength of the matrix material of present embodiment has improved 10.04%, and interlaminar shear strength has descended 12.86%.
Embodiment 8
Take by weighing liquid epoxies B (E-51) and solidifying agent aromatic amine C (4 at 1: 1 by mass ratio; 4 '-diamino diphenyl sulfone); With its mixture in 100～180 ℃ oil bath stir about 4～5min to uniform state; It is cooled fast to 70 ℃, in mixed solution, adds remaining epoxy resin B and epoxy resin A (CYD-011) again, at 80 ℃ of stirring in water bath 30～60min; To mix glue and put into vacuum drying oven again and be-0.1MPa held 10min, so that the sloughing of bubble at 80 ℃, vacuum tightness.Above-mentioned even glue is poured on the release paper; Be on 60～90 ℃ the platform in temperature; Adopt the knifing legal system be equipped with thickness evenly, smooth surface, tack-free, sticking paper and the random glued membrane of bending; The control film thickness, the preparation gel content is the prepreg (mass fraction with prepreg is 100 parts) of 40 (± 2) %.Let the carbon fiber bundle and the resin glued membrane that are arranged in parallel on the preimpregnation machine, meet, in the fibrous bundle embedded resin film, after compressing, cooling off prepreg.Be laid on compression moulding on platen-press in the mould that scribbles releasing agent to prepreg on request.The composite material preparation process condition is: 140 ℃/2h+160 ℃/2h+180 ℃/2h, forming pressure is 0.4MPa, t=1h when pressurization constantly is 140 ℃.Obtain the flexural strength 1478MPa of unidirectional shop layer matrix material, interlaminar shear strength is 82MPa.With identical gel content, forming pressure is that the unidirectional carbon fiber dimension reinforcing epoxy resin composite material (being embodiment 2) of 0.4MPa is compared; The matrix material of present embodiment prepares in the process in compression moulding; When 140 ℃ of 1h, pressurize; The flexural strength of the matrix material that obtains has improved 9.08%, and interlaminar shear strength has improved 17.14%.
Embodiment 9
Take by weighing liquid epoxies B (E-51) and solidifying agent aromatic amine C (4 at 1: 1 by mass ratio; 4 '-diamino diphenyl sulfone); With its mixture in 100～180 ℃ oil bath stir about 4～5min to uniform state; It is cooled fast to 70 ℃, in mixed solution, adds remaining epoxy resin B and epoxy resin A (CYD-011) again, at 80 ℃ of stirring in water bath 30～60min; To mix glue and put into vacuum drying oven again and be-0.1MPa held 10min, so that the sloughing of bubble at 80 ℃, vacuum tightness.Above-mentioned even glue is poured on the release paper; Be on 60～90 ℃ the platform in temperature; Adopt the knifing legal system be equipped with thickness evenly, smooth surface, tack-free, sticking paper and the random glued membrane of bending; The control film thickness, the preparation gel content is the prepreg (mass fraction with prepreg is 100 parts) of 40 (± 2) %.Let the carbon fiber bundle and the resin glued membrane that are arranged in parallel on the preimpregnation machine, meet, in the fibrous bundle embedded resin film, after compressing, cooling off prepreg.Be laid on compression moulding on platen-press in the mould that scribbles releasing agent to prepreg on request.The composite material preparation process condition is: 140 ℃/2h+160 ℃/2h+180 ℃/2h, forming pressure is 0.4MPa, t=2h when pressurization constantly is 140 ℃.Obtain the flexural strength 1393MPa of unidirectional shop layer matrix material, interlaminar shear strength is 76MPa.With identical gel content, forming pressure is that the unidirectional carbon fiber dimension reinforcing epoxy resin composite material (being embodiment 2) of 0.4MPa is compared; The matrix material of present embodiment prepares in the process in compression moulding; When 140 ℃ of pressurization 2h; The flexural strength of the matrix material that obtains has improved 2.80%, and interlaminar shear strength has improved 8.57%.
Prepreg gel content among previous embodiment 1～embodiment 9 is by the thickness decision of glued membrane; The gel content fluctuation is ± 2% (mass fraction); The thickness of prepreg is 0.17～0.18mm, and volatile content≤1%, the prepreg of preparation are put under sealed state under-18 ℃ the environment and preserved.
Being merely the preferred embodiment of invention in sum, is not to be used for limiting practical range of the present invention.Be that all equivalences of doing according to the content of claim of the present invention change and modification, all should be technological category of the present invention.
Claims (9)
1. a resin combination is characterized in that, comprises A composition, B composition and C composition, wherein:
A composition: solid epoxy;
B composition: liquid epoxies;
C composition: aromatic amine curing agent;
The mass fraction of said epoxy resin composition A is 20～80 parts, and the mass fraction of epoxy resin composition B is 20～80 parts, and the mass fraction of solidifying agent aromatic amine is 13～35 parts.
2. resin combination according to claim 1; It is characterized in that; Said is a kind of among liquid epoxies E-55, E-51, E-44, E-42, E-33, E-21 or the E-20, and solid epoxy is a kind of among CYD-011, CYD-012, CYD-014 or the CYD-128.
3. resin combination according to claim 1 is characterized in that, said aromatic amine is Ursol D, mphenylenediamine, 4,4 '-MDA, 4, a kind of in 4 '-diamino diphenyl sulfone.
4. form the preparation method of glued membrane by each described resin combination of claim 1～3 for one kind, it is characterized in that, said method comprising the steps of:
Step 1:, under 70～180 ℃, mix even back to be mixed and deaeration under 80 ℃ of vacuum states with epoxy resin and solidifying agent aromatic amine;
Step 2: on separate-type paper, 60～90 ℃ the resin combination glues that mix are utilized the glued membrane that the knifing method is prepared into to be needed.
5. the preparation method of glued membrane according to claim 4 is characterized in that, said step 1 further is:
Step 1.1: partially liq epoxy resin and aromatic amine curing agent are placed be warming up to 100～180 ℃ under vessel in heating, the agitation condition earlier, stir, and be quickly cooled to below 70 ℃;
Step 1.2: more remaining epoxy resin is joined in the said mixture, under 90 ℃ of conditions, stir, and deaeration in 80 ℃ of vacuum drying ovens.
6. a use is characterized in that according to the method for each preparing method's gained Resin adhesive membrane prepare prepreg of claim 4 to 5 its method may further comprise the steps:
Step 1: carbon fiber bundle meets with the composition epoxy resin glued membrane for preparing according to each said method of claim 5～6, is entrenched togather;
Wherein, the mass fraction of composition epoxy resin glued membrane is: 30～50 parts is 100 parts of calculating with the total mass umber of prepreg;
Step 2: through the hot pressing roller, resin combination and thomel are evenly inlayed the block polymer of above-mentioned resin glued membrane and thomel.
7. the method for preparing prepreg according to claim 6 is characterized in that, said thomel is a kind of among general purpose grade thomel T300, T400H, T700, T800, IM6, IM7 or the IM8, and every bundle thomel is 3K, 6K or 12K.
8. the method for preparing prepreg according to claim 6 is characterized in that, prepreg in the said method steps 2 volatilization content≤1%, and also be included in step 2 accomplish after with prepreg in the environment preservation down of putting into-18 ℃ under the sealed state.
9. a use is according to the method for each preparing method's gained equipment of preimpregnated material manufacture unidirectional carbon fiber dimension reinforcing epoxy resin composite material of claim 6 to 8; It is characterized in that, said method comprising the steps of: adopt each described prepreg of claim 6 to 8 to carry out cutting, the shop layer is in mould; Mold pressing is prepared into unidirectional composite material; The processing condition of said mold pressing are 140 ℃/2h+160 ℃/2h+180 ℃/2h, and forming pressure is 0～0.8MPa, and pressurization is t=0～2h constantly.
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103540233A (en) * | 2013-09-27 | 2014-01-29 | 东莞市大兴化工有限公司 | Nano electronic coating as well as preparation method thereof |
| CN103665769A (en) * | 2013-11-26 | 2014-03-26 | 上海复合材料科技有限公司 | Method for preparing nanometer-micrometer multi-scale fiber prepreg |
| CN104371125A (en) * | 2014-11-07 | 2015-02-25 | 安徽威尔玛渔具科技有限公司 | Manufacturing method of insulating light-weight high-property fishing rod |
| CN104448242A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Epoxy resin composition |
| CN104610529A (en) * | 2015-02-04 | 2015-05-13 | 广东博汇新材料科技有限公司 | Epoxy resin composition, preparation method of epoxy resin composition and composite material for wind power blade |
| CN104861422A (en) * | 2015-05-20 | 2015-08-26 | 叶芳 | Novel epoxy resin laminated composite for snowboard and preparation method of novel epoxy resin laminated composite |
| CN105061992A (en) * | 2015-07-17 | 2015-11-18 | 河南科技大学 | Fishing rod capable of preventing coating peeling and preparation method of fishing rod |
| CN105348732A (en) * | 2015-09-15 | 2016-02-24 | 广东生益科技股份有限公司 | Circuit substrate and preparation method therefor |
| CN105733193A (en) * | 2016-03-23 | 2016-07-06 | 航天材料及工艺研究所 | Preparation method of epoxy resin based composite material with controllable toughness |
| CN105885351A (en) * | 2016-05-20 | 2016-08-24 | 江苏兆鋆新材料股份有限公司 | Preparation method of low-gummosis carbon fiber prepreg |
| CN106397811A (en) * | 2016-09-06 | 2017-02-15 | 吉林大学 | Carbon fiber composite material hand brake pulling cable 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 |
| CN106985306A (en) * | 2017-03-24 | 2017-07-28 | 武汉纺织大学 | A kind of preparation method of carbon fiber phenolic resin preimpregnation material |
| CN108544608A (en) * | 2018-04-23 | 2018-09-18 | 浙江省林业科学研究院 | A kind of preparation method of bamboo beam thin bamboo strips used for weaving shuffling prepreg and its laminate |
| CN111203005A (en) * | 2020-01-15 | 2020-05-29 | 长江大学 | Oil-containing wastewater demulsifier and preparation method and application thereof |
| CN112629324A (en) * | 2020-11-12 | 2021-04-09 | 湖南欧亚碳纤维复合材料有限公司 | Carbon fiber composite bulletproof plate and preparation process thereof |
| CN115027073A (en) * | 2022-04-20 | 2022-09-09 | 佛山铂瑞天辰医疗器械科技有限公司 | Fiber reinforced resin composite material capable of being digitally cut and preparation method and application thereof |
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| CN104448242A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Epoxy resin composition |
| CN103540233B (en) * | 2013-09-27 | 2016-04-13 | 东莞市大兴化工有限公司 | A kind of nanoelectronic coating and preparation method thereof |
| CN103540233A (en) * | 2013-09-27 | 2014-01-29 | 东莞市大兴化工有限公司 | Nano electronic coating as well as preparation method thereof |
| CN103665769A (en) * | 2013-11-26 | 2014-03-26 | 上海复合材料科技有限公司 | Method for preparing nanometer-micrometer multi-scale fiber prepreg |
| CN104371125A (en) * | 2014-11-07 | 2015-02-25 | 安徽威尔玛渔具科技有限公司 | Manufacturing method of insulating light-weight high-property fishing rod |
| CN104610529A (en) * | 2015-02-04 | 2015-05-13 | 广东博汇新材料科技有限公司 | Epoxy resin composition, preparation method of epoxy resin composition and composite material for wind power blade |
| CN104861422A (en) * | 2015-05-20 | 2015-08-26 | 叶芳 | Novel epoxy resin laminated composite for snowboard and preparation method of novel epoxy resin laminated composite |
| CN105061992B (en) * | 2015-07-17 | 2017-04-12 | 河南科技大学 | Preparation method for fishing rod capable of preventing coating peeling |
| CN105061992A (en) * | 2015-07-17 | 2015-11-18 | 河南科技大学 | Fishing rod capable of preventing coating peeling and preparation method of fishing rod |
| CN105348732A (en) * | 2015-09-15 | 2016-02-24 | 广东生益科技股份有限公司 | Circuit substrate and preparation method therefor |
| CN105733193A (en) * | 2016-03-23 | 2016-07-06 | 航天材料及工艺研究所 | Preparation method of epoxy resin based composite material with controllable toughness |
| CN105885351A (en) * | 2016-05-20 | 2016-08-24 | 江苏兆鋆新材料股份有限公司 | Preparation method of low-gummosis carbon fiber prepreg |
| CN106397811A (en) * | 2016-09-06 | 2017-02-15 | 吉林大学 | Carbon fiber composite material hand brake pulling cable and preparation method thereof |
| CN106397811B (en) * | 2016-09-06 | 2018-11-16 | 吉林大学 | A kind of carbon fibre composite hand brake stay cable 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 |
| CN106985306A (en) * | 2017-03-24 | 2017-07-28 | 武汉纺织大学 | A kind of preparation method of carbon fiber phenolic resin preimpregnation material |
| CN108544608A (en) * | 2018-04-23 | 2018-09-18 | 浙江省林业科学研究院 | A kind of preparation method of bamboo beam thin bamboo strips used for weaving shuffling prepreg and its laminate |
| CN108544608B (en) * | 2018-04-23 | 2023-07-04 | 浙江省林业科学研究院 | Preparation method of bamboo bundle and thin bamboo strip mixed woven prepreg and laminated board thereof |
| CN111203005A (en) * | 2020-01-15 | 2020-05-29 | 长江大学 | Oil-containing wastewater demulsifier and preparation method and application thereof |
| CN112629324A (en) * | 2020-11-12 | 2021-04-09 | 湖南欧亚碳纤维复合材料有限公司 | Carbon fiber composite bulletproof plate and preparation process thereof |
| CN115027073A (en) * | 2022-04-20 | 2022-09-09 | 佛山铂瑞天辰医疗器械科技有限公司 | Fiber reinforced resin composite material capable of being digitally cut and preparation method and application thereof |
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