CN102532484A - Epoxy resin composition and method for preparing prepreg and composite material by using same - Google Patents
Epoxy resin composition and method for preparing prepreg and composite material by using same Download PDFInfo
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Abstract
The invention relates to a composition, in particular to an epoxy resin composition and a method for preparing prepreg and a composite material by using the epoxy resin composition. The composition comprises 33-35 mass parts of liquid bisphenol A epoxy resin, 65-67 mass parts of solid bisphenol A epoxy resin, 46-51 mass parts of anhydride curing agent, 1-2.5 mass parts of hyamine accelerating agent, and 0.05-1 mass part of acetylacetone metal salt accelerating agent; in addition, the preparation process of forming an epoxy resin coating by the resin formula, the preparation process of forming the prepreg by compositing the epoxy resin coating and a reinforced fiber, and the preparation process of forming the composite material by the prepreg are all adopted. The composite material prepared by the prepreg provided by the invention has excellent mechanical property and heat-resistant quality and has wide application prospect in the entertainment aspects and related sports products.
Description
Technical field
The present invention relates to a kind of compsn, relate in particular to a kind of composition epoxy resin and use the method that it prepares prepreg and matrix material.
Background technology
Because epoxy resin has mechanical property and thermal property preferably, in various fields, have comparatively widely and use.Be that epoxy resin is used as matrix resin more in the field of compound material at center with fibre reinforced plastics particularly, spun glass, thomel, boron fibre etc. are used as fortifying fibre more.
Fiber reinforced plastic composite material since its specific tenacity, corrosion-resistant, weight compare with metallic substance always special good, so especially in the purposes that requires purposes such as light-weighted aircraft and motion goods such as Veronicastrum Herb, golf club, tennis racket by application widely.
Current advanced fiber reinforced plastic composite material product more than 70% changes to solidify with the prepreg shop and forms.Prepreg is the middle base material of preparation matrix material, and its quality directly has influence on the quality of composite element.Prepreg is hot setting (more than 180 ℃) according to different parts of solidification value, intermediate temperature setting (120～180 ℃), low-temperature curing (room temperature～100 ℃).
For the employed epoxy resin of prepreg; Employed heat-resistant resin in the purposes of relevant aircraft for example; The known aromatic polyamine resin combination that polyfunctional epoxy resins such as four Racemic glycidol diamino-YLENE and diamino diphenyl sulfone and so on are arranged; In addition; Be used in the widely used prepreg of the purposes of relevant motion goods, known by the epoxy resin of phenol aldehyde type epoxy resin and bisphenol A type epoxy resin etc. and the resin combination of forming as their curing agent dicyandiamide.The resin that is used for aircraft application needs better heat-resisting property; Its second-order transition temperature requires to reach more than 200 ℃; So the high price polyfunctional epoxy resin as major ingredient; And the prepreg condition of cure that itself and fiber composite prepare reaches 180 ℃～200 ℃/2～4 hours for 180 ℃ of curing two hours, but such moulding process needs high temperature and long-time.And often in matrix material, produce bigger internal stress during the matrix material of hot setting prepreg moulding; Thereby influence dimensional precision, and complex forming technology, it is higher to consume energy; And subsidiary material selection ranges such as preparation core, mould are narrow, finally cause the moulding cost of matrix material expensive.Show that according to related data the manufacturing cost of die material has accounted for more than 60% of matrix material manufacturing cost.Thereby be used in this prepreg that uses in motion and the recreational use, especially and in price, be worthless from production efficiency.
In order to solve the problems referred to above that the hot setting prepreg occurs, people have done many work.Research and development microcapsule solidifying agent technology and latent curing system are the effective ways of contradiction during solution prepreg low-temperature curing and the longer room temperature storage, also are the current main developing direction of low temperature curing agent.For example in USP 5567792 specification sheetss and USP 5859096 specification sheetss, propose to adopt emulsifying technology that solidifying agent is coated the formation microcapsule with thermoplastic resin, this microcapsule median size 5～50 μ m can be in harmonious proportion the glue that comes true with epoxy resin.Isolated solidifying agent contacts with epoxy resin under the room temperature, and when reaching solidification value, the thermoplastic resin film dissolving discharges solidifying agent and epoxy resin cure, can solve room temperature storage phase stability and low-temperature curing simultaneously.But the microcapsule size generally need be under 5 μ m; Under at present difficult this size of preparation microcapsule; Because particle is bigger, can't get between fiber and evenly part loose, can't prepare the high quality prepreg; In view of its productive rate and price, be difficult to be useful on the prepreg as purposes such as relevant leisure, sports goods simultaneously.
In addition, people utilize on the imidazole ring 3 nitrogen-atoms to imidazoles carry out modification in the hope of reach an ability low-temperature curing and when cooperating with epoxy resin storage period long effect.For example 3 nitrogen-atoms alkalescence are stronger, can in organic acid salifies such as isocyanuric acid, trimellitic acid, lactic acid, isocaprylic acid.Acid amount how much determine this solidifying agent the solidification value height and storage period length; This method during to the modified product cured epoxy resin of imidazoles long solidification value of room temperature storage phase low; But this title complex shortcoming is bad with the consistency of epoxy-resin systems; Affect the mechanical properties, simultaneously from product performance and widely-used property, on the also difficult prepreg that is useful in as purposes such as relevant leisure, sports goods.
Summary of the invention
The technical problem that the present invention will solve is the deficiency that overcomes prior art; It is 8 days and can be at the 85 ℃ of composition epoxy resins that can accomplish primary solidification down following storage periods that a kind of room temperature is provided; Also provide a kind of raw material sources extensively, the preparation method of the prepreg of features simple and practical process, with low cost, good product quality, and the preparation method of this prepreg forming composite.
For solving the problems of the technologies described above, the invention provides a kind of liquid epoxy resin composition, the composition epoxy resin that it is made up of following A composition, B composition, C composition, D composition and E composition.
A composition: liquid bisphenol A epoxy resin
B composition: solid-state bisphenol A epoxide resin
C composition: anhydride curing agent
D composition: quaternary ammonium salt promotor
E composition: acetyl acetone salt promotor
To be us analyse the relative merits of the resin molding that a series of prescriptions make comprehensive part to technique scheme, and on the basis of the prepreg room temperature storage phase that makes of binding resin film and fiber composite and solidification value, definite a kind of composition epoxy resin.Said liquid bisphenol A epoxy resin composition A; In whole epoxy-resin systems, to contain 35% mass parts at least; Liquid bisphenol A epoxy resin among the present invention; Do not specify that can use commercially available liquid bisphenol A epoxy resin, adducible especially example has: E-54, E-51 and E-44 epoxy resin; Said solid-state bisphenol A epoxide resin composition B; At least 65% mass parts in whole epoxy-resin systems; Solid-state bisphenol A epoxide resin among the present invention; Do not specify that can use commercially available solid-state bisphenol A epoxide resin, adducible especially example has: CYD-001, CYD-012 or E-31 epoxy resin.
Employed epoxy resin anhydride curing agent C among the present invention; Can not only the short at low temperatures time can accomplish primary solidification epoxy resin; And the prepreg that finally makes has the long room temperature storage phase, and the solvability in common bisphenol A epoxide resin (liquid state and solid mixt) is better with part diffusing property simultaneously.Anhydride curing agent among the present invention does not specify, can use the anhydride curing agent of commercially available usefulness, like methyl tetrahydrophthalic anhydride, dodecenylsuccinic acid acid anhydride or methyl carbic anhydride.The usage quantity of solidifying agent with respect to epoxy resin 100 mass parts, is 48～51 mass parts; If surpass this weight; Unreacted solidifying agent is remained in the resin, thereby influence the performance of epoxy resin cured product, the most important thing is to influence the viscosity under the prepreg room temperature.If be lower than this weight, can make unreacted epoxy resin left behind, the set time of meeting overspending, finally also can influence simultaneously by the prepared performance of composites of prepreg.
Quaternary ammonium salt vulkacit D of the present invention does not specify, can be the commercially available quaternary ammonium salt that often is used as cationic surfactant and phase-transfer catalyst, like benzyltriethylammoinium chloride, diethylammonium ethanol based ammonium chloride and benzyl tributyl ammonium chloride.Generally with respect to the epoxy resin of 100 mass parts, its consumption is 1～2.5 mass parts, if surpass this weight, then can shorten under the prepreg room temperature storage period; If be lower than this weight, then do not play the effect of promotor, make prepreg the at room temperature short time can not accomplish primary solidification.
Chromium acetylacetonate E of the present invention does not specify, can be commercially available acetyl acetone salt, like aluminium acetylacetonate, titanium acetylacetone and chromium acetylacetonate.Generally with respect to the epoxy resin of 100 mass parts, its consumption is 0.05～1 mass parts, if surpass this weight, then can shorten under the prepreg room temperature storage period; If be lower than this weight, then do not play the effect of promotor, make prepreg the at room temperature short time can not accomplish primary solidification.
Long-acting low-temperature curing prepreg of the present invention is immersed in above-mentioned epoxy-resin systems in the fortifying fibre and obtains.For fortifying fibre; Employed any fiber can in the general prepreg; For example: thomel, spun glass, aramid fiber or the like, in addition, do not do special restriction about the shape of fiber yet; Can enumerate, for example can be the band arranged by certain orientation, one-way fabric, drills or the like.
The blending process of low-temperature long acting Cured epoxy resin compositions of the present invention is following: liquid bisphenol A epoxy resin A is heated; Add solid-state bisphenol A epoxide resin B simultaneously; After stirring under 90 ℃, cool the temperature to 70 ℃ then, after adding anhydride curing agent C stirs.Under 70 ℃, add latent quaternary ammonium salt vulkacit D and acetyl acetone salt E, stir once more the blending epoxy glue.
The technology that the above-mentioned epoxy resin adhesive liquid for preparing prepares the epoxy resin glued membrane is: when the epoxy resin glue liquid temp is in 55 ℃～80 ℃; The epoxy resin glue fluid viscosity is between 10～30Pas the time, adopts to scrape embrane method above-mentioned mixed epoxy resin adhesive liquid is coated on the separate-type paper.According to scraper and separate-type paper between the thickness of speed control epoxy resin glued membrane of gap and feed.
On above-mentioned epoxy resin glued membrane, put and draw neat fortifying fibre, the cylinder pressurization with heating makes thermoplastic resin-impregnated fibers.The temperature of heating drum is 65 ℃～70 ℃, is lower than this temperature resin and soaks into not fiber thoroughly, can produce shredded dried bean curd, and surpassing this temperature resin can be extruded by resin.The rotating speed of heating drum is 3～4m/min, can soak into fiber though be lower than this rotating speed resin, influences production efficiency.Surpass this rotating speed, same resin soaks into fiber and fills part inadequately, has shredded dried bean curd and occurs.The hot pressing number of times of cylinder is 12～16 times, is lower than this number of times, and resin soaks into fiber and fills part inadequately.Be higher than this number of times,, can reduce production efficiency though resin can soak into fiber.
Above-mentioned prepreg lamination is laid in the forming mould, and close die heats, pressurization and moulding.Its moulding process is: after 85 ℃ of beginning primary solidification, pressure applying moment were 85 ℃ of curing 30min～45min, pressure was 1MPa.Behind the primary solidification 2h, the temperature of moulding press heated up carry out after fixing, the curing system of after fixing is 120 ℃/2h+140 ℃/2h+180 ℃/2h.
Long-acting temperature curing epoxy low resin of the present invention not only can be accomplished primary solidification in (85 ℃) short period of time at low temperatures, and at room temperature arranged good storage period (8 days).Each component for preparing the employed epoxy-resin systems of this prepreg all adopts marketable material to be mixed and forms, and compatible effective between each component is good to the fibre reinforcement effect of impregnation may.Simultaneously, the fibre reinforced epoxy resin composite by this prepreg moulding has mechanical property and resistance toheat preferably.The application prospects that in recreational use and relevant motion goods, has.
Once the present invention is explained particularly through embodiment and comparative example
Embodiment
Embodiment 1
Solid-state CYD-011 (Ba Ling petro-chemical corporation) epoxy resin of the liquid E-54 epoxy resin (Shanghai Resin Factory) of 33 mass parts and 67 mass parts is heated to 90 ℃ is dissolved into after the uniform mixture; Then this mixture temperature is cooled to 70 ℃; The methyl carbic anhydride (Italian polynt company) that in this mixture, adds 48 mass parts fills after part stirs; Add the benzyl tributyl ammonium chloride promotor (source, Shanghai leaf bio tech ltd) of 2 mass parts and aluminium acetylacetonate (the U.S. Sigma-Aldrich company) promotor of 0.5 mass parts again, mix the composition epoxy resin of modulating embodiment 1.
With synthetic like this composition epoxy resin, when the viscosity of composition epoxy resin is 15Pas, with scraping the skill in using a kitchen knife in cookery epoxy resin adhesive liquid is coated on the separate-type paper down at 60 ℃, the mass area ratio of system is 80g/m
2Resin film.
In addition, on above-mentioned resin film, thomel is drawn neat putting, at first on the prepreg machine, cold pressing 3～4 times, use 70 ℃ heating drum to carry out the dipping of opening fibre, resin of fiber then.The travelling speed of fiber is 4m/min, and the roll-in number of times is 16 times, thereby makes fiber areal densities 108g/m
2, resin content is the carbon fiber/epoxy resin unidirectional pre-immersion material of 35% (mass percent).Resulting carbon fiber/epoxy resin unidirectional pre-immersion material, thomel fill a part infiltration, and have appropriate cohesiveness.Do not stick polyvinylidene film on its surface, room temperature held 8 days is observed the variation of its cementability, thereby confirms that be 8 days the storage period under its room temperature.
Secondly, for making the thick fibre reinforced epoxy resin composite veneer sheet of 2mm,,, put into mould by 16 layers of same direction stacks with the above-mentioned carbon fiber/epoxy resin unidirectional pre-immersion material that makes.At pressure is 0MPa, and temperature is to solidify 30 minutes in 85 ℃ the moulding press, and the pressure with moulding press rises to 1MPa then, continues to solidify 90min minute down at 85 ℃, to accomplish primary solidification.After the primary solidification, again temperature is risen to 120 ℃ of beginning high temperature after fixing, whole rear curing time is 6 hours, and the curing system is 120 ℃ solidified 2 hours down, and 140 ℃ solidify 2h down then, and 180 ℃ solidified 2 hours down then.By the veneer sheet of such moulding, with cutting out 0 ° of test film and interlaminar shear strength test film that the direction pliability test is used of model machine excision.Adopt China Shenzhen CMT5105 electronic universal tester to carry out physicals test separately; The flexural strength test is with reference to GB3356-1999 " the crooked bending property TP of unidirectional fibre reinforced plastics ", and interlaminar shear strength is with reference to JC/T773-96 " unidirectional fibre reinforced plastics interlayer shear strength test method ".Flexural strength is 1056MPa, and modulus in flexure is 118GPa, and interlaminar shear strength is 70MPa.
Embodiment 2
Solid-state CYD-012 (Ba Ling petro-chemical corporation) epoxy resin of liquid E-44 (Shanghai Resin Factory) epoxy resin of 35 mass parts and 65 mass parts is heated to 90 ℃ is dissolved into after the uniform mixture; Then this mixture temperature is cooled to 70 ℃; The methyl carbic anhydride (Italian polynt company) that in this mixture, adds 46 mass parts fills after part stirs; Add the benzyltriethylammoinium chloride promotor (source, Shanghai leaf bio tech ltd) of 1 mass parts and the chromium acetylacetonate promotor (U.S. Sigma-Aldrich company) of 0.5 mass parts again, mix the composition epoxy resin of modulating embodiment 2.
With synthetic like this composition epoxy resin, when the viscosity of composition epoxy resin is 10Pas, with scraping the skill in using a kitchen knife in cookery epoxy resin adhesive liquid is coated on the separate-type paper down at 65 ℃, the mass area ratio of system is 82g/m
2Resin film.
In addition, on above-mentioned resin film, thomel is drawn neat putting, at first on the prepreg machine, cold pressing 3～4 times, use 70 ℃ heating drum to carry out the dipping of opening fibre, resin of fiber then.The travelling speed of fiber is 3m/min, and the roll-in number of times is 14 times, thereby makes fiber areal densities 108g/m
2, resin content is the carbon fiber/epoxy resin unidirectional pre-immersion material of 35% (mass percent).Resulting carbon fiber/epoxy resin unidirectional pre-immersion material, thomel fill a part infiltration, and have appropriate cohesiveness.Do not stick polyvinylidene film on its surface, room temperature held 8 days is observed the variation of its cementability, thereby confirms that be 8 days the storage period under its room temperature.
Secondly, for making the thick fibre reinforced epoxy resin composite veneer sheet of 2mm,,, put into mould by 16 layers of same direction stacks with the above-mentioned carbon fiber/epoxy resin unidirectional pre-immersion material that makes.At pressure is 0MPa, and temperature is to solidify 45 minutes in 85 ℃ the moulding press, and the pressure with moulding press rises to 1MPa then, continues to solidify 75min minute down at 85 ℃, to accomplish primary solidification.After the primary solidification, again temperature is risen to 120 ℃ of beginning high temperature after fixing, whole rear curing time is 6h, and the curing system is 120 ℃ solidified 2 hours down, and 140 ℃ solidify 2h down then, and 180 ℃ solidified 2 hours down then.By the veneer sheet of such moulding, with cutting out 0 ° of test film and interlaminar shear strength test film that the direction pliability test is used of model machine excision.Adopt China Shenzhen CMT5105 electronic universal tester to carry out physicals test separately; The flexural strength test is with reference to GB3356-1999 " the crooked bending property TP of unidirectional fibre reinforced plastics ", and interlaminar shear strength is with reference to JC/T773-96 " unidirectional fibre reinforced plastics interlayer shear strength test method ".Flexural strength is 1036MPa, and modulus in flexure is 110GPa, and interlaminar shear strength is 71MPa.
Embodiment 3
Solid-state CYD-012 (Ba Ling petro-chemical corporation) epoxy resin of liquid E-44 (Shanghai Resin Factory) epoxy resin of 34 mass parts and 66 mass parts is heated to 90 ℃ is dissolved into after the uniform mixture; Then this mixture temperature is cooled to 70 ℃; The methyl carbic anhydride (Italian polynt company) that in this mixture, adds 46 mass parts fills after part stirs; Add the benzyltriethylammoinium chloride promotor (source, Shanghai leaf bio tech ltd) of 2.5 mass parts and the chromium acetylacetonate promotor (U.S. Sigma-Aldrich company) of 0.5 mass parts again, mix the composition epoxy resin of modulating embodiment 2.
With synthetic like this composition epoxy resin, when the viscosity of composition epoxy resin is 12Pas, with scraping the skill in using a kitchen knife in cookery epoxy resin adhesive liquid is coated on the separate-type paper down at 70 ℃, the mass area ratio of system is 84g/m
2Resin film.
In addition, on above-mentioned resin film, thomel is drawn neat putting, at first on the prepreg machine, cold pressing 3～4 times, use 70 ℃ heating drum to carry out the dipping of opening fibre, resin of fiber then.The travelling speed of fiber is 3m/min, and the roll-in number of times is 16 times, thereby makes fiber areal densities 109g/m
2, resin content is the carbon fiber/epoxy resin unidirectional pre-immersion material of 35% (mass percent).Resulting carbon fiber/epoxy resin unidirectional pre-immersion material, thomel fill a part infiltration, and have appropriate cohesiveness.Do not stick polyvinylidene film on its surface, room temperature held 8 days is observed the variation of its cementability, thereby confirms that be 8 days the storage period under its room temperature.
Secondly, for making the thick fibre reinforced epoxy resin composite veneer sheet of 2mm,,, put into mould by 16 layers of same direction stacks with the above-mentioned carbon fiber/epoxy resin unidirectional pre-immersion material that makes.At pressure is 0MPa, and temperature is to solidify 45 minutes in 85 ℃ the moulding press, and the pressure with moulding press rises to 1MPa then, continues to solidify 75min minute down at 85 ℃, to accomplish primary solidification.After the primary solidification, again temperature is risen to 120 ℃ of beginning high temperature after fixing, whole rear curing time is 6h, and the curing system is 120 ℃ solidified 2 hours down, and 140 ℃ solidify 2h down then, and 180 ℃ solidified 2 hours down then.By the veneer sheet of such moulding, with cutting out 0 ° of test film and interlaminar shear strength test film that the direction pliability test is used of model machine excision.Adopt China Shenzhen CMT5105 electronic universal tester to carry out physicals test separately; The flexural strength test is with reference to GB3356-1999 " the crooked bending property TP of unidirectional fibre reinforced plastics ", and interlaminar shear strength is with reference to JC/T773-96 " unidirectional fibre reinforced plastics interlayer shear strength test method ".Flexural strength is 1026MPa, and modulus in flexure is 109GPa, and interlaminar shear strength is 70MPa.
Comparative example 1
Is peer-level for making the prepared glued membrane of resin combination with prepared glued membrane solidification value of the resin combination of embodiment 1 and embodiment 2 and the viscosity storage period under the room temperature; So the usage quantity of (Italian polynt company) respectively is 35 mass parts liquid E-51 epoxy resin (Shanghai Resin Factory), solid-state CYD-011 epoxy resin (Ba Ling petro-chemical corporation) and methyl carbic anhydride; 65 mass parts and 45 mass parts; The usage quantity of benzyltriethylammoinium chloride promotor (source, Shanghai leaf bio tech ltd) and aluminium acetylacetonate (U.S. Sigma-Aldrich company) respectively is 1.5 mass parts and 0.5 mass parts, and according to the composition epoxy resin of the identical process methodes modulation comparative example 1 of embodiment 1 and embodiment 2.
With synthetic like this composition epoxy resin, when the viscosity of composition epoxy resin is 12Pas, with scraping the skill in using a kitchen knife in cookery epoxy resin adhesive liquid is coated on the separate-type paper down at 68 ℃, the mass area ratio of system is 84g/m
2Resin film.
In addition, on above-mentioned resin film, thomel is drawn neat putting, at first on the prepreg machine, cold pressing 3～4 times, use 70 ℃ heating drum to carry out the dipping of opening fibre, resin of fiber then.The travelling speed of fiber is 3m/min, and the roll-in number of times is 14 times, thereby makes fiber areal densities 108g/m
2, resin content is the carbon fiber/epoxy resin unidirectional pre-immersion material of 35% (mass percent).Resulting carbon fiber/epoxy resin unidirectional pre-immersion material, thomel fill a part infiltration, and have appropriate cohesiveness.Do not stick polyvinylidene film on its surface, room temperature held 8 days is observed the variation of its cementability, thereby confirms that be 8 days the viscosity storage period under its room temperature.
Secondly, for making the thick fibre reinforced epoxy resin composite veneer sheet of 2mm,,, put into mould by 16 layers of same direction stacks with the above-mentioned carbon fiber/epoxy resin unidirectional pre-immersion material that makes.At pressure is 0MPa, and temperature is to solidify 2h in 85 ℃ the moulding press, to accomplish primary solidification.After the primary solidification, the pressure with moulding press rises to 1MPa earlier, again temperature is risen to 120 ℃ of beginning high temperature after fixing, and whole rear curing time is 6h, and the curing system is 120 ℃ solidified 2 hours down, and 140 ℃ solidify 2h down then, and 180 ℃ solidified 2 hours down then.By the veneer sheet of such moulding, with cutting out 0 ° of test film and interlaminar shear strength test film that the direction pliability test is used of model machine excision.Adopt China Shenzhen CMT5105 electronic universal tester to carry out physicals test separately; The flexural strength test is with reference to GB3356-1999 " the crooked bending property TP of unidirectional fibre reinforced plastics ", and interlaminar shear strength is with reference to JC/T773-96 " unidirectional fibre reinforced plastics interlayer shear strength test method ".Flexural strength is 1025MPa, and modulus in flexure is 109GPa, and interlaminar shear strength is 45MPa.
Comparative example 2
Is peer-level for making the prepared glued membrane of resin combination with prepared glued membrane solidification value of the resin combination of embodiment 1 and embodiment 2 and the viscosity storage period under the room temperature; So the usage quantity of (Italian polynt company) respectively is 35 mass parts liquid E-51 epoxy resin (Shanghai Resin Factory), solid-state CYD-012 epoxy resin (Ba Ling petro-chemical corporation) and methyl carbic anhydride; 65 mass parts and 45 mass parts; Benzyltriethylammoinium chloride promotor (source, Shanghai leaf bio tech ltd) and aluminium acetylacetonate (U.S. Sigma-Aldrich company) usage quantity respectively are 2 mass parts and 1 mass parts, and according to the composition epoxy resin of the identical process methodes modulation comparative example 2 of embodiment 1 and embodiment 2.
With synthetic like this composition epoxy resin, when the viscosity of composition epoxy resin is 15Pas, with scraping the skill in using a kitchen knife in cookery epoxy resin adhesive liquid is coated on the separate-type paper down at 70 ℃, the mass area ratio of system is 83g/m
2Resin film.
In addition, on above-mentioned resin film, thomel is drawn neat putting, at first on the prepreg machine, cold pressing 3～4 times, use 90 ℃ heating drum to carry out the dipping of opening fibre, resin of fiber then.The travelling speed of fiber is 10m/min, and the roll-in number of times is 14 times, thereby makes fiber areal densities 120g/m
2, resin content is the carbon fiber/epoxy resin unidirectional pre-immersion material of 30% (mass percent).Resulting carbon fiber/epoxy resin unidirectional pre-immersion material, thomel fill a part infiltration, and have appropriate cohesiveness.Do not stick polyvinylidene film on its surface, room temperature held 8 days is observed the variation of its cementability, thereby confirms that be 8 days the viscosity storage period under its room temperature.
Secondly, for making the thick fibre reinforced epoxy resin composite veneer sheet of 2mm,,, put into mould by 16 layers of same direction stacks with the above-mentioned carbon fiber/epoxy resin unidirectional pre-immersion material that makes.At pressure is 0MPa, and temperature is to solidify 45 minutes in 85 ℃ the moulding press, and the pressure with moulding press rises to 1MPa then, continues to solidify 75min minute down at 85 ℃, to accomplish primary solidification.After the primary solidification, the pressure with moulding press rises to 1MPa earlier, again temperature is risen to 120 ℃ of beginning high temperature after fixing, and whole rear curing time is 6h, and the curing system is 120 ℃ solidified 2 hours down, and 140 ℃ solidify 2h down then, and 180 ℃ solidified 2 hours down then.By the veneer sheet of such moulding, with cutting out 0 ° of test film and interlaminar shear strength test film that the direction pliability test is used of model machine excision.Adopt China Shenzhen CMT5105 electronic universal tester to carry out physicals test separately; The flexural strength test is with reference to GB3356-1999 " the crooked bending property TP of unidirectional fibre reinforced plastics ", and interlaminar shear strength is with reference to JC/T773-96 " unidirectional fibre reinforced plastics interlayer shear strength test method ".Flexural strength is 890MPa, and modulus in flexure is 86GPa, and interlaminar shear strength is 40MPa.
Comparative example 3
Except not adding quaternary ammonium salt promotor; And be peer-level with the prepared glued membrane solidification value of resin combination of embodiment 1 and embodiment 2 in order to make the prepared glued membrane of resin combination; And and become three-(dimethylamino methyl) phenol (Italian polynt company) the foregoing description 1 and embodiment 2 used promotor; Usage quantity is 1 mass parts; The usage quantity of same liquid E-51 epoxy resin (Shanghai Resin Factory), solid-state CYD-011 epoxy resin (Ba Ling petro-chemical corporation) and methyl carbic anhydride (Italian polynt company) respectively is 35 mass parts; 65 mass parts and 45 mass parts, and according to the composition epoxy resin of the identical process methodes modulation comparative example 3 of embodiment 1 and embodiment 2.
With synthetic like this composition epoxy resin, when the viscosity of composition epoxy resin is 17Pas, with scraping the skill in using a kitchen knife in cookery epoxy resin adhesive liquid is coated on the separate-type paper down at 70 ℃, the mass area ratio of system is 86g/m
2Resin film.
In addition, on above-mentioned resin film, thomel is drawn neat putting, at first on the prepreg machine, cold pressing 3～4 times, use 70 ℃ heating drum to carry out the dipping of opening fibre, resin of fiber then.The travelling speed of fiber is 3.8m/min, and the roll-in number of times is 16 times, thereby makes fiber areal densities 100g/m
2, resin content is the carbon fiber/epoxy resin unidirectional pre-immersion material of 40% (mass percent).Resulting carbon fiber/epoxy resin unidirectional pre-immersion material, thomel fill a part infiltration.Prepreg is placed under the room temperature, observes the variation of its viscosity, thereby confirm that be 6 days the viscosity storage period under its room temperature.
Secondly, for making the thick fibre reinforced epoxy resin composite veneer sheet of 2mm,,, put into mould by 16 layers of same direction stacks with the above-mentioned carbon fiber/epoxy resin unidirectional pre-immersion material that makes.At pressure is 0MPa, and temperature is to solidify 45 minutes in 85 ℃ the moulding press, and the pressure with moulding press rises to 1MPa then, continues to solidify 75min minute down at 85 ℃, to accomplish primary solidification.After the primary solidification, temperature is risen to 120 ℃ of beginning high temperature after fixing, whole rear curing time is 6h, and the curing system is 120 ℃ solidified 2 hours down, and 140 ℃ solidify 2h down then, and 180 ℃ solidified 2 hours down then.By the veneer sheet of such moulding, with cutting out 0 ° of test film and interlaminar shear strength test film that the direction pliability test is used of model machine excision.Adopt China Shenzhen CMT5105 electronic universal tester to carry out physicals test separately; The flexural strength test is with reference to GB3356-1999 " the crooked bending property TP of unidirectional fibre reinforced plastics ", and interlaminar shear strength is with reference to JC/T773-96 " unidirectional fibre reinforced plastics interlayer shear strength test method ".Flexural strength is 1020MPa, and modulus in flexure is 102GPa, and interlaminar shear strength is 68MPa.
Comparative example 4
Except not adding quaternary ammonium salt promotor; And be peer-level with the prepared glued membrane solidification value of resin combination of embodiment 1 and embodiment 2 in order to make the prepared glued membrane of resin combination; And and become 2-ethyl-4-methylimidazole (Tianjin A Faaisha chemistry ltd) the foregoing description 1 and embodiment 2 used same promotor; Content is 1 mass parts; The usage quantity of same liquid E-51 epoxy resin (Shanghai Resin Factory), solid-state CYD-011 epoxy resin (Ba Ling petro-chemical corporation) and methyl carbic anhydride (Italian po lynt company) respectively is 35 mass parts; 65 mass parts and 45 mass parts, and according to the composition epoxy resin of the identical process methodes modulation comparative example 4 of embodiment 1 and embodiment 2.
With synthetic like this composition epoxy resin, when the viscosity of composition epoxy resin is 18Pas, with scraping the skill in using a kitchen knife in cookery epoxy resin adhesive liquid is coated on the separate-type paper down at 70 ℃, the mass area ratio of system is 83g/m
2Resin film.
In addition, on above-mentioned resin film, thomel is drawn neat putting, at first on the prepreg machine, cold pressing 3～4 times, use 70 ℃ heating drum to carry out the dipping of opening fibre, resin of fiber then.The travelling speed of fiber is 3.8m/min, and the roll-in number of times is 14 times, thereby makes fiber areal densities 100g/m
2, resin content is the carbon fiber/epoxy resin unidirectional pre-immersion material of 40% (mass percent).Resulting carbon fiber/epoxy resin unidirectional pre-immersion material, thomel fill a part infiltration.Prepreg is placed under the room temperature, observes the variation of its viscosity, thereby confirm that be 5 days the storage period under its room temperature.
Secondly, for making the thick fibre reinforced epoxy resin composite veneer sheet of 2mm,,, put into mould by 16 layers of same direction stacks with the above-mentioned carbon fiber/epoxy resin unidirectional pre-immersion material that makes.At pressure is 0MPa, and temperature is to solidify 45 minutes in 85 ℃ the moulding press, and the pressure with moulding press rises to 1MPa then, continues to solidify 75min minute down at 85 ℃, to accomplish primary solidification.After the primary solidification, again temperature is risen to 120 ℃ of beginning high temperature after fixing.The after fixing system is 120 ℃ solidified 2 hours down, solidified 2 hours for 140 times then, and last 180 ℃ solidified 2 hours down.By the veneer sheet of such moulding, with cutting out 0 ° of test film and interlaminar shear strength test film that the direction pliability test is used of model machine excision.Adopt China Shenzhen CMT5105 electronic universal tester to carry out physicals test separately; The flexural strength test is with reference to GB3356-1999 " the crooked bending property TP of unidirectional fibre reinforced plastics ", and interlaminar shear strength is with reference to JC/T773-96 " unidirectional fibre reinforced plastics interlayer shear strength test method ".Flexural strength is 1025MPa, and modulus in flexure is 108GPa, and interlaminar shear strength is 70MPa.
Comparative example 5
Except not adding anhydride curing agent; And for the prepared glued membrane of resin viscosity and resin combination be peer-level with the resin combination of embodiment 1 and embodiment 2 prepared glued membrane viscosity storage period; And and become 4 at the foregoing description 1 and embodiment 2 used same solidifying agent; 4-diaminodiphenylsulfone(DDS) (Chemical Reagent Co., Ltd., Sinopharm Group); Content is 25 mass parts; Same liquid E-51 epoxy resin (Shanghai Resin Factory), the usage quantity of solid-state CYD-011 epoxy resin (Ba Ling petro-chemical corporation) they respectively are 45 mass parts, 55 mass parts, and modulate the compsn of the epoxy resin of comparative example 5 according to embodiment 1 and embodiment 2 identical process methodes.
With synthetic like this composition epoxy resin, when the viscosity of composition epoxy resin is 20Pas, with scraping the skill in using a kitchen knife in cookery epoxy resin adhesive liquid is coated on the separate-type paper down at 75 ℃, the mass area ratio of system is 84g/m
2Resin film.
In addition, on above-mentioned resin film, thomel is drawn neat putting, at first on the prepreg machine, cold pressing 3～4 times, use 90 ℃ heating drum to carry out the dipping of opening fibre, resin of fiber then.The travelling speed of fiber is 3.8m/min, and the roll-in number of times is 16 times, thereby makes fiber areal densities 100g/m
2, resin content is the carbon fiber/epoxy resin unidirectional pre-immersion material of 40% (mass percent).Resulting carbon fiber/epoxy resin unidirectional pre-immersion material, thomel fill a part infiltration.Prepreg is placed under the room temperature, observes the variation of its viscosity, thereby confirm that be 15 days the storage period under its room temperature.
Secondly, for making the thick fibre reinforced epoxy resin composite veneer sheet of 2mm,,, put into mould by 16 layers of same direction stacks with the above-mentioned carbon fiber/epoxy resin unidirectional pre-immersion material that makes.At pressure is 0MPa, and temperature is to solidify 45 minutes in 120 ℃ the moulding press, and the pressure with moulding press rises to 1MPa then, continues to solidify 75min minute down at 120 ℃, to accomplish primary solidification.After the primary solidification, again temperature is risen to 160 ℃ of beginning high temperature after fixing, whole rear curing time is 6h, and the after fixing system is 160 ℃ solidified 2 hours down, solidified 2 hours for 180 times then, and last 210 ℃ solidified 2 hours down.By the veneer sheet of such moulding, with cutting out 0 ° of test film and interlaminar shear strength test film that the direction pliability test is used of model machine excision.Adopt China Shenzhen CMT5105 electronic universal tester to carry out physicals test separately; The flexural strength test is with reference to GB3356-1999 " the crooked bending property TP of unidirectional fibre reinforced plastics ", and interlaminar shear strength is with reference to JC/T773-96 " unidirectional fibre reinforced plastics interlayer shear strength test method ".Flexural strength is 1239MPa, and modulus in flexure is 112GPa, and interlaminar shear strength is 75MPa.
Comparative example 6
Except not adding anhydride curing agent; And for the prepared glued membrane of resin viscosity and resin combination be peer-level with the resin combination of embodiment 1 and embodiment 2 prepared glued membrane viscosity storage period; And becoming Dyhard RU 100 (Chemical Reagent Co., Ltd., Sinopharm Group) at the foregoing description 1 and embodiment 2 used same solidifying agent; Consumption is 6 mass parts; Same liquid E-51 epoxy resin (Shanghai Resin Factory), solid-state CYD-011 epoxy resin (Ba Ling petro-chemical corporation) usage quantity respectively are 40 mass parts, 60 mass parts, and modulate the composition epoxy resin of comparative example 6 according to embodiment 1 and embodiment 2 identical process methodes.
With synthetic like this composition epoxy resin, when the viscosity of composition epoxy resin is 23Pas, with scraping the skill in using a kitchen knife in cookery epoxy resin adhesive liquid is coated on the separate-type paper down at 70 ℃, the mass area ratio of system is 84g/m
2Resin film.
In addition, on above-mentioned resin film, thomel is drawn neat putting, at first on the prepreg machine, cold pressing 3～4 times, use 75 ℃ heating drum to carry out the dipping of opening fibre, resin of fiber then.The travelling speed of fiber is 4m/min, and the roll-in number of times is 15 times.Prepreg is placed under the room temperature, observes the variation of its viscosity, thereby confirm that be 13 days the storage period under its room temperature.
Secondly, for making the thick fibre reinforced epoxy resin composite veneer sheet of 2mm,,, put into mould by 16 layers of same direction stacks with the above-mentioned carbon fiber/epoxy resin unidirectional pre-immersion material that makes.At pressure is 0MPa, and temperature is to solidify 45 minutes in 120 ℃ the moulding press, and the pressure with moulding press rises to 1MPa then, continues to solidify 75min minute down at 120 ℃, to accomplish primary solidification.After the primary solidification, again temperature is risen to 150 ℃ of beginning high temperature after fixing, whole rear curing time is 6h, and the after fixing system is 150 ℃ solidified 2 hours down, solidified 2 hours for 180 times then, and last 200 ℃ solidified 2 hours down.By the veneer sheet of such moulding, with cutting out 0 ° of test film and interlaminar shear strength test film that the direction pliability test is used of model machine excision.Adopt China Shenzhen CMT5105 electronic universal tester to carry out physicals test separately; The flexural strength test is with reference to GB3356-1999 " the crooked bending property TP of unidirectional fibre reinforced plastics ", and interlaminar shear strength is with reference to JC/T773-96 " unidirectional fibre reinforced plastics interlayer shear strength test method ".Flexural strength is 1139MPa, and modulus in flexure is 109GPa, and interlaminar shear strength is 73MPa.
Long-acting temperature curing epoxy low resin provided by the invention; When at room temperature having good storage period; Also give at low temperatures and can accomplish primary solidification; And the matrix material after the prepreg moulding that makes after itself and fortifying fibre are compound has good mechanical performance and resistance toheat, can be used as be used in recreational use and relevant motion goods etc. must various uses in the intermediate materials of widely used matrix material.
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.
The concrete experiment condition of the foregoing description and comparative example is as shown in the table:
Table 1
The experimental result of above-mentioned experiment is as shown in the table:
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | |
| Flexural strength | 1056MPa | 1036MPa | 1026MPa | 1025MPa | 890MPa |
| Modulus in flexure | 118GPa | 110GPa | 109GPa | 109GPa | 86GPa |
| Interlaminar shear strength | 70MPa | 71MPa | 70MPa | 45MPa | 40MPa |
| Viscosity storage period | 8 days | 8 days | 8 days | 8 days | 8 days |
| Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | ||
| Flexural strength | 1020MPa | 1025MPa | 1239MPa | 1139MPa | |
| Modulus in flexure | 102GPa | 108GPa | 112GPa | 109GPa | |
| Interlaminar shear strength | 68MPa | 70MPa | 75MPa | 73MPa | |
| Viscosity storage period | 6 days | 5 days | 15 days | 13 days |
Table 2
Long-acting temperature curing epoxy low resin provided by the invention; When at room temperature having good storage period; Also give at low temperatures and can accomplish primary solidification; And the matrix material after the prepreg moulding that makes after itself and fortifying fibre are compound has good mechanical performance and resistance toheat, can be used as be used in recreational use and relevant motion goods etc. must various uses in the intermediate materials of widely used matrix material.
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 (10)
1. composition epoxy resin is characterized in that said composition comprises:
A composition: the liquid bisphenol A epoxy resin of 33～35 mass parts;
B composition: the solid-state bisphenol A epoxide resin of 65～67 mass parts;
C composition:, be the anhydride curing agent of 46～51 mass parts with respect to the epoxy resin of 100 mass parts;
D composition:, be the quaternary ammonium salt promotor of 1～2.5 mass parts with respect to the epoxy resin of 100 mass parts;
E composition:, be the acetyl acetone salt promotor of 0.05～1 mass parts with respect to the epoxy resin of 100 mass parts.
2. composition epoxy resin as claimed in claim 1 is characterized in that, said A composition liquid bisphenol A epoxy resin is E-54 or E-51 or E-44 epoxy resin.
3. composition epoxy resin as claimed in claim 1 is characterized in that, the solid-state bisphenol A epoxide resin of said B composition is CYD-011 or CYD-012 or E-31 epoxy resin.
4. composition epoxy resin as claimed in claim 1 is characterized in that, said C composition anhydride curing agent is methyl tetrahydrophthalic anhydride or dodecenylsuccinic acid acid anhydride or methyl carbic anhydride.
5. composition epoxy resin as claimed in claim 1 is characterized in that: said D composition quaternary ammonium salt promotor is benzyltriethylammoinium chloride or diethylammonium ethanol based ammonium chloride or benzyl tributyl ammonium chloride.
6. composition epoxy resin as claimed in claim 1 is characterized in that: said E composition acetyl acetone salt promotor is aluminium acetylacetonate or chromium acetylacetonate or titanium acetylacetone.
7. one kind is used the method for preparation of compositions prepreg according to claim 1, it is characterized in that, may further comprise the steps:
Step 1 will be described in claim 1 preparation of compositions resin film;
Step 2 adds fortifying fibre with the resin film of step 1 gained, on the prepreg machine, colds pressing 3～4 times, and the temperature of hot pressing roller is 55～75 ℃, and the rotating speed of hot pressing roller is 3～4m/min, and the hot pressing number of times is 12～16 times.
8. prepreg as claimed in claim 8 is characterized in that, fortifying fibre is unidirectional carbon fiber dimension or carbon cloth or glasscloth or boron fibre or aramid fiber.
9. the preparation method of a fibre reinforced epoxy resin composite is characterized in that, may further comprise the steps:
Step 1 is placed the prepreg like the said method preparation of claim 9 in forming mould;
Step 2 close die heats, pressurization and moulding.
10. preparation method as claimed in claim 9 is characterized in that, said step 2 may further comprise the steps:
Step 2.1 primary solidification: at pressure is 0MPa, and temperature is to solidify 30～45 minutes in 85 ℃ the moulding press, and the pressure with moulding press rises to 1MPa then, continues to solidify 75～90 minutes down at 85 ℃;
Step 2.2 after fixing: the curing system is 120 ℃ solidified 2 hours down, and 140 ℃ solidify 2h down then, and 180 ℃ solidified 2 hours down then.
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