CN102532484B - 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 formingthe 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 composition, relate in particular to a kind of composition epoxy resin and use the method that it prepares prepreg and matrix material.
Background technology
Because Resins, epoxy has preferably mechanical property and thermal characteristics, in various fields, have comparatively widely and use.Particularly in the field of compound material centered by fibre reinforced plastics, Resins, epoxy is used as matrix resin more, and glass fibre, carbon fiber, 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 good especially, so in the purposes that requires the motion goods such as the purposes such as light-weighted aircraft and Veronicastrum Herb, golf club, tennis racket, be widely used especially.
Current advanced fiber reinforced plastic composite material product more than 70% spreads repeatedly to solidify with prepreg 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 Resins, epoxy of prepreg, employed heat-resistant resin in the purposes of relevant aircraft for example, the known aromatic polyamine resin combination that the polyfunctional epoxy resins such as four Racemic glycidol diamino dimethylbenzene 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 phenol aldehyde type epoxy resin and bisphenol A type epoxy resin etc. Resins, epoxy and the resin combination that forms as their curing agent dicyandiamide.The resin that is used for aircraft application needs preferably thermotolerance, its second-order transition temperature requires to reach more than 200 ℃, so the high price polyfunctional Resins, epoxy as major ingredient, and the prepreg condition of cure that itself and fiber composite prepare is for solidifying two hours with 180 ℃, and 180 ℃～200 ℃/2～4 hours, but such moulding process needs high temperature and long-time.And often in matrix material, produce larger internal stress during the matrix material of hot setting prepreg moulding, thereby affect dimensional precision, and complex forming technology, consume energy higher, and the subsidiary material selection ranges such as preparation core, mould are narrow, finally cause the moulding cost of matrix material expensive.Show 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 from production efficiency and in price, be worthless.
The problems referred to above that occur in order to solve the hot setting prepreg, people have done many work.Research and development micro capsule curing agent technology and latent curing system are the effective ways that solve contradiction during prepreg low-temperature curing and the longer room temperature storage, also are the current main development directions of low temperature curing agent.For example propose to adopt emulsifying technology that solidifying agent is coated the formation microcapsule with thermoplastic resin in United States Patent (USP) 5567792 specification sheetss and United States Patent (USP) 5859096 specification sheetss, this microcapsule median size 5～50 μ m can be in harmonious proportion the glue that comes true with Resins, epoxy.Isolated solidifying agent contacts with Resins, epoxy under the room temperature, and when reaching solidification value, the thermoplastic resin film dissolving discharges solidifying agent and epoxy resin cure, can solve simultaneously room temperature storage phase stability and low-temperature curing.But the microcapsule size generally need to be under 5 μ m, get microcapsule under difficult this size of preparation at present, because particle is larger, can't enter between fiber and evenly part loose, can't prepare the high quality prepreg, on 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 to reach an energy low-temperature curing and when cooperating with Resins, epoxy storage period long effect.For example 3 nitrogen-atoms alkalescence are stronger, can in and the 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, the 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 being widely used property, also on the difficult prepreg that is useful in as purposes such as relevant leisure, sports goods.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, it is 8 days and can be at the 85 ℃ of lower composition epoxy resins that can finish primary solidification lower 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 of following A composition, B composition, C composition, D composition and E composition.
A composition: liquid bisphenol A Resins, epoxy
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 prepreg room temperature storage phase of making of binding resin film and fiber composite and solidification value, definite a kind of composition epoxy resin.Described liquid bisphenol A Resins, epoxy composition A, in whole epoxy-resin systems, to contain 35% mass parts at least, liquid bisphenol A Resins, epoxy among the present invention, be not specifically noted, can use commercially available liquid bisphenol A Resins, epoxy, adducible especially example has: E-54, E-51 and E-44 Resins, epoxy; Described 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, be not specifically noted, can use commercially available solid-state bisphenol A epoxide resin, adducible especially example has: CYD-001, CYD-012 or E-31 Resins, epoxy.
Employed Resins, epoxy anhydride curing agent C among the present invention, can not only the shorter at low temperatures time can finish primary solidification Resins, epoxy, 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) and part loose property are better simultaneously.Anhydride curing agent among the present invention is not specifically noted, and can use the anhydride curing agent of commercially available usefulness, such as methyl tetrahydrophthalic anhydride, dodecenylsuccinic acid acid anhydride or methyl carbic anhydride.The usage quantity of solidifying agent with respect to Resins, epoxy 100 mass parts, is 48～51 mass parts, if surpass this weight, unreacted solidifying agent is remained in the resin, thereby affect the performance of epoxy resin cured product, the most important thing is to affect the viscosity under the prepreg room temperature.If be lower than this weight, meeting the set time of meeting overspending, finally also can affect the performance by the prepared matrix material of prepreg simultaneously so that unreacted Resins, epoxy left behind.
Quaternary ammonium salt vulkacit D of the present invention is not specifically noted, and can be commercially available through being commonly used for the quaternary ammonium salt of cationic surfactant and phase-transfer catalyst, such as benzyltriethylammoinium chloride, diethyl ethanol based ammonium chloride and benzyl tributyl ammonium chloride.Generally with respect to the Resins, epoxy of 100 mass parts, its consumption is 1～2.5 mass parts, if surpass this weight, then can shorten under the prepreg room temperature getting storage period; If be lower than this weight, then do not play the effect of promotor, so that can not be the at room temperature shorter time of prepreg can be finished primary solidification.
Chromium acetylacetonate E of the present invention is not specifically noted, and can be commercially available acetyl acetone salt, such as aluminium acetylacetonate, titanium acetylacetone and chromium acetylacetonate.Generally with respect to the Resins, epoxy of 100 mass parts, its consumption is 0.05～1 mass parts, if surpass this weight, then can shorten under the prepreg room temperature getting storage period; If be lower than this weight, then do not play the effect of promotor, so that can not be the at room temperature shorter time of prepreg can be finished 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: carbon fiber, glass fibre, aramid fiber etc., in addition, shape about fiber is not done special restriction yet, can enumerate, for example can be the band arranged by certain orientation, one-way fabric, drills etc.
The blending process of low-temperature long acting Cured epoxy resin compositions of the present invention is as follows: liquid bisphenol A Resins, epoxy A is heated, add simultaneously solid-state bisphenol A epoxide resin B, after stirring under 90 ℃, then cool the temperature to 70 ℃, after adding anhydride curing agent C stirs.Under 70 ℃, add latent quaternary ammonium salt vulkacit D and acetyl acetone salt E, blending epoxy glue again stirs to get.
The technique that the above-mentioned epoxy resin adhesive liquid for preparing prepares the Resins, epoxy 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 gap and the thickness of the speed control Resins, epoxy glued membrane of feed.
Put at above-mentioned Resins, epoxy glued membrane and to 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 infiltrates not thoroughly fiber, 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 infiltrate fiber although be lower than this rotating speed resin, affects production efficiency.Surpass this rotating speed, same resin infiltrates fiber and fills not part, 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 infiltrates fiber and fills not part.Be higher than this number of times, although resin can infiltrate fiber, can reduce production efficiency.
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 cycle 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 finished 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 preferably mechanical property and resistance toheat.The widely application prospect that in recreational use and relevant motion goods, has.
Once by embodiment and comparative example the present invention is illustrated particularly
Embodiment
Embodiment 1
Solid-state CYD-011 (Ba Ling petro-chemical corporation) Resins, epoxy of the liquid E-54 Resins, epoxy (Shanghai Resin Factory) of 33 mass parts and 67 mass parts is heated to 90 ℃ to be dissolved into after the uniform mixture, then this mixture temperature is cooled to 70 ℃, the methyl carbic anhydride (Italian polynt company) that adds 48 mass parts in this mixture fills after part stirs, add again 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, mix to modulate the composition epoxy resin of embodiment 1.
With the composition epoxy resin of modulating like this, when the viscosity of composition epoxy resin is 15Pas, under 60 ℃, with scraping the skill in using a kitchen knife in cookery epoxy resin adhesive liquid is coated on the separate-type paper, the mass area ratio of system is 80g/m
2Resin film.
In addition, on above-mentioned resin film, carbon fiber is drawn neat putting, at first cold pressing 3～4 times at the prepreg machine, then use 70 ℃ heating drum to carry out the dipping of opening fibre, resin of fiber.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, carbon fiber fill a part infiltration, and have appropriate cohesiveness.Do not stick polyethylene film on its surface, placed 8 days under the room temperature, observe the variation of its cementability, thereby determine 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, with the above-mentioned carbon fiber/epoxy resin unidirectional pre-immersion material that makes, by 16 layers of same direction stacks, put into mould.Be 0MPa at pressure, temperature is to solidify 30 minutes in 85 ℃ the moulding press, and then the pressure with moulding press rises to 1MPa, continues 85 ℃ of lower curing 90min minute, to finish primary solidification.After the primary solidification, temperature is risen to 120 ℃ of beginning high temperature after fixing, whole rear curing time is 6 hours again, and curing cycle is 120 ℃ of lower curing 2 hours, then 140 ℃ of lower 2h that solidify, then 180 ℃ of lower curing 2 hours.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.Employing China Shenzhen CMT5105 electronic universal tester carries out quantitative measurement separately, the flexural strength test is with reference to GB3356-1999 " the crooked bending property test method 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) Resins, epoxy of liquid E-44 (Shanghai Resin Factory) Resins, epoxy of 35 mass parts and 65 mass parts is heated to 90 ℃ to be dissolved into after the uniform mixture, then this mixture temperature is cooled to 70 ℃, the methyl carbic anhydride (Italian polynt company) that adds 46 mass parts in this mixture fills after part stirs, add again 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, mix to modulate the composition epoxy resin of embodiment 2.
With the composition epoxy resin of modulating like this, when the viscosity of composition epoxy resin is 10Pas, under 65 ℃, with scraping the skill in using a kitchen knife in cookery epoxy resin adhesive liquid is coated on the separate-type paper, the mass area ratio of system is 82g/m
2Resin film.
In addition, on above-mentioned resin film, carbon fiber is drawn neat putting, at first cold pressing 3～4 times at the prepreg machine, then use 70 ℃ heating drum to carry out the dipping of opening fibre, resin of fiber.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, carbon fiber fill a part infiltration, and have appropriate cohesiveness.Do not stick polyethylene film on its surface, placed 8 days under the room temperature, observe the variation of its cementability, thereby determine 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, with the above-mentioned carbon fiber/epoxy resin unidirectional pre-immersion material that makes, by 16 layers of same direction stacks, put into mould.Be 0MPa at pressure, temperature is to solidify 45 minutes in 85 ℃ the moulding press, and then the pressure with moulding press rises to 1MPa, continues 85 ℃ of lower curing 75min minute, to finish primary solidification.After the primary solidification, temperature is risen to 120 ℃ of beginning high temperature after fixing, whole rear curing time is 6h again, and curing cycle is 120 ℃ of lower curing 2 hours, then 140 ℃ of lower 2h that solidify, then 180 ℃ of lower curing 2 hours.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.Employing China Shenzhen CMT5105 electronic universal tester carries out quantitative measurement separately, the flexural strength test is with reference to GB3356-1999 " the crooked bending property test method 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) Resins, epoxy of liquid E-44 (Shanghai Resin Factory) Resins, epoxy of 34 mass parts and 66 mass parts is heated to 90 ℃ to be dissolved into after the uniform mixture, then this mixture temperature is cooled to 70 ℃, the methyl carbic anhydride (Italian polynt company) that adds 46 mass parts in this mixture fills after part stirs, add again 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, mix to modulate the composition epoxy resin of embodiment 2.
With the composition epoxy resin of modulating like this, when the viscosity of composition epoxy resin is 12Pas, under 70 ℃, with scraping the skill in using a kitchen knife in cookery epoxy resin adhesive liquid is coated on the separate-type paper, the mass area ratio of system is 84g/m
2Resin film.
In addition, on above-mentioned resin film, carbon fiber is drawn neat putting, at first cold pressing 3～4 times at the prepreg machine, then use 70 ℃ heating drum to carry out the dipping of opening fibre, resin of fiber.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, carbon fiber fill a part infiltration, and have appropriate cohesiveness.Do not stick polyethylene film on its surface, placed 8 days under the room temperature, observe the variation of its cementability, thereby determine 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, with the above-mentioned carbon fiber/epoxy resin unidirectional pre-immersion material that makes, by 16 layers of same direction stacks, put into mould.Be 0MPa at pressure, temperature is to solidify 45 minutes in 85 ℃ the moulding press, and then the pressure with moulding press rises to 1MPa, continues 85 ℃ of lower curing 75min minute, to finish primary solidification.After the primary solidification, temperature is risen to 120 ℃ of beginning high temperature after fixing, whole rear curing time is 6h again, and curing cycle is 120 ℃ of lower curing 2 hours, then 140 ℃ of lower 2h that solidify, then 180 ℃ of lower curing 2 hours.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.Employing China Shenzhen CMT5105 electronic universal tester carries out quantitative measurement separately, the flexural strength test is with reference to GB3356-1999 " the crooked bending property test method 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
Be peer-level for making the prepared glued membrane of resin combination with the prepared glued membrane solidification value of the resin combination of embodiment 1 and embodiment 2 and the viscosity storage period under the room temperature, therefore liquid E-51 Resins, epoxy (Shanghai Resin Factory), the usage quantity of solid-state CYD-011 Resins, epoxy (Ba Ling petro-chemical corporation) and methyl carbic anhydride (Italian polynt company) respectively is 35 mass parts, 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 processing methodes modulation comparative example 1 of embodiment 1 and embodiment 2.
With the composition epoxy resin of modulating like this, when the viscosity of composition epoxy resin is 12Pas, under 68 ℃, with scraping the skill in using a kitchen knife in cookery epoxy resin adhesive liquid is coated on the separate-type paper, the mass area ratio of system is 84g/m
2Resin film.
In addition, on above-mentioned resin film, carbon fiber is drawn neat putting, at first cold pressing 3～4 times at the prepreg machine, then use 70 ℃ heating drum to carry out the dipping of opening fibre, resin of fiber.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, carbon fiber fill a part infiltration, and have appropriate cohesiveness.Do not stick polyethylene film on its surface, placed under the room temperature 8 days, observe the variation of its cementability, thereby determine 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, with the above-mentioned carbon fiber/epoxy resin unidirectional pre-immersion material that makes, by 16 layers of same direction stacks, put into mould.Be 0MPa at pressure, temperature is to solidify 2h in 85 ℃ the moulding press, to finish primary solidification.After the primary solidification, the pressure with moulding press rises to 1MPa first, temperature is risen to 120 ℃ of beginning high temperature after fixing again, and whole rear curing time is 6h, and curing cycle is 120 ℃ of lower curing 2 hours, then 140 ℃ of lower 2h that solidify, then 180 ℃ of lower curing 2 hours.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.Employing China Shenzhen CMT5105 electronic universal tester carries out quantitative measurement separately, the flexural strength test is with reference to GB3356-1999 " the crooked bending property test method 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
Be peer-level for making the prepared glued membrane of resin combination with the prepared glued membrane solidification value of the resin combination of embodiment 1 and embodiment 2 and the viscosity storage period under the room temperature, therefore liquid E-51 Resins, epoxy (Shanghai Resin Factory), the usage quantity of solid-state CYD-012 Resins, epoxy (Ba Ling petro-chemical corporation) and methyl carbic anhydride (Italian polynt company) respectively is 35 mass parts, 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 processing methodes modulation comparative example 2 of embodiment 1 and embodiment 2.
With the composition epoxy resin of modulating like this, when the viscosity of composition epoxy resin is 15Pas, under 70 ℃, with scraping the skill in using a kitchen knife in cookery epoxy resin adhesive liquid is coated on the separate-type paper, the mass area ratio of system is 83g/m
2Resin film.
In addition, on above-mentioned resin film, carbon fiber is drawn neat putting, at first cold pressing 3～4 times at the prepreg machine, then use 90 ℃ heating drum to carry out the dipping of opening fibre, resin of fiber.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, carbon fiber fill a part infiltration, and have appropriate cohesiveness.Do not stick polyethylene film on its surface, placed under the room temperature 8 days, observe the variation of its cementability, thereby determine 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, with the above-mentioned carbon fiber/epoxy resin unidirectional pre-immersion material that makes, by 16 layers of same direction stacks, put into mould.Be 0MPa at pressure, temperature is to solidify 45 minutes in 85 ℃ the moulding press, and then the pressure with moulding press rises to 1MPa, continues 85 ℃ of lower curing 75min minute, to finish primary solidification.After the primary solidification, the pressure with moulding press rises to 1MPa first, temperature is risen to 120 ℃ of beginning high temperature after fixing again, and whole rear curing time is 6h, and curing cycle is 120 ℃ of lower curing 2 hours, then 140 ℃ of lower 2h that solidify, then 180 ℃ of lower curing 2 hours.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.Employing China Shenzhen CMT5105 electronic universal tester carries out quantitative measurement separately, the flexural strength test is with reference to GB3356-1999 " the crooked bending property test method 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 in order to make the prepared glued membrane of resin combination with the prepared glued membrane solidification value of the resin combination of embodiment 1 and embodiment 2, and and become three-(dimethylamino methyl) phenol (Italian polynt company) above-described embodiment 1 and embodiment 2 used promotor, usage quantity is 1 mass parts, same liquid E-51 Resins, epoxy (Shanghai Resin Factory), the usage quantity of solid-state CYD-011 Resins, epoxy (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 processing methodes modulation comparative example 3 of embodiment 1 and embodiment 2.
With the composition epoxy resin of modulating like this, when the viscosity of composition epoxy resin is 17Pas, under 70 ℃, with scraping the skill in using a kitchen knife in cookery epoxy resin adhesive liquid is coated on the separate-type paper, the mass area ratio of system is 86g/m
2Resin film.
In addition, on above-mentioned resin film, carbon fiber is drawn neat putting, at first cold pressing 3～4 times at the prepreg machine, then use 70 ℃ heating drum to carry out the dipping of opening fibre, resin of fiber.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, carbon fiber fill a part infiltration.Prepreg is put at room temperature, observed the variation of its viscosity, thereby determine 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, with the above-mentioned carbon fiber/epoxy resin unidirectional pre-immersion material that makes, by 16 layers of same direction stacks, put into mould.Be 0MPa at pressure, temperature is to solidify 45 minutes in 85 ℃ the moulding press, and then the pressure with moulding press rises to 1MPa, continues 85 ℃ of lower curing 75min minute, to finish primary solidification.After the primary solidification, temperature is risen to 120 ℃ of beginning high temperature after fixing, whole rear curing time is 6h, and curing cycle is 120 ℃ of lower curing 2 hours, then 140 ℃ of lower 2h that solidify, then 180 ℃ of lower curing 2 hours.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.Employing China Shenzhen CMT5105 electronic universal tester carries out quantitative measurement separately, the flexural strength test is with reference to GB3356-1999 " the crooked bending property test method 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 in order to make the prepared glued membrane of resin combination with the prepared glued membrane solidification value of the resin combination of embodiment 1 and embodiment 2, and and become 2-ethyl-4-methylimidazole (Tianjin A Faaisha chemistry company limited) above-described embodiment 1 and embodiment 2 used same promotor, content is 1 mass parts, same liquid E-51 Resins, epoxy (Shanghai Resin Factory), the usage quantity of solid-state CYD-011 Resins, epoxy (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 processing methodes modulation comparative example 4 of embodiment 1 and embodiment 2.
With the composition epoxy resin of modulating like this, when the viscosity of composition epoxy resin is 18Pas, under 70 ℃, with scraping the skill in using a kitchen knife in cookery epoxy resin adhesive liquid is coated on the separate-type paper, the mass area ratio of system is 83g/m
2Resin film.
In addition, on above-mentioned resin film, carbon fiber is drawn neat putting, at first cold pressing 3～4 times at the prepreg machine, then use 70 ℃ heating drum to carry out the dipping of opening fibre, resin of fiber.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, carbon fiber fill a part infiltration.Prepreg is put at room temperature, observed the variation of its viscosity, thereby determine 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, with the above-mentioned carbon fiber/epoxy resin unidirectional pre-immersion material that makes, by 16 layers of same direction stacks, put into mould.Be 0MPa at pressure, temperature is to solidify 45 minutes in 85 ℃ the moulding press, and then the pressure with moulding press rises to 1MPa, continues 85 ℃ of lower curing 75min minute, to finish primary solidification.After the primary solidification, again temperature is risen to 120 ℃ of beginning high temperature after fixing.The after fixing system is 120 ℃ of lower curing 2 hours, then solidifies 2 hours for 140 times, last 180 ℃ of lower curing 2 hours.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.Employing China Shenzhen CMT5105 electronic universal tester carries out quantitative measurement separately, the flexural strength test is with reference to GB3356-1999 " the crooked bending property test method 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 above-described embodiment 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 Resins, epoxy (Shanghai Resin Factory), the usage quantity of solid-state CYD-011 Resins, epoxy (Ba Ling petro-chemical corporation) respectively is 45 mass parts, 55 mass parts, and according to the composition of the Resins, epoxy of the identical processing methodes modulation comparative example 5 of embodiment 1 and embodiment 2.
With the composition epoxy resin of modulating like this, when the viscosity of composition epoxy resin is 20Pas, under 75 ℃, with scraping the skill in using a kitchen knife in cookery epoxy resin adhesive liquid is coated on the separate-type paper, the mass area ratio of system is 84g/m
2Resin film.
In addition, on above-mentioned resin film, carbon fiber is drawn neat putting, at first cold pressing 3～4 times at the prepreg machine, then use 90 ℃ heating drum to carry out the dipping of opening fibre, resin of fiber.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, carbon fiber fill a part infiltration.Prepreg is put at room temperature, observed the variation of its viscosity, thereby determine 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, with the above-mentioned carbon fiber/epoxy resin unidirectional pre-immersion material that makes, by 16 layers of same direction stacks, put into mould.Be 0MPa at pressure, temperature is to solidify 45 minutes in 120 ℃ the moulding press, and then the pressure with moulding press rises to 1MPa, continues 120 ℃ of lower curing 75min minute, to finish primary solidification.After the primary solidification, temperature is risen to 160 ℃ of beginning high temperature after fixing, whole rear curing time is 6h again, and the after fixing system is 160 ℃ of lower curing 2 hours, then solidifies 2 hours for 180 times, last 210 ℃ of lower curing 2 hours.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.Employing China Shenzhen CMT5105 electronic universal tester carries out quantitative measurement separately, the flexural strength test is with reference to GB3356-1999 " the crooked bending property test method 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 above-described embodiment 1 and embodiment 2 used same solidifying agent, consumption is 6 mass parts, same liquid E-51 Resins, epoxy (Shanghai Resin Factory), solid-state CYD-011 Resins, epoxy (Ba Ling petro-chemical corporation) usage quantity respectively is 40 mass parts, 60 mass parts, and according to the composition epoxy resin of the identical processing methodes modulation comparative example 6 of embodiment 1 and embodiment 2.
With the composition epoxy resin of modulating like this, when the viscosity of composition epoxy resin is 23Pas, under 70 ℃, with scraping the skill in using a kitchen knife in cookery epoxy resin adhesive liquid is coated on the separate-type paper, the mass area ratio of system is 84g/m
2Resin film.
In addition, on above-mentioned resin film, carbon fiber is drawn neat putting, at first cold pressing 3～4 times at the prepreg machine, then use 75 ℃ heating drum to carry out the dipping of opening fibre, resin of fiber.The travelling speed of fiber is 4m/min, and the roll-in number of times is 15 times.Prepreg is put at room temperature, observed the variation of its viscosity, thereby determine 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, with the above-mentioned carbon fiber/epoxy resin unidirectional pre-immersion material that makes, by 16 layers of same direction stacks, put into mould.Be 0MPa at pressure, temperature is to solidify 45 minutes in 120 ℃ the moulding press, and then the pressure with moulding press rises to 1MPa, continues 120 ℃ of lower curing 75min minute, to finish primary solidification.After the primary solidification, temperature is risen to 150 ℃ of beginning high temperature after fixing, whole rear curing time is 6h again, and the after fixing system is 150 ℃ of lower curing 2 hours, then solidifies 2 hours for 180 times, last 200 ℃ of lower curing 2 hours.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.Employing China Shenzhen CMT5105 electronic universal tester carries out quantitative measurement separately, the flexural strength test is with reference to GB3356-1999 " the crooked bending property test method 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 finish primary solidification, and the matrix material after the prepreg moulding that makes after itself and fortifying fibre are compound has good mechanical property 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.
Only for the preferred embodiment of invention, be not to limit practical range of the present invention in sum.Be that all equivalences of doing according to the content of the present patent application claim change and modification, all should be technology category of the present invention.
The concrete experiment condition of above-described embodiment 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 finish primary solidification, and the matrix material after the prepreg moulding that makes after itself and fortifying fibre are compound has good mechanical property 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.
Only for the preferred embodiment of invention, be not to limit practical range of the present invention in sum.Be that all equivalences of doing according to the content of the present patent application claim change and modification, all should be technology category of the present invention.
Claims (10)
1. a composition epoxy resin is characterized in that, said composition comprises:
A composition: the liquid bisphenol A Resins, epoxy of 33～35 mass parts;
B composition: the solid-state bisphenol A epoxide resin of 65～67 mass parts;
C composition: with respect to the Resins, epoxy of 100 mass parts, be the anhydride curing agent of 46～51 mass parts;
D composition: with respect to the Resins, epoxy of 100 mass parts, be the quaternary ammonium salt promotor of 1～2.5 mass parts;
With the E composition: with respect to the Resins, epoxy of 100 mass parts, be the acetyl acetone salt promotor of 0.05～1 mass parts.
2. composition epoxy resin as claimed in claim 1 is characterized in that, described A composition liquid bisphenol A Resins, epoxy is E-54 or E-51 or E-44 Resins, epoxy.
3. composition epoxy resin as claimed in claim 1 is characterized in that, the solid-state bisphenol A epoxide resin of described B composition is CYD-011 or CYD-012 or E-31 Resins, epoxy.
4. composition epoxy resin as claimed in claim 1 is characterized in that, described 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, it is characterized in that: described D composition quaternary ammonium salt promotor is benzyltriethylammoinium chloride or benzyl tributyl ammonium chloride.
6. composition epoxy resin as claimed in claim 1, it is characterized in that: described E composition acetyl acetone salt promotor is aluminium acetylacetonate or chromium acetylacetonate or titanium acetylacetone.
7. a method of using composition as claimed in claim 1 to prepare prepreg is characterized in that, may further comprise the steps:
Step 1 will be prepared into resin film by composition described in claim 1;
Step 2 adds fortifying fibre with the resin film of step 1 gained, colds pressing 3～4 times at the prepreg machine, then uses hot-pressing roller hot pressing, 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. the method for preparing prepreg as claimed in claim 7 is characterized in that, fortifying fibre is Unidirectional fiber 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 as claimed in claim 7 prepreg of method preparation in forming mould;
Step 2 close die heats, pressurization and moulding.
10. preparation method as claimed in claim 9 is characterized in that, described step 2 comprises
Following steps:
Step 2.1 primary solidification: be 0MPa at pressure, temperature is to solidify 30～45 minutes in 85 ℃ the moulding press, and then the pressure with moulding press rises to 1MPa, continues 85 ℃ of lower curing 75～90 minutes;
Step 2.2 after fixing: curing cycle is 120 ℃ of lower curing 2 hours, then 140 ℃ of lower 2h that solidify, then 180 ℃ of lower curing 2 hours.
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| CN103772912A (en) * | 2012-10-18 | 2014-05-07 | 中国石油化工股份有限公司 | Epoxy resin membrane for low temperature long-acting hot melt prepreg and preparation method thereof |
| CN104098873A (en) * | 2013-04-15 | 2014-10-15 | 中国石油化工股份有限公司 | Manufacturing method for composite-material plate for packer slips and composite-material plate |
| CN103342798B (en) * | 2013-07-16 | 2015-08-19 | 华东理工大学 | A kind of synthetic method of low viscosity, fire resistant modified epoxy |
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| CN104650542A (en) * | 2015-01-16 | 2015-05-27 | 中航复合材料有限责任公司 | Colorless transparent epoxy resin for prepreg and method for preparing composite material |
| CN104647636A (en) * | 2015-01-16 | 2015-05-27 | 中国航空工业集团公司基础技术研究院 | Preparation method of gradient prepreg with air guiding passage in layer |
| CN105552794A (en) * | 2016-02-05 | 2016-05-04 | 嘉兴学院 | Automobile line protection sleeve |
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| 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 |
| CN105820513B (en) * | 2016-05-27 | 2018-12-14 | 江苏兆鋆新材料股份有限公司 | A kind of cured epoxy resin carbon fiber prepreg of high temperature resistant and its preparation method and application |
| CN105968731B (en) * | 2016-05-27 | 2018-05-15 | 江苏兆鋆新材料股份有限公司 | A kind of temperature curing epoxy low resin carbon fibre prepreg and preparation method thereof |
| 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 |
| CN106987095B (en) * | 2017-05-16 | 2018-09-28 | 广东博汇新材料科技股份有限公司 | High transparency epoxy resin composition for prepreg and preparation method thereof |
| CN107652415A (en) * | 2017-09-12 | 2018-02-02 | 陕西飞机工业（集团）有限公司 | A kind of heating cure method of polymer matrix composites epoxy-resin systems |
| CN109777039B (en) * | 2018-12-04 | 2022-03-18 | 中山大学 | Epoxy resin composition rubber cake for chip LED packaging and preparation method and packaging process thereof |
| CN115819921B (en) * | 2022-11-14 | 2024-03-08 | 华北电力大学 | Preparation method and application of interface modified aramid fiber/epoxy resin composite material |
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