CN102964780A - Epoxy resin composition for vacuum introduction formation of fibre reinforced composite material and preparation method of epoxy resin composition - Google Patents
Epoxy resin composition for vacuum introduction formation of fibre reinforced composite material and preparation method of epoxy resin composition Download PDFInfo
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- CN102964780A CN102964780A CN2012105292276A CN201210529227A CN102964780A CN 102964780 A CN102964780 A CN 102964780A CN 2012105292276 A CN2012105292276 A CN 2012105292276A CN 201210529227 A CN201210529227 A CN 201210529227A CN 102964780 A CN102964780 A CN 102964780A
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Abstract
The invention relates to an epoxy resin composition for vacuum introduction formation of a fibre reinforced composite material and a preparation method of the epoxy resin composition. The epoxy resin composition comprises a component A and a component B, wherein the component A comprises the following ingredients in parts by mass: 100 parts of epoxy resin, 5-20 parts of diluent, 0.5-5.0 parts of silane coupling agent, 0.5-5.0 parts of inorganic filler; and the component B comprises the following ingredients in parts by mass: 25-45 parts of amine curing agent and 0.5-5.0 parts of accelerant. According to the invention, blend type epoxy resins of hydantoin epoxy resins and low-viscosity epoxy resins (4,5-epoxy cyclohexane-1,2-dioctyl phthalate diglycidyl ester, bisphenol F type glycidyl ether epoxy resin or bisphenol A type glycidyl ether epoxy resin) are adopted as a resin matrix, so that the requirement of vacuum introduction formation of the fibre reinforced composite material for the resin low viscosity can be met, and a composite material product has excellent high temperature resistance property.
Description
Technical field
The present invention relates to a kind of composition epoxy resin and preparation method thereof, especially be applicable to composition epoxy resin of fibre reinforced composites vacuum guiding and forming technique and preparation method thereof.
Background technology
Vacuum introducing technology (Vacuum infusion proccss, being called for short VIP) patent records has appearred in nineteen fifty, so far have the history in more than 50 year, its principle is " to do " strongthener (glass fibre, carbon fiber, Sandwich materials etc.) on the mould upper berth, then seal with vacuum bag, and system is evacuated to vacuum state, in mold cavity, form a negative pressure, the pressure that the recycling vacuum produces is pressed into resin in the layer of fibers by the pipeline that the top spreads, and allows resin infiltrate strongthener and is full of at last whole mould.Goods are thrown off vacuum bag material after solidifying, and obtain required composite product from mould.Because the lay that its technological process comprises preform and the injection of resin and solidify two and go on foot to separate and carry out, the vacuum introducing technology has handiness and the associativity of height thus, be convenient to realize " design of material ", be widely used at present the industrial circles such as building, automobile, boats and ships, wind-powered electricity generation.
Resins, epoxy be widely used at present, the fibre reinforced composites body material of superior performance.But there is the shortcoming of toughness deficiency in Resins, epoxy after curing, can not effectively bring into play the performance of fortifying fibre, when carry load often because the destruction that the premature failure of Resins, epoxy causes matrix material.In order to adapt to high performance composites to the demand of matrix resin, the modification of Resins, epoxy is the study hotspot of association area always, and the Resins, epoxy that has toughness, intensity, thermotolerance and excellent processing characteristics concurrently is the developing direction of epoxy resin modification always.
In order to satisfy the requirement of vacuum guiding and forming technique, required resin matrix need to have that viscosity is low, intensity is high, good toughness, with the fiber cohesiveness good processing performance such as good.Yet, be used in the market the large or thermotolerance of the general viscosity of Resins, epoxy of vacuum guiding and forming technique, poor toughness, therefore the exploitation composition epoxy resin that is applicable to vacuum guiding and forming technique becomes study hotspot in recent years.
Summary of the invention
The invention provides a kind of composition epoxy resin that imports moulding for the fibre reinforced composites vacuum and preparation method thereof, the technical problem of its solution is that the Resins, epoxy that is used in the market vacuum guiding and forming technique exists that viscosity is large, the defective of thermotolerance and poor toughness.
A kind of composition epoxy resin that imports moulding for the fibre reinforced composites vacuum, it comprises component A and B component, and wherein component A comprises following compositions: 100 mass parts Resins, epoxy, 5-20 mass parts thinner, 0.5-5.0 mass parts silane coupling agent, the mineral filler of 0.5-5.0 mass parts; B component comprises following compositions: 25-45 mass parts amine curing agent, 0.5-5.0 mass parts promotor.
Further, described Resins, epoxy is the combination of Resins, epoxy a and Resins, epoxy b, and the mass ratio of Resins, epoxy a and Resins, epoxy b is: 50-80:20-50; Described Resins, epoxy a is for comprising glycidic amine type, glycidyl ether type or the glycidyl ester type glycolylurea epoxide resin of one or more glycolylurea rings (five yuan of diazacyclos), glycolylurea ring (five yuan of diazacyclos) structural formula is as follows, substituent R in glycolylurea ring (the five yuan of diazacyclos) structural formula
1And R
2Be H, CH
3, C
2H
5, aryl or aralkyl:
Described Resins, epoxy b is at least a in following several Resins, epoxy: 4,5-oxirane ring ethane-1,2-dioctyl phthalate 2-glycidyl ester, Bisphenol F type glycidyl ether based epoxy resin or bisphenol A-type glycidyl ether based epoxy resin; Wherein, Bisphenol F type glycidyl ether based epoxy resin or bisphenol A-type glycidyl ether based epoxy resin preferred viscosity ranges: 500-4000mPas(25 ℃).
Further, described Resins, epoxy a is the 2-glycidyl amine type glycolylurea epoxide resin that contains a glycolylurea ring, and chemical structural formula is as follows:
Substituent R wherein
1And R
2There is following combination selection mode: 1) R
1Be H, R
2Compound for H; 2) R
1Be CH
3, R
2Compound for H; 3) R
1Be CH
3, R
2Be CH
3Compound; 4) R
1Be C
2H
5, R
2Compound for H; 5) R
1Be C
2H
5, R
2Be CH
3Compound.
Further, described amine curing agent is the combination of amine curing agent a and amine curing agent b, and the mass ratio of amine curing agent a and amine curing agent b is: 20-40:5-25; Described amine curing agent a is the polyether monoamine compound that comprises two or more amido functional groups, preferably from molecular weight ranges 200-2500, range of viscosities: 5-300mPas(25 ℃) the polyether monoamine compound in one or more; Described amine curing agent b is one or more of aliphatics amine and modified aliphatic aminated compounds, preferably from: diethylenetriamine, triethylene tetramine, tetraethylene pentamine, one or more in diamines, methylol quadrol, methylol diethylenetriamine, the beta-hydroxyethyl quadrol.
Further, described promotor is selected from: one or more in 2,4,6-three (dimethylamino methyl) phenol, boron trifluoride complex, the trolamine.
Further, described thinner is the compound that comprises two epoxy functionality and at least one ehter bond, preferably certainly: one or more in ethylene glycol diglycidylether, butanediol diglycidyl ether, hexanediol diglycidyl ether, cylohexanediol diglycidyl ether, cyclohexanedimethanodiglycidyl diglycidyl ether, neopentylglycol diglycidyl ether, polyethyleneglycol diglycidylether, the resorcinol diglycidyl ether.
Further, described coupling agent is the silane coupling agent that comprises epoxy functionality; Be preferably γ-aminopropyl triethoxysilane, a kind of in γ-glycidyl ether oxygen propyl trimethoxy silicane or γ-(methacryloxy) propyl trimethoxy silicane.
Further, mineral filler is selected from: one or more in kaolin, bauxitic clay, aluminium hydroxide, titanium stone flour or the metal oxide.
A kind ofly import the preparation method of the composition epoxy resin of moulding for the fibre reinforced composites vacuum, may further comprise the steps: step 1, with the composition Resins, epoxy a among the component A and b below 40 ℃ with 800-1000 rev/min speed mechanical dispersed with stirring 5-10 minute; Step 2, add successively mineral filler, thinner and coupling agent while stirring, with 800-1000 rev/min speed mechanical dispersed with stirring set aside for use under the room temperature after 5-10 minute; Step 3, with the composition amine curing agent a in the B component and b at room temperature with 600-800 rev/min speed mechanical dispersed with stirring 5-10 minute; Step 4, add promotor while stirring, at room temperature with 600-800 rev/min speed mechanical dispersed with stirring 5-10 minute; Step 5, at room temperature (25 ℃) component A and B component are mixed, with 3000-3500 rev/min speed mechanical dispersed with stirring 3-5 minute; Namely get the described composition epoxy resin that imports moulding for the fibre reinforced composites vacuum after step 6, the vacuum defoamation.
The present invention is used for composition epoxy resin of fibre reinforced composites vacuum importing moulding and preparation method thereof and compares with existing composition epoxy resin that is used for fibre reinforced composites vacuum importing moulding and preparation method thereof, has following beneficial effect:
(1) the present invention adopts glycolylurea epoxide resin and low viscosity epoxy resin (4,5-oxirane ring ethane-1,2-dioctyl phthalate 2-glycidyl ester, Bisphenol F type glycidyl ether based epoxy resin or bisphenol A-type glycidyl ether based epoxy resin) commixed type Resins, epoxy as resin matrix, can not only satisfy the fibre reinforced composites vacuum and import moulding to the low viscous requirement of resin, can also make composite product possess excellent resistance to elevated temperatures.
(2) glycolylurea epoxide resin that uses among the present invention has low, the good manufacturability of viscosity, glass fibre, carbon fiber and multiple filler there is good wetting property, owing to comprise five yuan of diazacyclos in its structure, also have the characteristics such as Heat stability is good, thermotolerance is high, weather resisteant is good concurrently.
(3) comprise the toughness functional groups such as a plurality of ehter bonds in the polyether monoamine solidifying agent structure of using among the present invention, can make composite product have the shock resistance of high-strength and high ductility, by adopting the commixed type curing system of polyether monoamine solidifying agent and aliphatics amine solidifying agent, can effectively solve the problems such as cured article fragility, elongation at break are little.
(4) the present invention adopts a certain amount of promotor to cooperate the commixed type amine curing agent to use together, can effectively solve the problem of self-vulcanizing overlong time, has guaranteed that the intensity of cured article remains unchanged substantially when shortening set time.
(5) the present invention adopts mineral filler can reduce the shrinking percentage of goods, improves dimensional stability, surface smoothness and the smoothness etc. of goods, also can improve to a certain extent shock strength and the compressive strength of goods; In addition, the adding of filler can reduce the consumption of Resins, epoxy, reduces cost.
(6) auxiliary agent of the present invention's employing also comprises silane coupling agent and thinner.Wherein silane coupling agent can improve bond strength between reinforcing fiber materials and the resin, improves interfacial state, is conducive to improve mechanical property and the electrical insulation capability of composite product; The effect of thinner can reduce the viscosity of whole composition.
Embodiment
Below embodiment of the present invention will be described, further understand the present invention.
Embodiment 1: with 50.0g glycolylurea epoxide resin MHR-070(available from Wuxi Meihua Chemical Co., Ltd., oxirane value is 0.70-0.74), 50.0g bisphenol A-type glycidyl ether based epoxy resin E-51(is available from Wuxi Resin Factory of Blue Star New Chemical Material Co., Ltd., oxirane value is 0.48-0.54) under 30 ℃ with 800 rev/mins speed mechanical dispersed with stirring 5 minutes, add successively while stirring 0.5g kaolin, 10.0g 1, the 4-butanediol diglycidyl ether, 0.5g γ-glycidyl ether oxygen propyl trimethoxy silicane, with 800 rev/mins speed mechanical dispersed with stirring set aside for use under the room temperature after 10 minutes, with 20.0g polyetheramine D230 and 10.0g triethylene tetramine at room temperature with 600 rev/mins speed mechanical dispersed with stirring 5 minutes, add 0.5g 2 while stirring, 4,6-three (dimethylamino methyl) phenol is at room temperature with 600 rev/mins speed mechanical dispersed with stirring 5 minutes.At room temperature said components is mixed, with 3000 rev/mins speed mechanical dispersed with stirring 3 minutes, namely get described composition epoxy resin after the vacuum defoamation, then pour die casting into and solidify.The exothermic heat of reaction curve of dsc (DSC method) test wrapper epoxy resin system, 5 ℃/min of temperature rise rate and 15 ℃/min, obtaining program curing by extrapotation is 35 ℃ of curing 1 hour, and 110 ℃ solidified 2 hours, and 180 ℃ solidified 2 hours.According to standard GB/T/T 16421-1996 tensile strength, tension set, the modulus in tension of the epoxy matrix resin of preparation are tested, specimen size is as follows: length is 100mm ± 0.5mm, the end width is 10mm ± 0.5mm, narrow parallel portion length 30mm ± 0.5mm, narrow parallel portion width 5mm ± 0.2mm, thickness is 2.2mm ± 0.2mm.Experiment repeats six times, and the tensile strength that records this epoxy matrix resin is 59MPa, tension set 4.0%, modulus in tension 2.5GPa.According to standard GB/T/T 16419-1996 flexural strength, the bending elastic modulus of the epoxy matrix resin of preparation are tested, specimen size is as follows: length is 40mm, and width is 3mm ± 0.2mm, and thickness is 2mm ± 0.2mm.Experiment repeats six times, and the flexural strength that records this epoxy matrix resin is 106MPa, bending elastic modulus 3.3GPa.Dsc (DSC method) is surveyed second-order transition temperature, 5 ℃/min of temperature rise rate, and the second-order transition temperature that records epoxy matrix resin is 155 ℃, adopts NDJ-8S type rotational viscosimeter testing tree oil/fat composition viscosity, the viscosity in the time of 25 ℃ is 480mPas.
Embodiment 2: with 80.0g glycolylurea epoxide resin MHR-070(available from Wuxi Meihua Chemical Co., Ltd., oxirane value is 0.70-0.74), 20.0g bisphenol A-type glycidyl ether based epoxy resin E-51(is available from Wuxi Resin Factory of Blue Star New Chemical Material Co., Ltd., oxirane value is 0.48-0.54) under 40 ℃ with 900 rev/mins speed mechanical dispersed with stirring 8 minutes, add successively while stirring 2.5g kaolin, 20.0g 1, the 4-butanediol diglycidyl ether, 2.5g γ-glycidyl ether oxygen propyl trimethoxy silicane, with 900 rev/mins speed mechanical dispersed with stirring set aside for use under the room temperature after 10 minutes, with 40.0g polyetheramine D230 and 5.0g triethylene tetramine at room temperature with 600 rev/mins speed mechanical dispersed with stirring 5 minutes, add 5.0g 2 while stirring, 4,6-three (dimethylamino methyl) phenol is at room temperature with 600 rev/mins speed mechanical dispersed with stirring 10 minutes.At room temperature said components is mixed, with 3000 rev/mins speed mechanical dispersed with stirring 5 minutes, namely get described composition epoxy resin after the vacuum defoamation, then pour die casting into and solidify.The exothermic heat of reaction curve of dsc (DSC method) test wrapper epoxy resin system, 5 ℃/min of temperature rise rate and 15 ℃/min, obtaining program curing by extrapotation is 41 ℃ of curing 1 hour, and 116 ℃ solidified 2 hours, and 180 ℃ solidified 2 hours.According to standard GB/T/T 16421-1996 tensile strength, tension set, the modulus in tension of the epoxy matrix resin of preparation are tested, specimen size is as follows: length is 100mm ± 0.5mm, the end width is 10mm ± 0.5mm, narrow parallel portion length 30mm ± 0.5mm, narrow parallel portion width 5mm ± 0.2mm, thickness is 2.2mm ± 0.2mm.Experiment repeats six times, and the tensile strength that records this epoxy matrix resin is 65MPa, tension set 4.3%, modulus in tension 2.6GPa.According to standard GB/T/T 16419-1996 flexural strength, the bending elastic modulus of the epoxy matrix resin of preparation are tested, specimen size is as follows: length is 40mm, and width is 3mm ± 0.2mm, and thickness is 2mm ± 0.2mm.Experiment repeats six times, and the flexural strength that records this epoxy matrix resin is 110MPa, bending elastic modulus 3.4GPa.Dsc (DSC method) is surveyed second-order transition temperature, 5 ℃/min of temperature rise rate, and the second-order transition temperature that records epoxy matrix resin is 162 ℃, adopts NDJ-8S type rotational viscosimeter testing tree oil/fat composition viscosity, the viscosity in the time of 25 ℃ is 375mPas.
Embodiment 3: with 80.0g glycolylurea epoxide resin MHR-070(available from Wuxi Meihua Chemical Co., Ltd., oxirane value is 0.70-0.74), 20.0g 4,5-oxirane ring ethane-1,2-dioctyl phthalate 2-glycidyl ester TDE-86(is available from the brilliant eastern chemically composited Materials Co., Ltd in Tianjin, oxirane value is 0.88) under 40 ℃ with 1000 rev/mins speed mechanical dispersed with stirring 8 minutes, add successively while stirring 5.0g aluminium hydroxide, 10.0g cylohexanediol diglycidyl ether, 5.0g γ-(methacryloxy) propyl trimethoxy silicane, with 1000 rev/mins speed mechanical dispersed with stirring set aside for use under the room temperature after 10 minutes, with 32.0g polyetheramine D230,8.0g polyetheramine D2000 and 5.0g tetraethylene pentamine are at room temperature with 700 rev/mins speed mechanical dispersed with stirring 10 minutes, add the 2.5g boron trifluoride ethylamine while stirring, at room temperature with 700 rev/mins speed mechanical dispersed with stirring 10 minutes.At room temperature said components is mixed, with 3500 rev/mins speed mechanical dispersed with stirring 5 minutes, namely get described composition epoxy resin after the vacuum defoamation, then pour die casting into and solidify.The exothermic heat of reaction curve of dsc (DSC method) test wrapper epoxy resin system, 5 ℃/min of temperature rise rate and 15 ℃/min, obtaining program curing by extrapotation is 39 ℃ of curing 1 hour, and 104 ℃ solidified 2 hours, and 166 ℃ solidified 2 hours.According to standard GB/T/T 16421-1996 tensile strength, tension set, the modulus in tension of the epoxy matrix resin of preparation are tested, specimen size is as follows: length is 100mm ± 0.5mm, the end width is 10mm ± 0.5mm, narrow parallel portion length 30mm ± 0.5mm, narrow parallel portion width 5mm ± 0.2mm, thickness is 2.2mm ± 0.2mm.Experiment repeats six times, and the tensile strength that records this epoxy matrix resin is 60MPa, tension set 4.1%, modulus in tension 2.5GPa.According to standard GB/T/T 16419-1996 flexural strength, the bending elastic modulus of the epoxy matrix resin of preparation are tested, specimen size is as follows: length is 40mm, and width is 3mm ± 0.2mm, and thickness is 2mm ± 0.2mm.Experiment repeats six times, and the flexural strength that records this epoxy matrix resin is 132MPa, bending elastic modulus 3.3GPa.Dsc (DSC method) is surveyed second-order transition temperature, 5 ℃/min of temperature rise rate, and the second-order transition temperature that records epoxy matrix resin is 171 ℃, adopts NDJ-8S type rotational viscosimeter testing tree oil/fat composition viscosity, the viscosity in the time of 25 ℃ is 441mPas.
Embodiment 4: with 65.0g glycolylurea epoxide resin MHR-070(available from Wuxi Meihua Chemical Co., Ltd., oxirane value is 0.70-0.74), 35.0g 4,5-oxirane ring ethane-1,2-dioctyl phthalate 2-glycidyl ester TDE-86(is available from the brilliant eastern chemically composited Materials Co., Ltd in Tianjin, oxirane value is 0.88) under 40 ℃ with 900 rev/mins speed mechanical dispersed with stirring 8 minutes, add successively while stirring 2.5g aluminium hydroxide, 20.0g cylohexanediol diglycidyl ether, 2.5g γ-(methacryloxy) propyl trimethoxy silicane, with 900 rev/mins speed mechanical dispersed with stirring set aside for use under the room temperature after 10 minutes, with 16.0g polyetheramine D230,4.0g polyetheramine D2000 and 5.0g tetraethylene pentamine are at room temperature with 600 rev/mins speed mechanical dispersed with stirring 5 minutes, add the 2.5g boron trifluoride ethylamine while stirring, at room temperature with 600 rev/mins speed mechanical dispersed with stirring 10 minutes.At room temperature said components is mixed, with 3300 rev/mins speed mechanical dispersed with stirring 5 minutes, namely get described composition epoxy resin after the vacuum defoamation, then pour die casting into and solidify.The exothermic heat of reaction curve of dsc (DSC method) test wrapper epoxy resin system, 5 ℃/min of temperature rise rate and 15 ℃/min, obtaining program curing by extrapotation is 43 ℃ of curing 1 hour, and 120 ℃ solidified 2 hours, and 170 ℃ solidified 2 hours.According to standard GB/T/T 16421-1996 tensile strength, tension set, the modulus in tension of the epoxy matrix resin of preparation are tested, specimen size is as follows: length is 100mm ± 0.5mm, the end width is 10mm ± 0.5mm, narrow parallel portion length 30mm ± 0.5mm, narrow parallel portion width 5mm ± 0.2mm, thickness is 2.2mm ± 0.2mm.Experiment repeats six times, and the tensile strength that records this epoxy matrix resin is 63MPa, tension set 4.3%, modulus in tension 2.6GPa.According to standard GB/T/T 16419-1996 flexural strength, the bending elastic modulus of the epoxy matrix resin of preparation are tested, specimen size is as follows: length is 40mm, and width is 3mm ± 0.2mm, and thickness is 2mm ± 0.2mm.Experiment repeats six times, and the flexural strength that records this epoxy matrix resin is 126MPa, bending elastic modulus 3.3GPa.Dsc (DSC method) is surveyed second-order transition temperature, 5 ℃/min of temperature rise rate, and the second-order transition temperature that records epoxy matrix resin is 174 ℃, adopts NDJ-8S type rotational viscosimeter testing tree oil/fat composition viscosity, the viscosity in the time of 25 ℃ is 341mPas.
Embodiment 5: with 50.0g glycolylurea epoxide resin MHR-070(available from Wuxi Meihua Chemical Co., Ltd., oxirane value is 0.70-0.74), 50.0g 4,5-oxirane ring ethane-1,2-dioctyl phthalate 2-glycidyl ester TDE-86(is available from the brilliant eastern chemically composited Materials Co., Ltd in Tianjin, oxirane value is 0.88) under 40 ℃ with 900 rev/mins speed mechanical dispersed with stirring 8 minutes, add successively while stirring 2.5g aluminium hydroxide, 20.0g cylohexanediol diglycidyl ether, 2.5g γ-aminopropyl triethoxysilane, with 900 rev/mins speed mechanical dispersed with stirring set aside for use under the room temperature after 10 minutes, with 32.0g polyetheramine D230,8.0g polyetheramine D2000 and 5.0g tetraethylene pentamine are at room temperature with 600 rev/mins speed mechanical dispersed with stirring 5 minutes, add the 5.0g boron trifluoride ethylamine while stirring, at room temperature with 600 rev/mins speed mechanical dispersed with stirring 10 minutes.At room temperature said components is mixed, with 3300 rev/mins speed mechanical dispersed with stirring 5 minutes, namely get described composition epoxy resin after the vacuum defoamation, then pour die casting into and solidify.The exothermic heat of reaction curve of dsc (DSC method) test wrapper epoxy resin system, 5 ℃/min of temperature rise rate and 15 ℃/min, obtaining program curing by extrapotation is 52 ℃ of curing 1 hour, and 133 ℃ solidified 2 hours, and 180 ℃ solidified 2 hours.According to standard GB/T/T 16421-1996 tensile strength, tension set, the modulus in tension of the epoxy matrix resin of preparation are tested, specimen size is as follows: length is 100mm ± 0.5mm, the end width is 10mm ± 0.5mm, narrow parallel portion length 30mm ± 0.5mm, narrow parallel portion width 5mm ± 0.2mm, thickness is 2.2mm ± 0.2mm.Experiment repeats six times, and the tensile strength that records this epoxy matrix resin is 66MPa, tension set 4.2%, modulus in tension 2.5GPa.According to standard GB/T/T 16419-1996 flexural strength, the bending elastic modulus of the epoxy matrix resin of preparation are tested, specimen size is as follows: length is 40mm, and width is 3mm ± 0.2mm, and thickness is 2mm ± 0.2mm.Experiment repeats six times, and the flexural strength that records this epoxy matrix resin is 130MPa, bending elastic modulus 3.4GPa.Dsc (DSC method) is surveyed second-order transition temperature, 5 ℃/min of temperature rise rate, and the second-order transition temperature that records epoxy matrix resin is 176 ℃, adopts NDJ-8S type rotational viscosimeter testing tree oil/fat composition viscosity, the viscosity in the time of 25 ℃ is 363mPas.
Embodiment 6: with 50.0g glycolylurea epoxide resin MHR-070(available from Wuxi Meihua Chemical Co., Ltd., oxirane value is 0.70-0.74), 50.0g bisphenol F epoxy resin 862(is available from Shenzhen letter Rong Xiang economy and trade company limited, oxirane value is 0.58-0.61) under 40 ℃ with 900 rev/mins speed mechanical dispersed with stirring 7 minutes, add successively while stirring 3.0g titanium stone flour, 15.0g cyclohexanedimethanodiglycidyl diglycidyl ether, 3.0g γ-aminopropyl triethoxysilane, with 900 rev/mins speed mechanical dispersed with stirring set aside for use under the room temperature after 7 minutes, with 35.0g polyetheramine D400 and 10.0g methylol diethylenetriamine at room temperature with 600 rev/mins speed mechanical dispersed with stirring 5 minutes, add the 5.0g boron trifluoride ethylamine while stirring, at room temperature with 600 rev/mins speed mechanical dispersed with stirring 10 minutes.At room temperature said components is mixed, with 3300 rev/mins speed mechanical dispersed with stirring 4 minutes, namely get described composition epoxy resin after the vacuum defoamation, then pour die casting into and solidify.The exothermic heat of reaction curve of dsc (DSC method) test wrapper epoxy resin system, 5 ℃/min of temperature rise rate and 15 ℃/min, obtaining program curing by extrapotation is 47 ℃ of curing 1 hour, and 113 ℃ solidified 2 hours, and 160 ℃ solidified 2 hours.According to standard GB/T/T 16421-1996 tensile strength, tension set, the modulus in tension of the epoxy matrix resin of preparation are tested, specimen size is as follows: length is 100mm ± 0.5mm, the end width is 10mm ± 0.5mm, narrow parallel portion length 30mm ± 0.5mm, narrow parallel portion width 5mm ± 0.2mm, thickness is 2.2mm ± 0.2mm.Experiment repeats six times, and the tensile strength that records this epoxy matrix resin is 63MPa, tension set 4.0%, modulus in tension 2.5GPa.According to standard GB/T/T 16419-1996 flexural strength, the bending elastic modulus of the epoxy matrix resin of preparation are tested, specimen size is as follows: length is 40mm, and width is 3mm ± 0.2mm, and thickness is 2mm ± 0.2mm.Experiment repeats six times, and the flexural strength that records this epoxy matrix resin is 126MPa, bending elastic modulus 3.3GPa.Dsc (DSC method) is surveyed second-order transition temperature, 5 ℃/min of temperature rise rate, and the second-order transition temperature that records epoxy matrix resin is 168 ℃, adopts NDJ-8S type rotational viscosimeter testing tree oil/fat composition viscosity, the viscosity in the time of 25 ℃ is 344mPas.
Embodiment 7: with 50.0g glycolylurea epoxide resin MHR-154(available from Wuxi Meihua Chemical Co., Ltd., oxirane value is 0.52-0.55), 50.0g bisphenol F epoxy resin 862(is available from Shenzhen letter Rong Xiang economy and trade company limited, oxirane value is 0.58-0.61) under 40 ℃ with 1000 rev/mins speed mechanical dispersed with stirring 10 minutes, add successively while stirring the 2.5g bauxitic clay, 20.0g ethylene glycol diglycidylether, 2.5g γ-glycidyl ether oxygen propyl trimethoxy silicane, with 1000 rev/mins speed mechanical dispersed with stirring set aside for use under the room temperature after 10 minutes, with 30.0g polyetheramine D2000 and 5.0g methylol quadrol at room temperature with 800 rev/mins speed mechanical dispersed with stirring 5 minutes, add the 2.5g trolamine while stirring, at room temperature with 800 rev/mins speed mechanical dispersed with stirring 10 minutes.At room temperature said components is mixed, with 3500 rev/mins speed mechanical dispersed with stirring 5 minutes, namely get described composition epoxy resin after the vacuum defoamation, then pour die casting into and solidify.The exothermic heat of reaction curve of dsc (DSC method) test wrapper epoxy resin system, 5 ℃/min of temperature rise rate and 15 ℃/min, obtaining program curing by extrapotation is 43 ℃ of curing 1 hour, and 120 ℃ solidified 2 hours, and 170 ℃ solidified 2 hours.According to standard GB/T/T 16421-1996 tensile strength, tension set, the modulus in tension of the epoxy matrix resin of preparation are tested, specimen size is as follows: length is 100mm ± 0.5mm, the end width is 10mm ± 0.5mm, narrow parallel portion length 30mm ± 0.5mm, narrow parallel portion width 5mm ± 0.2mm, thickness is 2.2mm ± 0.2mm.Experiment repeats six times, and the tensile strength that records this epoxy matrix resin is 52MPa, tension set 3.8%, modulus in tension 1.6GPa.According to standard GB/T/T 16419-1996 flexural strength, the bending elastic modulus of the epoxy matrix resin of preparation are tested, specimen size is as follows: length is 40mm, and width is 3mm ± 0.2mm, and thickness is 2mm ± 0.2mm.Experiment repeats six times, and the flexural strength that records this epoxy matrix resin is 101MPa, bending elastic modulus 3.1GPa.Dsc (DSC method) is surveyed second-order transition temperature, 5 ℃/min of temperature rise rate, and the second-order transition temperature that records epoxy matrix resin is 184 ℃, adopts NDJ-8S type rotational viscosimeter testing tree oil/fat composition viscosity, the viscosity in the time of 25 ℃ is 510mPas.
Embodiment 8: with 70.0g glycolylurea epoxide resin MHR-154(available from Wuxi Meihua Chemical Co., Ltd., oxirane value is 0.52-0.55), 30.0g bisphenol F epoxy resin 862(is available from Shenzhen letter Rong Xiang economy and trade company limited, oxirane value is 0.58-0.61) under 40 ℃ with 1000 rev/mins speed mechanical dispersed with stirring 10 minutes, add successively while stirring the 2.5g bauxitic clay, 20.0g 1, the 4-butanediol diglycidyl ether, 2.5g γ-glycidyl ether oxygen propyl trimethoxy silicane, with 1000 rev/mins speed mechanical dispersed with stirring set aside for use under the room temperature after 7 minutes, with 30.0g polyetheramine D400 and 5.0g tetraethylene pentamine at room temperature with 800 rev/mins speed mechanical dispersed with stirring 5 minutes, add the 2.5g boron trifluoride ethylamine while stirring, at room temperature with 800 rev/mins speed mechanical dispersed with stirring 7 minutes.At room temperature said components is mixed, with 3500 rev/mins speed mechanical dispersed with stirring 5 minutes, namely get described composition epoxy resin after the vacuum defoamation, then pour die casting into and solidify.The exothermic heat of reaction curve of dsc (DSC method) test wrapper epoxy resin system, 5 ℃/min of temperature rise rate and 15 ℃/min, obtaining program curing by extrapotation is 67 ℃ of curing 1 hour, and 130 ℃ solidified 2 hours, and 180 ℃ solidified 2 hours.According to standard GB/T/T 16421-1996 tensile strength, tension set, the modulus in tension of the epoxy matrix resin of preparation are tested, specimen size is as follows: length is 100mm ± 0.5mm, the end width is 10mm ± 0.5mm, narrow parallel portion length 30mm ± 0.5mm, narrow parallel portion width 5mm ± 0.2mm, thickness is 2.2mm ± 0.2mm.Experiment repeats six times, and the tensile strength that records this epoxy matrix resin is 53MPa, tension set 3.9%, modulus in tension 1.6GPa.According to standard GB/T/T 16419-1996 flexural strength, the bending elastic modulus of the epoxy matrix resin of preparation are tested, specimen size is as follows: length is 40mm, and width is 3mm ± 0.2mm, and thickness is 2mm ± 0.2mm.Experiment repeats six times, and the flexural strength that records this epoxy matrix resin is 119MPa, bending elastic modulus 3.2GPa.Dsc (DSC method) is surveyed second-order transition temperature, 5 ℃/min of temperature rise rate, and the second-order transition temperature that records epoxy matrix resin is 182 ℃, adopts NDJ-8S type rotational viscosimeter testing tree oil/fat composition viscosity, the viscosity in the time of 25 ℃ is 490mPas.
The above has carried out exemplary description to the present invention in conjunction with the embodiments; obvious realization of the present invention is not subjected to the restriction of aforesaid way; as long as the various improvement of having adopted method design of the present invention and technical scheme to carry out; or without improving design of the present invention and technical scheme are directly applied to other occasion, all in protection scope of the present invention.
Claims (9)
1. one kind is used for the composition epoxy resin that the fibre reinforced composites vacuum imports moulding, it is characterized in that: it comprises component A and B component, and wherein component A comprises following compositions: 100 mass parts Resins, epoxy, 5-20 mass parts thinner, 0.5-5.0 mass parts silane coupling agent, the mineral filler of 0.5-5.0 mass parts; B component comprises following compositions: 25-45 mass parts amine curing agent, 0.5-5.0 mass parts promotor.
2. the described composition epoxy resin that imports moulding for the fibre reinforced composites vacuum according to claim 1, it is characterized in that: described Resins, epoxy is the combination of Resins, epoxy a and Resins, epoxy b, and the mass ratio of Resins, epoxy a and Resins, epoxy b is: 50-80:20-50; Described Resins, epoxy a is for comprising glycidic amine type, glycidyl ether type or the glycidyl ester type glycolylurea epoxide resin of one or more glycolylurea rings (five yuan of diazacyclos), glycolylurea ring (five yuan of diazacyclos) structural formula is as follows, substituent R in glycolylurea ring (the five yuan of diazacyclos) structural formula
1And R
2Be H, CH
3, C
2H
5, aryl or aralkyl:
Described Resins, epoxy b is at least a in following several Resins, epoxy: 4,5-oxirane ring ethane-1,2-dioctyl phthalate 2-glycidyl ester, Bisphenol F type glycidyl ether based epoxy resin or bisphenol A-type glycidyl ether based epoxy resin; Wherein, Bisphenol F type glycidyl ether based epoxy resin or bisphenol A-type glycidyl ether based epoxy resin preferred viscosity ranges: 500-4000mPas(25 ℃).
3. describedly according to claim 2 import the composition epoxy resin of moulding for the fibre reinforced composites vacuum, it is characterized in that: described Resins, epoxy a is the 2-glycidyl amine type glycolylurea epoxide resin that contains a glycolylurea ring, and chemical structural formula is as follows:
Substituent R wherein
1And R
2There is following combination selection mode: 1) R
1Be H, R
2Compound for H; 2) R
1Be CH
3, R
2Compound for H; 3) R
1Be CH
3, R
2Be CH
3Compound; 4) R
1Be C
2H
5, R
2Compound for H; 5) R
1Be C
2H
5, R
2Be CH
3Compound.
4. the described composition epoxy resin that imports moulding for the fibre reinforced composites vacuum according to claim 1, it is characterized in that: described amine curing agent is the combination of amine curing agent a and amine curing agent b, and the mass ratio of amine curing agent a and amine curing agent b is: 20-40:5-25; Described amine curing agent a is the polyether monoamine compound that comprises two or more amido functional groups, preferably from molecular weight ranges 200-2500, range of viscosities: 5-300mPas(25 ℃) the polyether monoamine compound in one or more; Described amine curing agent b is one or more of aliphatics amine and modified aliphatic aminated compounds, preferably from: diethylenetriamine, triethylene tetramine, tetraethylene pentamine, one or more in diamines, methylol quadrol, methylol diethylenetriamine, the beta-hydroxyethyl quadrol.
5. the described composition epoxy resin that imports moulding for the fibre reinforced composites vacuum according to claim 1, it is characterized in that: described promotor is selected from: 2, in 4,6-three (dimethylamino methyl) phenol, boron trifluoride complex, the trolamine one or more.
6. the described composition epoxy resin that imports moulding for the fibre reinforced composites vacuum according to claim 1, it is characterized in that: described thinner is the compound that comprises two epoxy functionality and at least one ehter bond, preferably certainly: one or more in ethylene glycol diglycidylether, butanediol diglycidyl ether, hexanediol diglycidyl ether, cylohexanediol diglycidyl ether, cyclohexanedimethanodiglycidyl diglycidyl ether, neopentylglycol diglycidyl ether, polyethyleneglycol diglycidylether, the resorcinol diglycidyl ether.
7. describedly according to claim 1 import the composition epoxy resin of moulding for the fibre reinforced composites vacuum, it is characterized in that: described coupling agent is the silane coupling agent that comprises epoxy functionality; Be preferably γ-aminopropyl triethoxysilane, a kind of in γ-glycidyl ether oxygen propyl trimethoxy silicane or γ-(methacryloxy) propyl trimethoxy silicane.
8. describedly according to claim 1 import the composition epoxy resin of moulding for the fibre reinforced composites vacuum, it is characterized in that: mineral filler is selected from: one or more in kaolin, bauxitic clay, aluminium hydroxide, titanium stone flour or the metal oxide.
A claim 1-8 each describedly import the preparation method of the composition epoxy resin of moulding for the fibre reinforced composites vacuum, may further comprise the steps: step 1, with the composition Resins, epoxy a among the component A and b below 40 ℃ with 800-1000 rev/min speed mechanical dispersed with stirring 5-10 minute; Step 2, add successively mineral filler, thinner and coupling agent while stirring, with 800-1000 rev/min speed mechanical dispersed with stirring set aside for use under the room temperature after 5-10 minute; Step 3, with the composition amine curing agent a in the B component and b at room temperature with 600-800 rev/min speed mechanical dispersed with stirring 5-10 minute; Step 4, add promotor while stirring, at room temperature with 600-800 rev/min speed mechanical dispersed with stirring 5-10 minute; Step 5, at room temperature (25 ℃) component A and B component are mixed, with 3000-3500 rev/min speed mechanical dispersed with stirring 3-5 minute; Namely get the described composition epoxy resin that imports moulding for the fibre reinforced composites vacuum after step 6, the vacuum defoamation.
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