CN101914267A - High-performance epoxy resin composition for pulling and extrusion and preparation method thereof - Google Patents
High-performance epoxy resin composition for pulling and extrusion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-performance epoxy resin composition for pulling and extrusion and a preparation method thereof. The composition comprises the following components in part by mass: 100 parts of epoxy resin, 25 to 50 parts of amine curing agent, and 0.5 to 5.0 parts of small-molecule compound with an epoxy group. The high-performance epoxy resin composition for pulling and extrusion has the advantages of high-strength and high-toughness shock resistance, heat resistance, high toughness, low viscosity and lower cost.
Description
Technical field
The present invention relates to a kind of high-performance epoxy resin composition for pulling and extrusion and preparation method thereof, belong to chemical field.
Background technology
Resins, epoxy is the important thermosetting resin kind that a class includes many types, because it has advantages such as better heat-resisting, mechanical property and manufacturability, being used widely in a lot of fields, is one of the most frequently used matrix resin of carbon-fibre composite at present.Carbon/epoxy composite material has specific tenacity and specific modulus height, designability is good, fatigue resistance is good, scantlings of the structure good stability and the distinct advantages of being convenient to the big area global formation, has obtained using widely in field of aerospace.
But Resins, epoxy is deposited the insufficient shortcoming of toughness after curing, can not effectively bring into play properties of carbon, its carbon-fibre composite when carry load often because the destruction that the premature failure of Resins, epoxy causes matrix material.In order to adapt to the demand of high-performance carbon fibre matrix material to matrix resin, the modification of Resins, epoxy is the research focus 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.
Meanwhile, in order to satisfy the processing request of pultrusion, required resin matrix will have also that speed of response is fast, viscosity is low,, favorable manufacturability energy such as cure shrinkage little good with fiber cohesiveness.Yet, the general viscosity of Resins, epoxy that is used for pultrusion molding process at present is than big or thermotolerance, poor toughness, therefore exploitation is suitable for the epoxy-resin systems that pultrusion molding process uses becomes hot research in recent years, and this research can be satisfied the urgent day by day demand of civilian industry.
Summary of the invention
Technical problem to be solved by this invention provides a kind of high-performance epoxy resin composition for pulling and extrusion, and said composition has the shock resistance of high-strength and high ductility, thermotolerance, good toughness, and viscosity is low, and cost is lower.
Technical scheme provided by the invention is: a kind of high-performance epoxy resin composition for pulling and extrusion by mass, comprises following composition: 100 parts of Resins, epoxy, amine curing agent 25-50 part has micromolecular compound 0.5-5.0 part of epoxide group.
Described Resins, epoxy is selected from: one or more in glycidyl ether based epoxy resin, Racemic glycidol amine epoxy resin, glycidyl ester based epoxy resin, the alicyclic ring based epoxy resin, the combination of preferred glycidyl ether based epoxy resin and glycidyl ester based epoxy resin, the combination of further preferred bisphenol A-type glycidyl ether based epoxy resin and glycidyl ester based epoxy resin, both mass ratioes are: 2: 8-8: 2.
Described amine curing agent is selected from: quadrol, hexanediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, mphenylenediamine, diethyl toluene diamine, 4,4 '-diaminodiphenylmethane, 4,4 '-one or more of diaminodiphenylsulfone(DDS), diethyl toluene diamine, special optimization aromatic aminated compounds.
Described micromolecular compound with epoxide group is preferably from one or more in propylene oxide, propylene oxide methyl ether, phenyl glycidyl ether, butylglycidyl ether, glycidyl allyl ether, cresylglycidylether, ethylene glycol diglycidylether, butanediol diglycidyl ether, neopentylglycol diglycidyl ether, hexanediol diglycidyl ether, resorcinol diglycidyl ether, diglycidylaniline, the three methanol-based propane triglycidyl ether.
The present invention also provides the preparation method of described high-performance epoxy resin composition for pulling and extrusion, and this method adopts hot melt process to be prepared, and concrete preparation process is as follows:
(1) with Resins, epoxy 100-200 ℃ of heated and stirred to forming clear solution;
(2) clear solution is cooled to 50-100 ℃;
(3) micromolecular compound of adding amine curing agent and epoxide group in clear solution, stirring and dissolving;
(4) cast cured explosive.
The present invention has following beneficial effect:
1, adopts glycidyl ether based epoxy resin and the resinoid blending epoxy of glycidyl ester as the resin matrix of pultrusion product, make pultrusion product have the shock resistance of high-strength and high ductility, and possess outstanding high temperature resistance.
2, adopt amine curing agent (special optimization aromatic aminated compounds) as the solidifying agent of pultrusion product, make pultrusion product have lower solidification value and outstanding resistance toheat.
3, adopt the additive of the micromolecular compound of the simple function group of nontoxic or low toxicity or multifunction group epoxy base as pultrusion product, can reduce the viscosity of common bisphenol A type epoxy resin or epoxy resin composition within the specific limits, improve pultrusion product manufacturability and snappiness, satisfy the viscosity requirement of pultrusion molding process, can not cause mechanical properties such as its intensity, modulus significantly to reduce simultaneously resin system.
Simultaneously, by the self aggregation reactive group of epoxy group(ing) micromolecular compound and the effect of amine curing agent, prepare high-performance epoxy resin cheaply.
Embodiment
Embodiment 1
With 28.0g bisphenol A-type glycidyl ether based epoxy resin E-51 (available from Wuxi Resin Factory of Blue Star New Chemical Material Co., Ltd., oxirane value is 0.48-0.54), 12.0g glycidyl ester based epoxy resin TDE-86 is (available from the brilliant eastern chemically composited Materials Co., Ltd in Tianjin, oxirane value is 0.88) mix, be heated to 100 ℃ and be stirred to the formation clear solution, be cooled to 50 ℃ then, then in clear solution, add 16.68g diethyl toluene diamine (DETDA) and 0.2g propylene oxide, mix to be placed on and remove residual bubble, cast cured explosive then in the vacuum drying oven.Program curing is 78 ℃ and solidified 1 hour that 160 ℃ solidified 2 hours, and 200 ℃ solidified 2 hours, and obtained the solidified epoxy matrix resin.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 164 ℃, adopts NDJ-8S type rotational viscosimeter testing tree oil/fat composition viscosity, the viscosity in the time of 25 ℃ is 520mPas.According to standard GB/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.The experiment triplicate, the tensile strength that records this epoxy matrix resin is 95MPa, tension set 4.9%, modulus in tension 3.0GPa.According to standard GB/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.The experiment triplicate, the flexural strength that records this epoxy matrix resin is 85MPa, bending elastic modulus 2.9GPa.
Embodiment 2
With 12.0g bisphenol A-type glycidyl ether based epoxy resin E-51 (available from Wuxi Resin Factory of Blue Star New Chemical Material Co., Ltd., oxirane value is 0.48-0.54), 28.0g glycidyl ester based epoxy resin TDE-86 is (available from the brilliant eastern chemically composited Materials Co., Ltd in Tianjin, oxirane value is 0.88) mix, be heated to 100 ℃ and be stirred to the formation clear solution, be cooled to 50 ℃ then, then in described clear solution, add 13.96g diethyl toluene diamine (DETDA) and 2.0g propylene oxide, mix to be placed on and remove residual bubble, cast cured explosive then in the vacuum drying oven.Program curing is 85 ℃ and solidified 1 hour that 160 ℃ solidified 2 hours, and 210 ℃ solidified 2 hours, and obtained the solidified epoxy matrix resin.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 180 ℃.Adopt NDJ-8S type rotational viscosimeter testing tree oil/fat composition viscosity, the viscosity in the time of 25 ℃ is 480mPas.According to standard GB/T16421-1996 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.The experiment triplicate, the tensile strength that records this epoxy matrix resin is 101MPa, tension set 4.7%, modulus in tension 3.9GPa.According to standard GB/T16419-1996 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.The experiment triplicate, the flexural strength that records this epoxy matrix resin is 117MPa, bending elastic modulus 3.5GPa.
Embodiment 3
With 12.0g bisphenol A-type glycidyl ether based epoxy resin E-51 (available from Wuxi Resin Factory of Blue Star New Chemical Material Co., Ltd., oxirane value is 0.48-0.54), 28.0g glycidyl ester based epoxy resin TDE-86 is (available from the brilliant eastern chemically composited Materials Co., Ltd in Tianjin, oxirane value is 0.88) mix, be heated to 100 ℃ and be stirred to the formation clear solution, be cooled to 50 ℃ then, then in described clear solution, add 13.96g diethyl toluene diamine (DETDA) and 1.0g propylene oxide, mix to be placed on and remove residual bubble, cast cured explosive then in the vacuum drying oven.Program curing is 85 ℃ and solidified 1 hour that 160 ℃ solidified 2 hours, and 210 ℃ solidified 2 hours, and obtained the solidified epoxy matrix resin.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 178 ℃.Adopt NDJ-8S type rotational viscosimeter testing tree oil/fat composition viscosity, the viscosity in the time of 25 ℃ is 430mPas.According to standard GB/T16421-1996 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.The experiment triplicate, the tensile strength that records this epoxy matrix resin is 99MPa, tension set 4.5%, modulus in tension 3.8GPa.According to standard GB/T16419-1996 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.The experiment triplicate, the flexural strength that records this epoxy matrix resin is 114MPa, bending elastic modulus 3.5GPa.
Embodiment 4
With 20.0g bisphenol A-type glycidyl ether based epoxy resin E-51 (available from Wuxi Resin Factory of Blue Star New Chemical Material Co., Ltd., oxirane value is 0.48-0.54), 20.0g glycidyl ester based epoxy resin TDE-86 is (available from the brilliant eastern chemically composited Materials Co., Ltd in Tianjin, oxirane value is 0.88) mix, be heated to 100 ℃ and be stirred to the formation clear solution, be cooled to 50 ℃ then, then in described clear solution, add 12.60g diethyl toluene diamine (DETDA) and 0.4g propylene oxide, mix to be placed on and remove residual bubble, cast cured explosive then in the vacuum drying oven.Program curing is 85 ℃ and solidified 1 hour that 161 ℃ solidified 2 hours, and 230 ℃ solidified 2 hours, and obtained the solidified epoxy matrix resin.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 156 ℃.Adopt NDJ-8S type rotational viscosimeter test epoxy matrix resin viscosity, the viscosity in the time of 25 ℃ is 500mPas.According to standard GB/T16421-1996 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.The experiment triplicate, the tensile strength that records this epoxy matrix resin is 91MPa, tension set 4.3%, modulus in tension 3.2GPa.According to standard GB/T16419-1996 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.The experiment triplicate, the flexural strength that records this epoxy matrix resin is 120MPa, bending elastic modulus 3.8GPa.
Embodiment 5
With 20.0g bisphenol A-type glycidyl ether based epoxy resin E-51 (available from Wuxi Resin Factory of Blue Star New Chemical Material Co., Ltd., oxirane value is 0.48-0.54), 20.0g glycidyl ester based epoxy resin TDE-86 is (available from the brilliant eastern chemically composited Materials Co., Ltd in Tianjin, oxirane value is 0.88) mix, be heated to 100 ℃ and be stirred to the formation clear solution, be cooled to 50 ℃ then, then in described clear solution, add 12.60g diethyl toluene diamine (DETDA) and 2.0g phenyl glycidyl ether, mix to be placed on and remove residual bubble, cast cured explosive then in the vacuum drying oven.Program curing is 85 ℃ and solidified 1 hour that 160 ℃ solidified 2 hours, and 230 ℃ solidified 2 hours, and obtained the solidified epoxy matrix resin.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 160 ℃, adopts NDJ-8S type rotational viscosimeter testing tree oil/fat composition viscosity, the viscosity in the time of 25 ℃ is 511mPas.According to standard GB/T16421-1996 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.The experiment triplicate, the tensile strength that records this epoxy matrix resin is 84MPa, tension set 4.5%, modulus in tension 3.1GPa.According to standard GB/T16419-1996 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.The experiment triplicate, the flexural strength that records this epoxy matrix resin is 107MPa, bending elastic modulus 3.5GPa.
Embodiment 6
With 8.0g bisphenol A-type glycidyl ether based epoxy resin E-51 (available from Wuxi Resin Factory of Blue Star New Chemical Material Co., Ltd., oxirane value is 0.48-0.54), 32.0g glycidyl ester based epoxy resin TDE-86 is (available from the brilliant eastern chemically composited Materials Co., Ltd in Tianjin, oxirane value is 0.88) mix, be heated to 100 ℃ and be stirred to the formation clear solution, be cooled to 50 ℃ then, then in described clear solution, add 20.0g diethyl toluene diamine (DETDA) and 1.0g propylene oxide methyl ether, mix to be placed on and remove residual bubble, cast cured explosive then in the vacuum drying oven.Program curing is 88 ℃ and solidified 1 hour that 170 ℃ solidified 2 hours, and 180 ℃ solidified 2 hours, and obtained the solidified epoxy matrix resin.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 541mPas.According to standard GB/T16421-1996 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.The experiment triplicate, the tensile strength that records this epoxy matrix resin is 84MPa, tension set 4.1%, modulus in tension 3.1GPa.According to standard GB/T16419-1996 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.The experiment triplicate, the flexural strength that records this epoxy matrix resin is 107MPa, bending elastic modulus 3.5GPa.
Embodiment 7
With 8.0g bisphenol A-type glycidyl ether based epoxy resin E-51 (available from Wuxi Resin Factory of Blue Star New Chemical Material Co., Ltd., oxirane value is 0.48-0.54), 32.0g glycidyl ester based epoxy resin TDE-86 is (available from the brilliant eastern chemically composited Materials Co., Ltd in Tianjin, oxirane value is 0.88) mix, be heated to 100 ℃ and be stirred to the formation clear solution, be cooled to 50 ℃ then, then in described clear solution, add 20.0g diethyl toluene diamine (DETDA) and 0.8g glycidyl allyl ether, mix to be placed on and remove residual bubble, cast cured explosive then in the vacuum drying oven.Program curing is 88 ℃ and solidified 1 hour that 170 ℃ solidified 2 hours, and 180 ℃ solidified 2 hours, and obtained the solidified epoxy matrix resin.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 185 ℃, adopts NDJ-8S type rotational viscosimeter testing tree oil/fat composition viscosity, the viscosity in the time of 25 ℃ is 513mPas.According to standard GB/T164211996 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.The experiment triplicate, the tensile strength that records this epoxy matrix resin is 83MPa, tension set 4.1%, modulus in tension 3.1GPa.According to standard GB/T16419-1996 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.The experiment triplicate, the flexural strength that records this epoxy matrix resin is 102MPa, bending elastic modulus 3.4GPa.
Embodiment 8
With 32.0g bisphenol A-type glycidyl ether based epoxy resin E-51 (available from Wuxi Resin Factory of Blue Star New Chemical Material Co., Ltd., oxirane value is 0.48-0.54), 8.0g glycidyl ester based epoxy resin TDE-86 is (available from the brilliant eastern chemically composited Materials Co., Ltd in Tianjin, oxirane value is 0.88) mix, be heated to 100 ℃ and be stirred to the formation clear solution, be cooled to 50 ℃ then, then in described clear solution, add 10.0g diethyl toluene diamine (DETDA) and 1.0g propylene oxide, mix to be placed on and remove residual bubble, cast cured explosive then in the vacuum drying oven.Program curing is 90 ℃ and solidified 1 hour that 170 ℃ solidified 2 hours, and 180 ℃ solidified 2 hours, and obtained the solidified epoxy matrix resin.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 154 ℃, adopts NDJ-8S type rotational viscosimeter testing tree oil/fat composition viscosity, the viscosity in the time of 25 ℃ is 522mPas.According to standard GB/T16421-1996 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.The experiment triplicate, the tensile strength that records this epoxy matrix resin is 92MPa, tension set 3.9%, modulus in tension 3.4GPa.According to standard GB/T16419-1996 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.The experiment triplicate, the flexural strength that records this epoxy matrix resin is 105MPa, bending elastic modulus 3.4GPa.
Embodiment 9
With 16.0g bisphenol A-type glycidyl ether based epoxy resin E-51 (available from Wuxi Resin Factory of Blue Star New Chemical Material Co., Ltd., oxirane value is 0.48-0.54), 24.0g glycidyl ester based epoxy resin TDE-86 is (available from the brilliant eastern chemically composited Materials Co., Ltd in Tianjin, oxirane value is 0.88) mix, be heated to 100 ℃ and be stirred to the formation clear solution, be cooled to 50 ℃ then, then in described clear solution, add 10.5g diethyl toluene diamine (DETDA) and 4.0g 4,4 '-diaminodiphenylsulfone(DDS) (DDS), 1.0g propylene oxide, mix to be placed on and remove residual bubble, cast cured explosive then in the vacuum drying oven.Program curing is 90 ℃ and solidified 1 hour that 160 ℃ solidified 2 hours, and 210 ℃ solidified 2 hours, and obtained the solidified epoxy matrix resin.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 189 ℃, adopts NDJ-8S type rotational viscosimeter testing tree oil/fat composition viscosity, the viscosity in the time of 25 ℃ is 547mPas.According to standard GB/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.The experiment triplicate, the tensile strength that records this epoxy matrix resin is 89MPa, tension set 4.3%, modulus in tension 3.2GPa.According to standard GB/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.The experiment triplicate, the flexural strength that records this epoxy matrix resin is 97MPa, bending elastic modulus 3.3GPa.
Embodiment 10
With 24.0g bisphenol A-type glycidyl ether based epoxy resin E-51 (available from Wuxi Resin Factory of Blue Star New Chemical Material Co., Ltd., oxirane value is 0.48-0.54), 16.0g glycidyl ester based epoxy resin TDE-86 is (available from the brilliant eastern chemically composited Materials Co., Ltd in Tianjin, oxirane value is 0.88) mix, be heated to 100 ℃ and be stirred to the formation clear solution, be cooled to 50 ℃ then, then in described clear solution, add 13.28g diethyl toluene diamine (DETDA) and 2.0g propylene oxide, mix to be placed on and remove residual bubble, cast cured explosive then in the vacuum drying oven.Program curing is 87 ℃ and solidified 1 hour that 165 ℃ solidified 2 hours, and 210 ℃ solidified 2 hours, and obtained the solidified epoxy matrix resin.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 154 ℃, adopts NDJ-8S type rotational viscosimeter testing tree oil/fat composition viscosity, the viscosity in the time of 25 ℃ is 473mPas.According to standard GB/T16421-1996 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.The experiment triplicate, the tensile strength that records this epoxy matrix resin is 85MPa, tension set 4.3%, modulus in tension 3.2GPa.According to standard GB/T16419-1996 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.The experiment triplicate, the flexural strength that records this epoxy matrix resin is 92MPa, bending elastic modulus 3.2GPa.
Claims (8)
1. high-performance epoxy resin composition for pulling and extrusion by mass, comprises following composition: 100 parts of Resins, epoxy, amine curing agent 25-50 part has micromolecular compound 0.5-5.0 part of epoxide group.
2. high-performance epoxy resin composition for pulling and extrusion according to claim 1, it is characterized in that wherein said Resins, epoxy is selected from: one or more in glycidyl ether based epoxy resin, Racemic glycidol amine epoxy resin, glycidyl ester based epoxy resin, the alicyclic ring based epoxy resin.
3. composition epoxy resin according to claim 2 is characterized in that, described Resins, epoxy is the combination of glycidyl ether based epoxy resin and glycidyl ester based epoxy resin.
4. composition epoxy resin according to claim 2, it is characterized in that, described Resins, epoxy is the combination of bisphenol A-type glycidyl ether based epoxy resin and glycidyl ester based epoxy resin, and the mass ratio of wherein said bisphenol A-type glycidyl ether based epoxy resin and glycidyl ester based epoxy resin is: 2: 8-8: 2.
5. high-performance epoxy resin composition for pulling and extrusion according to claim 1, it is characterized in that: described amine curing agent is selected from: quadrol, hexanediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, mphenylenediamine, diethyl toluene diamine, 4,4 '-one or more of diaminodiphenylmethane, 4,4, diethyl toluene diamine.
6. high-performance epoxy resin composition for pulling and extrusion according to claim 4 is characterized in that: described amine curing agent is the aromatic amine compounds.
7. high-performance epoxy resin composition for pulling and extrusion according to claim 1 is characterized in that: described micromolecular compound with epoxide group is preferably from propylene oxide, the propylene oxide methyl ether, phenyl glycidyl ether, butylglycidyl ether, glycidyl allyl ether, cresylglycidylether, ethylene glycol diglycidylether, butanediol diglycidyl ether, neopentylglycol diglycidyl ether, hexanediol diglycidyl ether, resorcinol diglycidyl ether, diglycidylaniline, in the three methanol-based propane triglycidyl ether one or more.
8. the preparation method of high-performance epoxy resin composition for pulling and extrusion according to claim 1 is characterized in that comprising the steps:
(1) with Resins, epoxy 100-200 ℃ of heated and stirred to forming clear solution;
(2) clear solution is cooled to 50-100 ℃;
(3) micromolecular compound of adding amine curing agent and epoxide group in clear solution, stirring and dissolving;
(4) cast cured explosive.
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| CN103709602A (en) * | 2013-11-26 | 2014-04-09 | 蓝星（北京）特种纤维技术研发中心有限公司 | Toughening aging-resistant epoxy resin composition for pultrusion molding and preparation method thereof |
| CN105331320A (en) * | 2015-12-01 | 2016-02-17 | 苏州圣杰特种树脂有限公司 | Low-viscosity high-activity epoxy resin adhesive |
| CN106430500A (en) * | 2016-09-28 | 2017-02-22 | 同济大学 | Preparation method of catalytic coagulation agent suitable for oil field polymer-flooding oil-production sewage |
| CN113150499A (en) * | 2021-04-27 | 2021-07-23 | 嘉兴恒隆复合材料有限公司 | Epoxy resin composition for pultrusion and preparation method thereof |
| CN115724776A (en) * | 2022-12-10 | 2023-03-03 | 湖北长海新能源科技有限公司 | Monofunctional epoxy compound modified diamino diphenyl sulfone and application thereof |
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| CN102286138A (en) * | 2011-07-01 | 2011-12-21 | 蓝星(北京)化工机械有限公司 | Heat-resistant epoxide resin composition for rapid pultrusion |
| CN102295824A (en) * | 2011-07-08 | 2011-12-28 | 蓝星(北京)化工机械有限公司 | One-part high-performance epoxy resin composition for pultrusion |
| CN102977828B (en) * | 2011-09-07 | 2014-04-23 | 蓝星(北京)化工机械有限公司 | High-efficient epoxy resin adhesive and preparation method and applications thereof. |
| CN102977828A (en) * | 2011-09-07 | 2013-03-20 | 蓝星(北京)化工机械有限公司 | High-efficient epoxy resin adhesive and preparation method and applications thereof. |
| CN102977830B (en) * | 2011-09-07 | 2014-03-26 | 蓝星(北京)化工机械有限公司 | Epoxy resin adhesive and preparation method and applications thereof |
| CN102977830A (en) * | 2011-09-07 | 2013-03-20 | 蓝星(北京)化工机械有限公司 | Epoxy resin adhesive and preparation method and applications thereof |
| CN103709602A (en) * | 2013-11-26 | 2014-04-09 | 蓝星（北京）特种纤维技术研发中心有限公司 | Toughening aging-resistant epoxy resin composition for pultrusion molding and preparation method thereof |
| CN105331320A (en) * | 2015-12-01 | 2016-02-17 | 苏州圣杰特种树脂有限公司 | Low-viscosity high-activity epoxy resin adhesive |
| CN105331320B (en) * | 2015-12-01 | 2018-01-23 | 苏州圣杰特种树脂有限公司 | A kind of epoxyn of low viscosity high activity |
| CN106430500A (en) * | 2016-09-28 | 2017-02-22 | 同济大学 | Preparation method of catalytic coagulation agent suitable for oil field polymer-flooding oil-production sewage |
| CN106430500B (en) * | 2016-09-28 | 2019-04-26 | 同济大学 | A kind of preparation method of the catalysis coagulated agent suitable for oilfield injection oil extraction-generated waste water |
| CN113150499A (en) * | 2021-04-27 | 2021-07-23 | 嘉兴恒隆复合材料有限公司 | Epoxy resin composition for pultrusion and preparation method thereof |
| CN115724776A (en) * | 2022-12-10 | 2023-03-03 | 湖北长海新能源科技有限公司 | Monofunctional epoxy compound modified diamino diphenyl sulfone and application thereof |
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