CN101597417B - High-temperature resistant and high-toughness epoxy matrix resin as well as preparation method and application thereof - Google Patents
High-temperature resistant and high-toughness epoxy matrix resin as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses high-temperature resistant and high-toughness epoxy matrix resin as well as a preparation method and an application thereof. The epoxy matrix resin is prepared from the following components by weight portion: 100 portions of epoxy resin, 20-60 portions of curing agent, 0.5-5.0 portions of curing accelerator and 5-50 portions of thermoplastic resin. The epoxy matrix resin has the glass-transition temperature of 210-235 DEG C, the tensile strength of 80-86MPa, the elongation at break of 3.0-3.3% and the tensile elastic module of 3.2-3.5GPa. The epoxy matrix resin can meet the requirement of carbon fiber solvent for preimpregnation process and hot-melt preimpregnation process, and after being cured by a proper process, the epoxy matrix resin has excellent comprehensive performance and particularly high-temperature resistance and high toughness, thereby being used for preparing high-performance composite material used in the aerospace field and meeting the requirement of the high technology field represented by the aerospace field.
Description
Technical field
The present invention relates to a kind of epoxy matrix resin and preparation method thereof and application of high heat-resisting high tenacity.
Background technology
Resins, epoxy has advantages such as better heat-resisting, mechanical property and manufacturability, has been used widely in a lot of fields, and be 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 have obtained using widely in field of aerospace.But there is the insufficient shortcoming of toughness in Resins, epoxy 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.
The method of modifying of Resins, epoxy has a lot, and from adding the direction of second phase, common have rubber elastomer modified epoxy, nano particle modified epoxy resin, hyperbranched polymer modified epoxy and a thermoplastic resin modified Resins, epoxy etc.; And, mainly be to carry out modification from Resins, epoxy and solidifying agent molecular structure from the molecular chain structure of Resins, epoxy self.In these method of modifying, single method of modifying often has certain limitation, during such as the rubber elastomer modified epoxy, can effectively improve the toughness of epoxy-resin systems, but can reduce the thermotolerance and the rigidity of system.(Chinese patent CN1376737) points out to adopt rubber/clay composite toughening Resins, epoxy in the research of Lv Jiankun, beneficial Xiao Su, the adding of rubber has improved the toughness of Resins, epoxy, clay has remedied the caused rigidity of modified rubber and has descended, but the thermotolerance of resin system descends.The hyperbranched polymer modified epoxy is the method for modifying that a kind of newly-developed gets up, its characteristics are and can improving the Resins, epoxy flexible simultaneously, do not influence its viscosity, modulus and thermotolerance, but hyperbranched polymer is not good for the modified effect of the higher epoxy-resin systems of cross-linking density, (Polymer International in the research of Russell J Varley, 2004,53:78) just pointed out this problem.During thermoplastic resin modified Resins, epoxy, the adding of thermoplastic resin is bigger for the viscosity influence of resin system, makes the processing performance variation of matrix resin.
Summary of the invention
The purpose of this invention is to provide epoxy matrix resin of a kind of high heat-resisting high tenacity and preparation method thereof.
Epoxy matrix resin provided by the present invention is to be made by following compositions: the Resins, epoxy of 100 mass parts, the solidifying agent of 20-60 mass parts, the thermoplastic resin of the curing catalyst of 0.5-5.0 mass parts and 5-50 mass parts; The second-order transition temperature of described epoxy matrix resin is 210-235 ℃, and tensile strength is 80-86MPa, and tension set is 3.0%-3.3%, and modulus in tension is 3.2-3.5GPa.
The method for preparing epoxy matrix resin provided by the present invention, can adopt hot melt process to be prepared, concrete preparation method is as follows: Resins, epoxy and thermoplastic resin are mixed, 100-200 ℃ of heated and stirred to forming clear solution, clear solution is cooled to 50-100 ℃ then, then add solidifying agent and curing catalyst in described clear solution, stirring and dissolving obtains described epoxy matrix resin.
The method for preparing epoxy matrix resin provided by the present invention, also can adopt solvent method to be prepared, concrete preparation method is as follows: at room temperature be dissolved in thermoplastic resin in the solvent, obtain the solution of thermoplastic resin, add Resins, epoxy, solidifying agent and curing catalyst then in described solution, stirring and dissolving obtains described epoxy matrix resin.
Wherein, described solvent is a kind of or its arbitrary combination in following seven kinds of materials: tetrahydrofuran (THF), acetone, methylene dichloride, trichloromethane, N, N '-dimethyl formamide, N, N '-N,N-DIMETHYLACETAMIDE and N-N-methyl-2-2-pyrrolidone N-.
Resins, epoxy described in the present invention be following a) and/or b);
Described a) is following 1) to 5) at least a Racemic glycidol amine epoxy resin:
1) R in the formula (I)
1Be H, R
2Compound TGDDM for H;
2) R in the formula (I)
1Be Cl, R
2Compound D CTGDDM for H;
3) R in the formula (I)
1Be CH
3, R
2Compound D MTGDDM for H;
4) R in the formula (I)
1Be Cl, R
2Compound TCTGDDM for Cl;
5) R in the formula (I)
1Be CH
3, R
2Be CH
3Compound TMTGDDM;
Described b) is at least a in following six kinds of materials: terephthalic acid diglycidyl ester, o-phthalic acid diglycidyl ester, 1,2-epoxy cyclohexane-4,5-dioctyl phthalate 2-glycidyl ester, p-aminophenol Resins, epoxy, bisphenol f type epoxy resin and bisphenol A type epoxy resin;
Formula (I).
Solidifying agent described in the present invention is following c) and/or d);
Described c) be following 6)-12) at least a:
6) R in the formula (II)
1Be H, R
2Be H, R
3Be CH
2Compound D DM;
7) R in the formula (II)
1Be Cl, R
2Be H, R
3Be CH
2Compound D CDDM;
8) R in the formula (II)
1Be CH
3, R
2Be H, R
3Be CH
2Compound D MDDM;
9) R in the formula (II)
1Be Cl, R
2Be Cl, R
3Be CH
2Compound TCDDM;
10) R in the formula (II)
1Be CH
3, R
2Be CH
3, R
3Be CH
2Compound TMDDM;
11) R in the formula (II)
1Be H, R
2Be H, R
3Compound D DE for O;
12) R in the formula (II)
1Be H, R
2Be H, R
3Be SO
2Compound D DS;
Formula (II);
Described d) be following 13)-18) at least a:
13) R in the formula (III)
1Be H, R
2For
Compound 1,3,4-APB;
14) R in the formula (III)
1Be H, R
2For
Compound 1,4,4-APB;
15) R in the formula (III)
1Be H, R
2For
Compd B AB;
16) R in the formula (III)
1Be CF
3, R
2For
Compound 1,3,4-6FAPB;
17) R in the formula (III)
1Be CF
3, R
2For
Compound 1,4,4-6FAPB;
18) R in the formula (III)
1Be CF
3, R
2For
Compound 6FBAB;
Formula (III).
Curing catalyst of the present invention can be a kind of or its arbitrary combination in following six kinds of materials: meta-cresol, Resorcinol, 2,4,6-three (dimethylamino methyl)-phenol (DMP-30), boron triflouride-mono aminoethane, dithioglycol and nonylbenzene phenol.
Described thermoplastic resin can be a kind of or its arbitrary combination among PEK (formula IV), PSF (formula V), PES (formula VI) and the PEI (formula VII),
Formula (IV)
Formula V
Formula (VI)
Formula (VII)
Wherein, n is 1-60.
Epoxy matrix resin provided by the present invention, can satisfy the requirement of carbon fiber solvent preimpregnated process and hot melt preimpregnated process, can be used for preparing carbon fiber, after suitably technology is solidified, cured article has the excellent comprehensive performance, especially the characteristics that have high heat-resisting and high tenacity, its casting matrix tensile strength can reach more than the 80MPa, fracture is prolonged living rate and can be reached more than 3%, modulus in tension reaches more than the 3.2GPa, second-order transition temperature can be used for preparing space flight, aviation high performance composite more than 210 ℃, satisfies the demand that space flight and aviation is the high-tech sector of representative.
Embodiment
Embodiment 1
With 80g TGDDM (compound, wherein R shown in the formula (I)
1Be H, R
2Be H), 20g 1,2-epoxy cyclohexane 4,5-dioctyl phthalate 2-glycidyl ester and 15g thermoplastic resin PSF (polymkeric substance shown in the formula V, n=1) mix, be heated to 150 ℃ and be stirred to the formation clear solution, be cooled to 100 ℃ then, then in described clear solution, add 15g DDS (compound, wherein R shown in the formula (II)
1Be H, R
2Be H, R
3Be SO
2), 25g 1,4,4-6FAPB (compound, wherein R shown in the formula (III)
1Be CF
3, R
2For
) and the 0.5g boron triflouride-mono aminoethane, mix the back cast cured explosive.Program curing is 130 ℃ and solidified 1 hour that 180 ℃ solidified 2 hours, and 200 ℃ solidified 2 hours, and obtained the solidified epoxy matrix resin.DMA method (dynamic thermomechanometry) is surveyed second-order transition temperature, adopt the three-point bending loading mode, batten size (18 ± 0.5mm) * (5 ± 0.2mm) * (1.5 ± 0.2mm), frequency 1Hz, temperature rise rate 5C/min, the second-order transition temperature that records epoxy matrix resin is 225 ℃, according to the tensile strength of standard GB/T 16421-1996 to the epoxy matrix resin of preparation, tension set, modulus in tension is 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 3.2%, modulus in tension 3.3GPa.
Embodiment 2
With 70g TGDDM (compound, wherein R shown in the formula (I)
1Be H, R
2Be H), 30g p-aminophenol Resins, epoxy and the 20g thermoplastic resin PEI (polymkeric substance shown in the formula (VII), n=10) mix, be heated to 160 ℃ and be stirred to the formation clear solution, be cooled to 80 ℃ then, then in described clear solution, add 20gTMDDM (compound, wherein R shown in the formula (I)
1Be CH
3, R
2Be CH
3, R
3Be CH
2), 15g DDS (compound, wherein R shown in the formula (II)
1Be H, R
2Be H, R
3Be SO
2) and the 1.5g boron triflouride-mono aminoethane, mix the back cast cured explosive.Program curing is 130 ℃ and solidified 2 hours that 170 ℃ solidified 3 hours, and 200 ℃ solidified 2 hours, and obtained the solidified epoxy matrix resin.DMA method (dynamic thermomechanometry) is surveyed second-order transition temperature, adopt the three-point bending loading mode, batten size (18 ± 0.5mm) * (5 ± 0.2mm) * (1.5 ± 0.2mm), frequency 1Hz, 5 ℃/min of temperature rise rate, the second-order transition temperature that records epoxy matrix resin is 215 ℃, according to the tensile strength of standard GB/T 16421-1996 to the epoxy matrix resin of preparation, tension set, modulus in tension is 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.Test triplicate, record the tensile strength 83MPa of this epoxy matrix resin, tension set 3.3%, modulus in tension 3.2GPa.
Embodiment 3
With 95g DCTGDDM (compound, wherein R shown in the formula (I)
1Be Cl, R
2Be H), (polymkeric substance shown in the formula (IV) n=60) mixes, and is heated to 110 ℃ and is stirred to the formation clear solution, is cooled to 60 ℃ then, adds 25gDDM (compound shown in the formula (II), wherein R for 5g bisphenol A epoxide resin and 25g thermoplastic resin PEK
1Be H, R
2Be H, R
3Be CH
2), 20g 1,4,4-APB (compound, wherein R shown in the formula (III)
1Be H, R
2For
) and the 1.5g dithioglycol, mix the back cast cured explosive.Program curing is 130 ℃ and solidified 2 hours that 150 ℃ solidified 4 hours, and 180 ℃ solidified 4 hours, and obtained the solidified epoxy matrix resin.DMA method (dynamic thermomechanometry) is surveyed second-order transition temperature, adopt the three-point bending loading mode, batten size (18 ± 0.5mm) * (5 ± 0.2mm) * (1.5 ± 0.2mm), frequency 1Hz, 5 ℃/min of temperature rise rate, the second-order transition temperature that records epoxy matrix resin is 210 ℃, according to the tensile strength of standard GB/T 16421-1996 to the epoxy matrix resin of preparation, tension set, modulus in tension is 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.Test triplicate, record the tensile strength 85MPa of this epoxy matrix resin, tension set 3.3%, modulus in tension 3.2GPa.
Embodiment 4
With 90g TMTGDDM (compound shown in the formula (I), wherein R
1Be CH
3, R
2Be CH
3), 10g bisphenol F epoxy resin and the 30g thermoplastic resin PES (polymkeric substance shown in the formula (VI), n=15) mix, be heated to 120 ℃ and be stirred to the formation clear solution, be cooled to 90 ℃ then, then in described clear solution, add 15g DDE (compound, wherein R shown in the formula (II)
1Be H, R
2Be H, R
3Be O), 20g 1,3,4-APB (compound, wherein R shown in the formula (III)
1Be H, R
2For
) and 2.0g nonylbenzene phenol, mix the back cast cured explosive.Program curing is 130 ℃ and solidified 2 hours that 160 ℃ solidified 3 hours, and 190 ℃ solidified 3 hours, and obtained the solidified epoxy matrix resin.DMA method (dynamic thermomechanometry) is surveyed second-order transition temperature, adopt the three-point bending loading mode, batten size (18 ± 0.5mm) * (5 ± 0.2mm) * (1.5 ± 0.2mm), frequency 1Hz, 5 ℃/min of temperature rise rate, the second-order transition temperature that records epoxy matrix resin is 210 ℃, according to the tensile strength of standard GB/T16421-1996 to the epoxy matrix resin of preparation, tension set, modulus in tension is 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.Test triplicate, record the tensile strength 80MPa of this epoxy matrix resin, tension set 3.3%, modulus in tension 3.4GPa.
Embodiment 5
With 75g TCTGDDM (compound, wherein R shown in the formula (I)
1Be Cl, R
2Be C1), 25g o-phthalic acid diglycidyl ester and the 35g thermoplastic resin PEI (polymkeric substance shown in the formula (VII), n=25) mix, be heated to 140 ℃ and be stirred to the formation clear solution, be cooled to 80 ℃ then, then in described clear solution, add 20g 1,3,4-APB (compound, wherein R shown in the formula (III)
1Be H, R
2For
), 20g 6FBAB (compound, wherein R shown in the formula (III)
1Be CF
3, R
2For
), 0.5g boron triflouride-mono aminoethane and 1.0gDMP-30, mix the back cast cured explosive.Program curing is 120 ℃ and solidified 3 hours that 150 ℃ solidified 3 hours, and 180 ℃ solidified 4 hours, and obtained the solidified epoxy matrix resin.DMA method (dynamic thermomechanometry) is surveyed second-order transition temperature, adopt the three-point bending loading mode, batten size (18 ± 0.5mm) * (5 ± 0.2mm) * (1.5 ± 0.2mm), frequency 1Hz, 5 ℃/min of temperature rise rate, the second-order transition temperature that records epoxy matrix resin is 230 ℃, according to the tensile strength of standard GB/T 16421-1996 to the epoxy matrix resin of preparation, tension set, modulus in tension is 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.Test triplicate, record the tensile strength 84MPa of this epoxy matrix resin, tension set 3.1%, modulus in tension 3.4GPa.
Embodiment 6
With 70g DMTGDDM (compound, wherein R shown in the formula (I)
1Be CH
3, R
2Be H), 30g terephthalic acid diglycidyl ester and 30g thermoplastic resin PSF (compound shown in the formula V, n=20) mix, be heated to 130 ℃ and be stirred to the formation clear solution, be cooled to 90 ℃ then, then in described clear solution, add 10g TCDDM (compound shown in the formula (II), wherein R
1Be Cl, R
2Be Cl, R
3Be CH
2), 50g 1,4,4-6FAPB (compound, wherein R shown in the formula (III)
1Be CF
3, R
2For
) and 3.0gDMP-30, mix the back cast cured explosive.Program curing is 120 ℃ and solidified 3 hours that 150 ℃ solidified 2 hours, and 190 ℃ solidified 3 hours, and obtained the solidified epoxy matrix resin.DMA method (dynamic thermomechanometry) is surveyed second-order transition temperature, adopt the three-point bending loading mode, batten size (18 ± 0.5mm) * (5 ± 0.2mm) * (1.5 ± 0.2mm), frequency 1Hz, 5 ℃/min of temperature rise rate, the second-order transition temperature that records epoxy matrix resin is 230 ℃, according to the tensile strength of standard GB/T 16421-1996 to the epoxy matrix resin of preparation, tension set, modulus in tension is 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.Test triplicate, record the tensile strength 85MPa of this epoxy matrix resin, tension set 3.1%, modulus in tension 3.5GPa.
Embodiment 7
With 100g TGDDM (compound, wherein R shown in the formula (I)
1Be H, R
2Be H) and 5g thermoplastic resin PEK (polymkeric substance shown in the formula (IV) n=30) mixes, and is heated to 150 ℃ and is stirred to the formation clear solution, is cooled to 70 ℃ then, then adds 25g DDM (compound shown in the formula (II), wherein R in described clear solution
1Be H, R
2Be H, R
3Be CH
2), 20g 6FBAB (compound, wherein R shown in the formula (III)
1Be CF
3, R
2For
) and the 5.0g Resorcinol, mix the back cast cured explosive.Program curing is 130 ℃ and solidified 2 hours that 150 ℃ solidified 3 hours, and 180 ℃ solidified 4 hours, and obtained the solidified epoxy matrix resin.DMA method (dynamic thermomechanometry) is surveyed second-order transition temperature, adopt the three-point bending loading mode, batten size (18 ± 0.5mm) * (5 ± 0.2mm) * (1.5 ± 0.2mm), frequency 1Hz, 5 ℃/min of temperature rise rate, the second-order transition temperature that records epoxy matrix resin is 220 ℃, according to the tensile strength of standard GB/T 16421-1996 to the epoxy matrix resin of preparation, tension set, modulus in tension is 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.Test triplicate, record the tensile strength 86MPa of this epoxy matrix resin, tension set 3.0%, modulus in tension 3.2GPa.
Embodiment 8
With 50g TGDDM (compound, wherein R shown in the formula (I)
1Be H, R
2Be H), 50g DCTGDDM (compound, wherein R shown in the formula (I)
1Be Cl, R
2Be H) and 15g thermoplastic resin PES (polymkeric substance shown in the formula (VI) n=35) mixes, and is heated to 180 ℃ and is stirred to the formation clear solution, is cooled to 80 ℃ then, adds 10g DMDDM (compound, wherein R shown in the formula (II)
1Be CH
3, R
2Be H, R
3Be CH
2), 50g 1,3,4-6FAPB (compound shown in the formula (III), wherein R
1Be CF
3, R
2For
) and the 1.0g meta-cresol, mix the back cast cured explosive.Program curing is 130 ℃ and solidified 2 hours that 160 ℃ solidified 4 hours, and 190 ℃ solidified 3 hours, and obtained the solidified epoxy matrix resin.DMA method (dynamic thermomechanometry) is surveyed second-order transition temperature, adopt the three-point bending loading mode, batten size (18 ± 0.5mm) * (5 ± 0.2mm) * (1.5 ± 0.2mm), frequency 1Hz, 5 ℃/min of temperature rise rate, the second-order transition temperature that records epoxy matrix resin is 235 ℃, according to the tensile strength of standard GB/T 16421-1996 to the epoxy matrix resin of preparation, tension set, modulus in tension is 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.Test triplicate, record the tensile strength 80MPa of this epoxy matrix resin, tension set 3.2%, modulus in tension 3.2GPa.
Embodiment 9
With 50g 1,2-epoxy cyclohexane 4,5-dioctyl phthalate 2-glycidyl ester, 50g p-aminophenol Resins, epoxy, 15g thermoplastic resin PSF (compound shown in the formula V, n=40) and the 10g thermoplastic resin PEI (polymkeric substance shown in the formula (VII), n=22) mix, be heated to 100 ℃ and be stirred to the formation clear solution, be cooled to 50 ℃ then, then in described clear solution, add 55g 6FBAB (compound, wherein R shown in the formula (III)
1Be CF
3, R
2For
) and 1.5gDMP-30, mix the back cast cured explosive.Program curing is 130 ℃ and solidified 2 hours that 150 ℃ solidified 3 hours, and 180 ℃ solidified 4 hours, and obtained the solidified epoxy matrix resin.DMA method (dynamic thermomechanometry) is surveyed second-order transition temperature, adopt the three-point bending loading mode, batten size (18 ± 0.5mm) * (5 ± 0.2mm) * (1.5 ± 0.2mm), frequency 1Hz, 5 ℃/min of temperature rise rate, the second-order transition temperature that records epoxy matrix resin is 210 ℃, according to the tensile strength of standard GB/T 16421-1996 to the epoxy matrix resin of preparation, tension set, modulus in tension is 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.Test triplicate, record the tensile strength 85MPa of this epoxy matrix resin, tension set 3.0%, modulus in tension 3.5GPa.
Embodiment 10
(compound shown in the formula V n=28) joins in the mixed solvent of 232.5ml tetrahydrofuran (THF) and acetone (volume ratio is 2: 1) and stirs, and the dissolving back adds 70gTGDDM (compound, wherein R shown in the formula (I) in above-mentioned solution fully with the PSF of 15g under the room temperature
1Be H, R
2Be H) and 30g 1,2-epoxy cyclohexane 4,5-dioctyl phthalate 2-glycidyl ester, and 20gDDS (compound, wherein R shown in the formula (II)
1Be H, R
2Be H, R
3Be SO
2) and 20g 1,4,4-6FAPB (compound, wherein R shown in the formula (III)
1Be CF
3, R
2For
), 1.0gDMP-30 is mixed with the homogeneous clear solution, and heating removes solvent and prepares casting matrix under vacuum, and program curing is 120 ℃ and solidified 3 hours that 150 ℃ solidified 3 hours, and 180 ℃ solidified 3 hours, and obtained the solidified epoxy matrix resin.DMA method (dynamic thermomechanometry) is surveyed second-order transition temperature, adopt the three-point bending loading mode, batten size (18 ± 0.5mm) * (5 ± 0.2mm) * (1.5 ± 0.2mm), frequency 1Hz, 5 ℃/min of temperature rise rate, the second-order transition temperature that records epoxy matrix resin is 210 ℃, according to the tensile strength of standard GB/T16421-1996 to the epoxy matrix resin of preparation, tension set, modulus in tension is 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.Test triplicate, record the tensile strength 84MPa of this epoxy matrix resin, tension set 3.2%, modulus in tension 3.2GPa.
Embodiment 11
(polymkeric substance shown in the formula (IV) n=45) joins in the mixed solvent of 232.5ml tetrahydrofuran (THF) and acetone (volume ratio is 1: 3) and stirs, and the dissolving back adds 85g DCTGDDM (compound, wherein R shown in the formula (I) fully with the PEK of 20g under the room temperature
1Be Cl, R
2Be H) and 15g p-aminophenol Resins, epoxy, and 20gTMDDM (compound, wherein R shown in the formula (I)
1Be CH
3, R
2Be CH
3, R
3Be CH
2) and 15g DDS (compound, wherein R shown in the formula (II)
1Be H, R
2Be H, R
3Be SO
2), the 0.5g boron triflouride-mono aminoethane is mixed with the homogeneous clear solution, and heating removes solvent and prepares casting matrix under the vacuum, and program curing is 120 ℃ and solidified 3 hours that 150 ℃ solidified 2 hours, and 190 ℃ solidified 3 hours, and obtained the solidified epoxy matrix resin.DMA method (dynamic thermomechanometry) is surveyed second-order transition temperature, adopt the three-point bending loading mode, batten size (18 ± 0.5mm) * (5 ± 0.2mm) * (1.5 ± 0.2mm), frequency 1Hz, 5 ℃/min of temperature rise rate, the second-order transition temperature that records epoxy matrix resin is 210 ℃, according to the tensile strength of standard GB/T 16421-1996 to the epoxy matrix resin of preparation, tension set, modulus in tension is 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.Test triplicate, record the tensile strength 85MPa of this epoxy matrix resin, tension set 3.3%, modulus in tension 3.2GPa.
Embodiment 12
(polymkeric substance shown in the formula (VII) n=50) joins 255ml N, stirs in N '-N,N-DIMETHYLACETAMIDE, and the dissolving back adds 95g TGDDM (compound, wherein R shown in the formula (I) fully with the PEI of 25g under the room temperature
1Be H, R
2Be H) and the 5g o-phthalic acid diglycidyl ester, and 25g DDM (compound shown in the formula (II), wherein R
1Be H, R
2Be H, R
3Be CH
2) and 20g 1,3,4-APB (compound, wherein R shown in the formula (III)
1Be H, R
2For
), the 2.0g dithioglycol is mixed with the homogeneous clear solution, and heating removes solvent and prepares casting matrix under the vacuum, and program curing is 130 ℃ and solidified 2 hours that 150 ℃ solidified 3 hours, and 180 ℃ solidified 4 hours, and obtained the solidified epoxy matrix resin.DMA method (dynamic thermomechanometry) is surveyed second-order transition temperature, adopt the three-point bending loading mode, batten size (18 ± 0.5mm) * (5 ± 0.2mm) * (1.5 ± 0.2mm), frequency 1Hz, 5 ℃/min of temperature rise rate, the second-order transition temperature that records epoxy matrix resin is 230 ℃, according to the tensile strength of standard GB/T 16421-1996 to the epoxy matrix resin of preparation, tension set, modulus in tension is 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.Test triplicate, record the tensile strength 82MPa of this epoxy matrix resin, tension set 3.3%, modulus in tension 3.4GPa.
Embodiment 13
(compound shown in the formula V n=28) joins 262.5ml N, stirs in N '-dimethyl formamide, and the dissolving back adds 80g TMTGDDM (compound shown in the formula (I), wherein R fully with the PSF of 30g under the room temperature
1Be CH
3, R
2Be CH
3) and the 20g bisphenol F epoxy resin, and 20g DDE (compound, wherein R shown in the formula (II)
1Be H, R
2Be H, R
3Be O) and 25g 1,4,4-APB (compound, wherein R shown in the formula (III)
1Be H, R
2For
), 2.5g nonylbenzene phenol is mixed with the homogeneous clear solution, and heating removes solvent and prepares casting matrix under the vacuum, and program curing is 130 ℃ and solidified 2 hours that 160 ℃ solidified 4 hours, and 190 ℃ solidified 3 hours, and obtained the solidified epoxy matrix resin.DMA method (dynamic thermomechanometry) is surveyed second-order transition temperature, adopt the three-point bending loading mode, batten size (18 ± 0.5mm) * 5 ± 0.2mm * 1.5 ± 0.2mm, frequency 1Hz, 5 ℃/min of temperature rise rate, the second-order transition temperature that records epoxy matrix resin is 230 ℃, according to the tensile strength of standard GB/T16421-1996 to the epoxy matrix resin of preparation, tension set, modulus in tension is 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.Test triplicate, record the tensile strength 80MPa of this epoxy matrix resin, tension set 3.3%, modulus in tension 3.4GPa.
Embodiment 14
(polymkeric substance shown in the formula (VI) n=33) joins in the 225ml tetrahydrofuran (THF) and stirs, and the dissolving back adds 75g TCTGDDM (compound, wherein R shown in the formula (I) fully with the PES of 10g under the room temperature
1Be Cl, R
2Be Cl) and the 25g bisphenol A epoxide resin, and 20g 1,4,4-APB (compound, wherein R shown in the formula (III)
1Be H, R
2For
) and 20g 1,4,4-6FAPB (compound, wherein R shown in the formula (III)
1Be CF
3, R
2For
), the 0.5g boron triflouride-mono aminoethane is mixed with the homogeneous clear solution, and heating removes solvent and prepares casting matrix under the vacuum, and program curing is 130 ℃ and solidified 2 hours that 150 ℃ solidified 3 hours, and 180 ℃ solidified 4 hours, and obtained the solidified epoxy matrix resin.DMA method (dynamic thermomechanometry) is surveyed second-order transition temperature, adopt the three-point bending loading mode, batten size (18 ± 0.5mm) * (5 ± 0.2mm) * (1.5 ± 0.2mm), frequency 1Hz, 5 ℃/min of temperature rise rate, the second-order transition temperature that records epoxy matrix resin is 220 ℃, according to the tensile strength of standard GB/T 16421-1996 to the epoxy matrix resin of preparation, tension set, modulus in tension is 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.Test triplicate, record the tensile strength 85MPa of this epoxy matrix resin, tension set 3.1%, modulus in tension 3.5GPa.
Embodiment 15
(polymkeric substance shown in the formula (VII) n=27) joins in the 240ml methylene dichloride and stirs, and the dissolving back adds 80g DMTGDDM (compound, wherein R shown in the formula (I) fully with the PEI of 15g under the room temperature
1Be CH
3, R
2Be H) and the 20g terephthalic acid diglycidyl ester, and 15g DDM (compound shown in the formula (II), wherein R
1Be H, R
2Be H, R
3Be CH
2) and 30g 6FBAB (compound, wherein R shown in the formula (III)
1Be CF
3, R
2For
), 2.0gDMP-30 is mixed with the homogeneous clear solution, and heating removes solvent and prepares casting matrix under the vacuum, and program curing is 130 ℃ and solidified 1 hour that 180 ℃ solidified 2 hours, and 200 ℃ solidified 2 hours, and obtained the solidified epoxy matrix resin.DMA method (dynamic thermomechanometry) is surveyed second-order transition temperature, adopt the three-point bending loading mode, batten size (18 ± 0.5mm) * (5 ± 0.2mm) * (1.5 ± 0.2mm), frequency 1Hz, 5 ℃/min of temperature rise rate, the second-order transition temperature that records epoxy matrix resin is 235 ℃, according to the tensile strength of standard GB/T 16421-1996 to the epoxy matrix resin of preparation, tension set, modulus in tension is 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.Test triplicate, record the tensile strength 85MPa of this epoxy matrix resin, tension set 3.1%, modulus in tension 3.2GPa.
Embodiment 16
(polymkeric substance shown in the formula (IV) n=55) joins in the mixed solvent of 225ml methylene dichloride and acetone (volume ratio is 3: 1) and stirs, and the dissolving back adds 80g TGDDM (compound, wherein R shown in the formula (I) fully with the PEK of 5g under the room temperature
1Be H, R
2Be H) and 20g 1,2-epoxy cyclohexane 4,5-dioctyl phthalate 2-glycidyl ester, and 25g TCDDM (compound shown in the formula (II), wherein R
1Be Cl, R
2Be Cl, R
3Be CH
2) and 20g 1,4,4-6FAPB (compound, wherein R shown in the formula (III)
1Be CF
3, R
2For
), the 3.5g Resorcinol is mixed with the homogeneous clear solution, and heating removes solvent and prepares casting matrix under the vacuum, and program curing is 130 ℃ and solidified 2 hours that 170 ℃ solidified 3 hours, and 200 ℃ solidified 2 hours, and obtained the solidified epoxy matrix resin.DMA method (dynamic thermomechanometry) is surveyed second-order transition temperature, adopt the three-point bending loading mode, batten size (18 ± 0.5mm) * (5 ± 0.2mm) * (1.5 ± 0.2mm), frequency 1Hz, 5 ℃/min of temperature rise rate, the second-order transition temperature that records epoxy matrix resin is 210 ℃, according to the tensile strength of standard GB/T 16421-1996 to the epoxy matrix resin of preparation, tension set, modulus in tension is 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.Test triplicate, record the tensile strength 85MPa of this epoxy matrix resin, tension set 3.1%, modulus in tension 3.2GPa.
Embodiment 17
(polymkeric substance shown in the formula (VI) n=48) joins in the 255ml trichloromethane and stirs, and the dissolving back adds 50g TGDDM (compound, wherein R shown in the formula (I) fully with the PES of 10g under the room temperature
1Be H, R
2Be H) and 50g TMTGDDM (compound shown in the formula (I), wherein R
1Be CH
3, R
2Be CH
3), and 10g DMDDM (compound, wherein R shown in the formula (II)
1Be CH
3, R
2Be H, R
3Be CH
2) and 50g1,3,4-6FAPB (compound shown in the formula (III), wherein R
1Be CF
3, R
2For
), the 1.5g meta-cresol is mixed with the homogeneous clear solution, and heating removes solvent and prepares casting matrix under the vacuum, and program curing is 130 ℃ and solidified 2 hours that 150 ℃ solidified 4 hours, and 180 ℃ solidified 4 hours, and obtained the solidified epoxy matrix resin.DMA method (dynamic thermomechanometry) is surveyed second-order transition temperature, adopt the three-point bending loading mode, batten size (18 ± 0.5mm) * (5 ± 0.2mm) * (1.5 ± 0.2mm), frequency 1Hz, 5 ℃/min of temperature rise rate, the second-order transition temperature that records epoxy matrix resin is 225 ℃, according to the tensile strength of standard GB/T 16421-1996 to the epoxy matrix resin of preparation, tension set, modulus in tension is 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.Test triplicate, record the tensile strength 85MPa of this epoxy matrix resin, tension set 3.2%, modulus in tension 3.5GPa.
Embodiment 18
Under the room temperature with the PSF of 25g (compound shown in the formula V, n=28) and 25gPEI (polymkeric substance shown in the formula (VII) n=15) joins in 255ml N-methyl-2 pyrrolidone and stirs, and the dissolving back adds 50gTGDDM (compound, wherein R shown in the formula (I) fully
1Be H, R
2Be H) and 50g TMTGDDM (compound shown in the formula (I), wherein R
1Be CH
3, R
2Be CH
3), and 20g DDM (compound shown in the formula (II), wherein R
1Be H, R
2Be H, R
3Be CH
2), the 1.0g boron triflouride-mono aminoethane is mixed with the homogeneous clear solution, and heating removes solvent and prepares casting matrix under the vacuum, and program curing is 130 ℃ and solidified 2 hours that 160 ℃ solidified 3 hours, and 190 ℃ solidified 3 hours, and obtained the solidified epoxy matrix resin.DMA method (dynamic thermomechanometry) is surveyed second-order transition temperature, adopt the three-point bending loading mode, batten size (18 ± 0.5mm) * (5 ± 0.2mm) * (1.5 ± 0.2mm), frequency 1Hz, 5 ℃/min of temperature rise rate, the second-order transition temperature that records epoxy matrix resin is 215 ℃, according to the tensile strength of standard GB/T 16421-1996 to the epoxy matrix resin of preparation, tension set, modulus in tension is 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.Test triplicate, record the tensile strength 86MPa of this epoxy matrix resin, tension set 3.3%, modulus in tension 3.2GPa.
Claims (6)
1. an epoxy matrix resin is made by following compositions: the Resins, epoxy of 100 mass parts, the solidifying agent of 20-60 mass parts, the thermoplastic resin of the curing catalyst of 0.5-5.0 mass parts and 5-50 mass parts; The second-order transition temperature of described epoxy matrix resin is 210-235 ℃, and tensile strength is 80-86MPa, and tension set is 3.0%-3.3%, and modulus in tension is 3.2-3.5GPa;
Described Resins, epoxy be following a) and/or b);
Described a) is following 1) to 5) at least a Racemic glycidol amine epoxy resin:
1) compound, wherein R shown in the formula (I)
1Be H, R
2Be H;
2) compound, wherein R shown in the formula (I)
1Be Cl, R
2Be H;
3) compound, wherein R shown in the formula (I)
1Be CH
3, R
2Be H;
4) compound, wherein R shown in the formula (I)
1Be Cl, R
2Be C1;
5) compound, wherein R shown in the formula (I)
1Be CH
3, R
2Be CH
3
Described b) is at least a in following six kinds of materials: terephthalic acid diglycidyl ester, o-phthalic acid diglycidyl ester, 1,2-epoxy cyclohexane-4,5-dioctyl phthalate 2-glycidyl ester, p-aminophenol Resins, epoxy, bisphenol f type epoxy resin and bisphenol A type epoxy resin;
Described solidifying agent is following c) and/or d);
Described c) be following 6)-12) at least a:
6) compound, wherein R shown in the formula (II)
1Be H, R
2Be H, R
3Be CH
2
7) compound, wherein R shown in the formula (II)
1Be Cl, R
2Be H, R
3Be CH
2
8) compound, wherein R shown in the formula (II)
1Be CH
3, R
2Be H, R
3Be CH
2
9) compound, wherein R shown in the formula (II)
1Be Cl, R
2Be Cl, R
3Be CH
2
10) compound, wherein R shown in the formula (II)
1Be CH
3, R
2Be CH
3, R
3Be CH
2
11) compound, wherein R shown in the formula (II)
1Be H, R
2Be H, R
3Be O;
12) compound, wherein R shown in the formula (II)
1Be H, R
2Be H, R
3Be SO
2
Described d) be following 13)-18) at least a:
13) compound, wherein R shown in the formula (III)
1Be H, R
2For
14) compound, wherein R shown in the formula (III)
1Be H, R
2For
15) compound, wherein R shown in the formula (III)
1Be H, R
2For
16) compound, wherein R shown in the formula (III)
1Be CF
3, R
2For
17) compound, wherein R shown in the formula (III)
1Be CF
3, R
2For
18) compound, wherein R shown in the formula (III)
1Be CF
3, R
2For
Described curing catalyst is a kind of or its arbitrary combination in following six kinds of materials: meta-cresol, Resorcinol, 2,4,6-three (dimethylamino methyl)-phenol, boron triflouride-mono aminoethane, dithioglycol and nonylbenzene phenol;
Described thermoplastic resin is a kind of or its arbitrary combination in the polymkeric substance shown in following formula (IV)-Shi (VII):
Wherein, n is 1-60.
2. the method for preparing the described epoxy matrix resin of claim 1, its feature is mixed in: Resins, epoxy with claim 1 in the described epoxy matrix resin and thermoplastic resin, 100-200 ℃ of heated and stirred to forming clear solution, clear solution is cooled to 50-100 ℃ then, then add solidifying agent and curing catalyst in the described epoxy matrix resin of claim 1 in described clear solution, stirring and dissolving obtains epoxy matrix resin.
3. the method for preparing the described epoxy matrix resin of claim 1, its feature in: the thermoplastic resin with claim 1 in the described epoxy matrix resin at room temperature is dissolved in the solvent, obtain the solution of thermoplastic resin, add Resins, epoxy, solidifying agent and curing catalyst in the described epoxy matrix resin of claim 1 then in described solution, stirring and dissolving obtains epoxy matrix resin.
4. according to the method described in the claim 3, it is characterized in that: described solvent is a kind of or its arbitrary combination in following seven kinds of materials: tetrahydrofuran (THF), acetone, methylene dichloride, trichloromethane, N, N '-dimethyl formamide, N, N '-N,N-DIMETHYLACETAMIDE and N-N-methyl-2-2-pyrrolidone N-.
5. according to arbitrary described method among the claim 2-4, it is characterized in that: described method also comprises the step that described epoxy matrix resin is cured.
6. the application of the described epoxy matrix resin of claim 1 in the preparation carbon fiber.
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| CN101914195A (en) * | 2010-08-12 | 2010-12-15 | 蓝星(北京)化工机械有限公司 | Heat-resistant epoxy resin compound for forming RTM, epoxy base resin and preparation method thereof |
| US9068040B2 (en) * | 2010-10-12 | 2015-06-30 | Hexcel Corporation | Solvent resistant thermoplastic toughened epoxy |
| CN102899901A (en) * | 2012-10-23 | 2013-01-30 | 金发科技股份有限公司 | High-temperature-resistant emulsion type carbon fiber sizing agent and preparation and applications of carbon fiber sizing agent |
| CN103057024B (en) * | 2013-01-22 | 2015-06-03 | 桂林电子科技大学 | Photodiffusion sheet of epoxy resin composite coating with specific micro-phase structure and preparation method of photodiffusion sheet |
| KR102377100B1 (en) * | 2013-03-22 | 2022-03-21 | 린텍 가부시키가이샤 | Protective film-forming film and protective film-forming composite sheet |
| CN104277419A (en) * | 2013-07-09 | 2015-01-14 | 上海杰事杰新材料(集团)股份有限公司 | Tough epoxy resin curing system and preparation method thereof |
| CN104277418A (en) * | 2013-07-09 | 2015-01-14 | 上海杰事杰新材料(集团)股份有限公司 | Carbon fiber reinforced toughened epoxy resin composite material and preparation method thereof |
| CN103980231B (en) * | 2014-06-04 | 2016-03-30 | 中国科学院上海有机化学研究所 | A kind of synthetic method of pentafluorophenyl group propylene oxide |
| CN113930158B (en) * | 2021-10-15 | 2022-09-13 | 中国铁路设计集团有限公司 | Modified epoxy resin, preparation method thereof, epoxy resin emulsion and anticorrosive paint |
| CN116021671B (en) * | 2023-02-06 | 2024-09-17 | 陕西科技大学 | Preparation method of non-orthogonal thermoplastic laminated plate |
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