CN102746622A - Prepreg with moderate-temperature cured epoxy resin as substrate material and preparation method thereof - Google Patents

Prepreg with moderate-temperature cured epoxy resin as substrate material and preparation method thereof Download PDF

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Publication number
CN102746622A
CN102746622A CN2012102616080A CN201210261608A CN102746622A CN 102746622 A CN102746622 A CN 102746622A CN 2012102616080 A CN2012102616080 A CN 2012102616080A CN 201210261608 A CN201210261608 A CN 201210261608A CN 102746622 A CN102746622 A CN 102746622A
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epoxy resin
prepreg
temperature setting
intermediate temperature
body material
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林再文
李树茂
董鹏
高赫
王明寅
侯涤洋
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HARBIN FRP INSTITUTE
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HARBIN FRP INSTITUTE
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Abstract

The invention relates to a prepreg with moderate-temperature cured epoxy resin as a substrate material and a preparation method of the prepreg, relates to a prepreg and a preparation method of the prepreg, and is used for solving the problems that the prepreg is prepared at the curing temperature higher than 120 DEG C, so that the product is high in energy consumption and the dimensional accuracy of the product is difficult to control. The prepreg with moderate-temperature cured epoxy resin as the substrate material is composed of an epoxy resin mixture, a curing agent system mixture and a moderate-temperature cured epoxy resin infiltration reinforcing material prepared by a toughening agent, wherein the epoxy resin mixture is composed of solid or semisolid epoxy resin and liquid epoxy resin, and the curing agent system mixture is composed of a curing agent and a promoter. The preparation method comprises the steps of: (1) preparing the epoxy resin mixture; (2) preparing the curing agent system mixture; (3) preparing the moderate-temperature cured epoxy resin; and (4) preparing the prepreg. The prepared product can be used for preparing planes, spacecrafts, yachts, golf rods and the like, and has important commercial value.

Description

Prepreg that a kind of intermediate temperature setting epoxy resin is body material and preparation method thereof
Technical field
The present invention relates to a kind of prepreg and preparation method thereof.
Background technology
Advanced polymer matrix composites have critical role in fields such as aerospace, electronics, traffic, the energy, and become one of most hotly competitive in the world field of new gradually.Have epoxy prepreg specific tenacity, specific modulus height and performance can design and characteristics such as forming technology variety, are widely used in space flight and aviation and civil area etc.
When the solidification value of epoxy prepreg was higher than 120 ℃, resulting product can produce bigger internal stress, was unfavorable for the controlling dimension precision, even can cause material to destroy in advance.Higher solidification value is had relatively high expectations and the height that consumes energy to molding device, mold tooling and the subsidiary material of matrix material, and at room temperature period of storage is short, has limited the range of application of prepreg.
Summary of the invention
The present invention will solve the solidification value of existing epoxy prepreg height; The preparing product energy consumption is high; Be unfavorable for controlling the problem of dimensional accuracy of products; Short and the little problem of the scope of application of period of storage, and prepreg that a kind of intermediate temperature setting epoxy resin is provided is body material and preparation method thereof.
The prepreg that a kind of intermediate temperature setting epoxy resin is body material soaks into strongthener by intermediate temperature setting epoxy resin and forms; Wherein intermediate temperature setting epoxy resin is prepared from 50% ~ 90% epoxy resin composition, 5% ~ 30% curative systems mixture and 5% ~ 20% toughner by massfraction; Epoxy resin composition is that solid-state or semi-solid state epoxy resin and 20% ~ 80% liquid-state epoxy resin mix by 20% ~ 80% by massfraction; The curative systems mixture is to be mixed by 40% ~ 90% solidifying agent and 10% ~ 60% promotor by massfraction.
A kind of intermediate temperature setting epoxy resin is the preparation method of the prepreg of body material: one, with solid-state or semi-solid state epoxy resin exsiccant container internal heating to 50 ℃ ~ 140 ℃; Constant temperature 1 h ~ 12 hours; Get fused epoxy resin, add liquid-state epoxy resin therein, the rotating speed with 1700 commentaries on classics/min ~ 3000 commentaries on classics/min in container stirs; And, obtain epoxy resin composition 50 ℃ ~ 140 ℃ following constant temperature 0.1 h ~ 3 hours; Solid-state or the semi-solid state epoxy resin that wherein adds by mass percentage in the epoxy resin composition is 20% ~ 80%, and the liquid-state epoxy resin of adding is 20% ~ 80%; Two, with solidifying agent exsiccant container internal heating to 50 ℃ ~ 100 ℃, constant temperature 5 h ~ 20 hours add promotor therein, the rotating speed with 1700 commentaries on classics/min ~ 3000 commentaries on classics/min in container stirs 0.5h ~ 2h, obtains the curative systems mixture; The solidifying agent that adds by mass percentage in this curative systems mixture is 40% ~ 90%, and the promotor of adding is 10% ~ 60%; Three, epoxy resin composition in toughner, the step 1 and the curative systems mixture in the step 2 are joined in the exsiccant container; Mix; Promptly obtain intermediate temperature setting epoxy resin; The epoxy resin composition that adds by mass percentage in the said composition is 50% ~ 90%, and the curative systems mixture of adding is 6% ~ 30%, and the toughner of adding is 4% ~ 20%.Four, with the intermediate temperature setting epoxy resin that obtains in the step 3 at 50 ℃ ~ 140 ℃, constant temperature polymerization 10 minutes ~ 200 minutes; With polymeric intermediate temperature setting epoxy resin is that body material and strongthener prepare prepreg with hot melt process.
Advantage of the present invention: the solidification value of this prepreg is 70 ℃ ~ 100 ℃, and lower solidification value can reduce the manufacturing cost of composite products, improves product size stability; This prepreg is applicable to autoclave molding, vacuum forming, compression molding and matched-mold forming; The matrix material of this equipment of preimpregnated material manufacture has excellent mechanical property, and this type of prepreg has the storage period greater than 3 months at normal temperatures, helps storage, transportation and the production of prepreg.The present invention can be used for preparing national defence and civil areas such as aircraft, spacecraft, yacht, bike.
Embodiment
Below provide embodiment of the present invention and be further described, yet technical scheme of the present invention but is not limited to following cited embodiment.
Embodiment one: the prepreg that a kind of intermediate temperature setting epoxy resin is body material soaks into strongthener by intermediate temperature setting epoxy resin and forms; Wherein intermediate temperature setting epoxy resin is prepared from 50% ~ 90% epoxy resin composition, 5% ~ 30% curative systems mixture and 5% ~ 20% toughner by massfraction; Epoxy resin composition is that solid-state or semi-solid state epoxy resin and 20% ~ 80% liquid-state epoxy resin mix by 20% ~ 80% by massfraction; The curative systems mixture is to be mixed by 40% ~ 90% solidifying agent and 10% ~ 60% promotor by massfraction.
The solidification value of the prepreg that a kind of intermediate temperature setting epoxy resin of this embodiment design is body material is 70 ℃ ~ 100 ℃, and lower solidification value can reduce the manufacturing cost of composite products, improves product size stability; This prepreg is applicable to autoclave molding, vacuum forming, compression molding and matched-mold forming; The matrix material of this type of equipment of preimpregnated material manufacture has excellent mechanical property, and this type of prepreg has the storage period greater than 3 months at normal temperatures, helps storage, transportation and the production of prepreg.
Embodiment two: the difference of this embodiment and embodiment one is: described solid-state or semi-solid state epoxy resin is one or more the combination in bisphenol A type epoxy resin, bisphenol-s epoxy resin and the novolac epoxy; Liquid-state epoxy resin is one or more the combination in bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, trifunctional epoxy resin, four-functional group epoxy resin, phenolic resin varnish type epoxy resin and the formaldehyde varnish type epoxy resin.Other is identical with embodiment one.
Embodiment three: this embodiment with embodiment one or two difference is: described solidifying agent is Dyhard RU 100 compounds or Dyhard RU 100 compounds modifier; Described promotor is one or several the combination in urea compounds, polyureas compound, polyether monoamine compound, imidazoles and the imdazole derivatives; Described toughner is one or more the combination in core-shell particles class toughner, epoxy resin and rubber prepolymer, end epoxy group(ing) rubber and the terminal hydroxy group rubber.Other is identical with embodiment one or two.
Embodiment four: the difference of this embodiment and embodiment one to three is: described strongthener is one or more the combination in thomel, spun glass, aramid fiber, aromatic polyamide fibre, high molecular weight polyethylene fiber and the basalt fibre.Other is identical with one of embodiment one to three.
Embodiment five: this embodiment is the preparation method that a kind of intermediate temperature setting epoxy resin is the prepreg of body material, specifically accomplishes according to the following steps:
One, with solid-state or semi-solid state epoxy resin exsiccant container internal heating to 50 ℃ ~ 140 ℃; Constant temperature 1 h ~ 12 hours; Get fused epoxy resin, add liquid-state epoxy resin therein, the rotating speed with 1700 commentaries on classics/min ~ 3000 commentaries on classics/min in container stirs; And, obtain epoxy resin composition 50 ℃ ~ 140 ℃ following constant temperature 0.1 h ~ 3 hours; Solid-state or the semi-solid state epoxy resin that wherein adds by mass percentage in the epoxy resin composition is 20% ~ 80%, and the liquid-state epoxy resin of adding is 20% ~ 80%;
Two, with solidifying agent exsiccant container internal heating to 50 ℃ ~ 100 ℃, constant temperature 5 h ~ 20 hours add promotor therein, the rotating speed with 1700 commentaries on classics/min ~ 3000 commentaries on classics/min in container stirs 0.5h ~ 2h, obtains the curative systems mixture; The solidifying agent that adds by mass percentage in this curative systems mixture is 40% ~ 90%, and the promotor of adding is 10% ~ 60%;
Three, epoxy resin composition in toughner, the step 1 and the curative systems mixture in the step 2 are joined in the exsiccant container; Mix; Promptly obtain intermediate temperature setting epoxy resin; The epoxy resin composition that adds by mass percentage in the said composition is 50% ~ 90%, and the curative systems mixture of adding is 6% ~ 30%, and the toughner of adding is 4% ~ 20%;
Four, with the intermediate temperature setting epoxy resin that obtains in the step 3 at 50 ℃ ~ 140 ℃, constant temperature polymerization 10 minutes ~ 200 minutes; With polymeric intermediate temperature setting epoxy resin is that body material and strongthener prepare prepreg with hot melt process.
Embodiment six: this embodiment and embodiment five differences are: the solid-state or semi-solid state epoxy resin in the described step 1 is one or more the combination in bisphenol A type epoxy resin, bisphenol-s epoxy resin and the novolac epoxy; Liquid-state epoxy resin in the step 1 is one or more the combination in bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, trifunctional epoxy resin, four-functional group epoxy resin, phenolic resin varnish type epoxy resin and the formaldehyde varnish type epoxy resin.Other is identical with embodiment five.
Embodiment seven: this embodiment with embodiment five or six differences is: the solidifying agent in the described step 2 is Dyhard RU 100 compounds or Dyhard RU 100 compounds modifier; Promotor in the step 2 is one or several the combination in urea compounds, polyureas compound, polyether monoamine compound, the glyoxaline compound; Toughner in the step 3 is one or more the combination in core-shell particles class toughner, epoxy resin and rubber prepolymer, end epoxy group(ing) rubber and the terminal hydroxy group rubber.Other and embodiment five or six phase with.
Embodiment eight: this embodiment and embodiment five to eight differences are: the hot melt process in the described step 4 prepares the prepreg method for being under 50 ℃ ~ 140 ℃ the condition polymeric intermediate temperature setting epoxy resin to be prepared into glued membrane being coated with film temperature earlier, is to carry out the hot melt preimpregnation under 50 ℃ ~ 140 ℃ the condition in the preimpregnation temperature with the glued membrane for preparing and strongthener again.Other is identical with one of embodiment five to eight.
Embodiment nine: this embodiment and embodiment five to seven differences are: the strongthener in the described step 4 is one or more the combination in thomel, spun glass, aramid fiber, aromatic polyamide fibre, high molecular weight polyethylene fiber and the basalt fibre.Other is identical with one of embodiment five to seven.
Embodiment ten: this embodiment with embodiment five to nine differences is: described strongthener is fibrous braid that obtains through braiding or the fibrous bundle that obtains through unilateral stretching; Wherein, the ratio of the mass area ratio of fortifying fibre cloth and thickness is 300 ~ 1700; The unit of mass area ratio is g/m 2, the unit of thickness is mm; The Tex number of reinforcing fiber bundles is 100 ~ 10000.Other is identical with one of embodiment five to nine.
Adopt following verification experimental verification effect of the present invention:
Test one: a kind of intermediate temperature setting epoxy resin is the preparation method of the prepreg of body material, specifically accomplishes according to the following steps:
One, with bisphenol A type epoxy resin CYD012 at exsiccant container internal heating to 100 ℃; Constant temperature 2 hours; Get fused bisphenol A type epoxy resin CYD012, add trifunctional epoxy resin TDE85 therein, the rotating speed with 2000 commentaries on classics/min in container stirs; And, obtain epoxy resin composition 90 ℃ of following constant temperature 2 hours; The bisphenol A type epoxy resin CYD012 that wherein adds by mass percentage in the epoxy resin composition is 66.7%, and the trifunctional epoxy resin TDE85 of adding is 33.3%;
Two, with curing agent dicyandiamide at exsiccant container internal heating to 70 ℃, constant temperature 8 hours adds promotor passivation imidazoles therein, in container, carries out stirring 1h with the rotating speed of 2000 commentaries on classics/min, obtains the curative systems mixture; The curing agent dicyandiamide that adds by mass percentage in this curative systems mixture is 72.7%; The promotor passivation imidazoles that adds is 27.3%;
Three, epoxy resin composition in terminal hydroxy group rubber-like toughner 1800XB, the step 1 and the curative systems mixture in the step 2 are joined in the exsiccant container; Mix; Promptly obtain intermediate temperature setting epoxy resin; The epoxy resin composition that adds by mass percentage in the said composition is 81.1%, and the curative systems mixture of adding is 9.9%, and the toughner 1800XB of adding is 9%.
Four, with the intermediate temperature setting epoxy resin that obtains in the step 3 at 80 ℃, constant temperature polyase 13 0 minute; With polymeric intermediate temperature setting epoxy resin is that body material and strongthener prepare prepreg with hot melt process; Described strongthener is carbon fiber bundle T700, and the tex number is 800, and being coated with film temperature is 80 ℃, 100 ℃ of preimpregnation temperature.
This prepreg is when the storage time is 113 days at normal temperatures, its viscosity diminishes.The use characteristics of prepreg of testing a gained is as shown in table 1.
Prepreg use characteristics in table 1 test one
Performance Characteristic
Viscosity under the room temperature Have viscosity, can be bonding between the prepreg
50 ℃ of gel times Greater than 2 hours
90 ℃ of gel times Less than 50 minutes
The following shelf lives of normal temperature 113 days
Prepreg is equipped with matrix material with the autoclave legal system, and its processing parameter is pressure 0.5MPa, and solidification value is earlier 60 ℃ of constant temperature 2 hours, and 80 ℃ of constant temperature 10 hours, measured composite property was as shown in table 2 again.
Table 2 test one composite property
Performance Test value
Fiber volume fraction ?60%
Voidage ?0.32%
0 ° of tensile strength ?2119MPa
0 ° of tensile modulus ?165GPa
Flexural strength ?1563MPa
Modulus in flexure ?136GPa
0 ° of compressive strength ?1033MPa
0 ° of modulus of compression ?146GPa
The short beam interlaminar shear strength ?72MPa
Test two: a kind of intermediate temperature setting epoxy resin is the preparation method of the prepreg of body material, specifically accomplishes according to the following steps:
One, with phenol aldehyde type epoxy resin F54 at exsiccant container internal heating to 100 ℃; Constant temperature 2 hours; Get fused phenol aldehyde type epoxy resin F54, add bisphenol A type epoxy resin E51 therein, the rotating speed with 2000 commentaries on classics/min in container stirs; And, obtain epoxy resin composition 90 ℃ of following constant temperature 2 hours; The phenol aldehyde type epoxy resin F54 that wherein adds by mass percentage in the epoxy resin composition is 70%, and the bisphenol A type epoxy resin E51 of adding is 30%;
Two, with curing agent dicyandiamide at exsiccant container internal heating to 80 ℃; Constant temperature 3 hours; Add polyether monoamine solidifying agent D2000 and polyureas vulkacit D yhradUR500 therein, the rotating speed with 2000 commentaries on classics/min in container stirs 1h, obtains the curative systems mixture; The curing agent dicyandiamide that adds by mass percentage in this curative systems mixture is 46.7%, and the polyether monoamine solidifying agent D2000 of adding is 33.3%, and the polyureas vulkacit D yhrad UR500 of adding is 20%;
Three, epoxy resin composition in terminal hydroxy group rubber-like toughner DTBN401, the step 1 and the curative systems mixture in the step 2 are joined in the exsiccant container; Mix; Promptly obtain intermediate temperature setting epoxy resin; The epoxy resin composition that adds by mass percentage in the said composition is 83.3%, and the curative systems mixture of adding is 12.5%, and the toughner DTBN401 of adding is 4.2%;
Four, with the intermediate temperature setting epoxy resin that obtains in the step 3 at 60 ℃, constant temperature polyase 13 0 minute; With polymeric intermediate temperature setting epoxy resin is that body material and strongthener prepare prepreg with hot melt process.Described strongthener is carbon fiber bundle T700, and the tex number is 800, and being coated with film temperature is 80 ℃, 100 ℃ of preimpregnation temperature.
This prepreg is at normal temperatures during 102 days storage times, its viscosity diminishes.The use characteristics of prepreg of testing two gained is as shown in table 3.
The prepreg use characteristics of table 3 test two
Performance Characteristic
Viscosity under the room temperature Have viscosity, can be bonding between the prepreg
50 ℃ of gel times Greater than 2 hours
90 ℃ of gel times Less than 50 minutes
The following shelf lives of normal temperature 102 days
This prepreg prepares matrix material with vacuum bag molding, and its processing parameter is pressure 0.08MPa, and solidification value is earlier 60 ℃ of constant temperature 1 hour, and 90 ℃ of constant temperature 5 hours, measured composite property was as shown in table 4 again.
Table 4 test two composite properties
Performance Test value
Fiber volume fraction ?58%
Voidage ?0.46%
0 ° of tensile strength ?1980MPa
0 ° of tensile modulus ?161GPa
Flexural strength ?1543MPa
Modulus in flexure ?132GPa
0 ° of compressive strength ?1043MPa
0 ° of modulus of compression ?138GPa
The short beam interlaminar shear strength ?68MPa
Test three: a kind of intermediate temperature setting epoxy resin is the preparation method of the prepreg of body material, specifically accomplishes according to the following steps:
One, be that phenol aldehyde type epoxy resin DEN438 and the bisphenol A type epoxy resin CYD012 of 6:5 is at exsiccant container internal heating to 70 ℃ with mass ratio; Constant temperature 6 hours; Get the compsn of fused phenol aldehyde type epoxy resin DEN438 and bisphenol A type epoxy resin CYD012; In this compsn, adding mass ratio is the bisphenol f type epoxy resin 170 and bisphenol A type epoxy resin E54 of 5:4; Rotating speed with 2000 commentaries on classics/min in container stirs, and 70 ℃ of following constant temperature 2 hours, obtains epoxy resin composition; Phenol aldehyde type epoxy resin DEN438 that wherein adds by mass percentage in the epoxy resin composition and the compsn of bisphenol A type epoxy resin CYD012 are 55%; Bisphenol f type epoxy resin 170 that adds and the compsn of bisphenol A type epoxy resin E54 are 45%;
Two, with curing agent dicyandiamide at exsiccant container internal heating to 70 ℃, constant temperature 8 hours adds promotor passivation imidazoles therein, the rotating speed with 2000 commentaries on classics/min in container stirs 1h, obtains the curative systems mixture; The curing agent dicyandiamide that adds by mass percentage in this curative systems mixture is 72.7%, and the promotor passivation imidazoles of adding is 27.3%;
Three, epoxy resin composition in terminal hydroxy group rubber-like toughner 1800XB, the step 1 and the curative systems mixture in the step 2 are joined in the exsiccant container; Mix; Promptly obtain intermediate temperature setting epoxy resin; The epoxy resin composition that adds by mass percentage in the said composition is 82.6%, and the curative systems mixture of adding is 9.1%, and the toughner 1800XB of adding is 8.3%;
Four, with the intermediate temperature setting epoxy resin that obtains in the step 3 at 80 ℃, constant temperature polyase 13 0 minute; With polymeric intermediate temperature setting epoxy resin is that body material and strongthener prepare prepreg with hot melt process; Described strongthener is a glasscloth, and the ratio of its mass area ratio and thickness is 400; The unit of mass area ratio is g/m 2, the unit of thickness is mm; Being coated with film temperature is 90 ℃, 90 ℃ of preimpregnation temperature.
During 107 days storage times, it is viscosity diminishes at room temperature at normal temperatures for this prepreg.The use characteristics of prepreg of testing three gained is as shown in table 5.
Table 5 test three prepreg use characteristics
Performance Characteristic
Viscosity under the room temperature Have viscosity, can be bonding between the prepreg
50 ℃ of gel times Greater than 2 hours
100 ℃ of gel times Less than 50 minutes
The following shelf lives of normal temperature 107 days
This prepreg is with matched-mold forming prepared matrix material, and its processing parameter is: solidification value for earlier 60 ℃ of constant temperature 1 hour, again 80 ℃ of constant temperature 1 hour, at last 100 ℃ of constant temperature 3 hours.Measured composite property is as shown in table 6.
Table 6 test three composite properties
Performance Test value
Fiber volume fraction 60%
Voidage 0.52%
0 ° of tensile strength 581MPa
0 ° of tensile modulus 61GPa
90 ° of tensile strengths 572MPa
90 ° of tensile moduluses 60GPa
0 ° of compressive strength 573MPa
0 ° of modulus of compression 55GPa
90 ° of compressive strengths 571MPa
90 ° of modulus of compression 56GPa
Shearing resistance 95MPa

Claims (10)

1. prepreg that intermediate temperature setting epoxy resin is body material is characterized in that intermediate temperature setting epoxy resin is that the prepreg of body material soaks into strongthener by intermediate temperature setting epoxy resin and forms; Wherein intermediate temperature setting epoxy resin is prepared from 50% ~ 90% epoxy resin composition, 5% ~ 30% curative systems mixture and 5% ~ 20% toughner by massfraction; Epoxy resin composition is to be mixed by 20% ~ 80% liquid-state epoxy resin solid-state or semi-solid state epoxy resin and 20% ~ 80% by massfraction; The curative systems mixture is to be mixed by 40% ~ 90% solidifying agent and 10% ~ 60% promotor by massfraction.
2. the prepreg that a kind of intermediate temperature setting epoxy resin according to claim 1 is body material is characterized in that described solid-state or semi-solid state epoxy resin is one or more the combination in bisphenol A type epoxy resin, bisphenol-s epoxy resin and the novolac epoxy; Liquid-state epoxy resin is one or more the combination in bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, trifunctional epoxy resin, four-functional group epoxy resin, phenolic resin varnish type epoxy resin and the formaldehyde varnish type epoxy resin.
3. the prepreg that a kind of intermediate temperature setting epoxy resin according to claim 1 is body material is characterized in that described solidifying agent is Dyhard RU 100 compounds or Dyhard RU 100 compounds modifier; Described promotor is one or several the combination in urea compounds, polyureas compound, polyether monoamine compound, imidazoles and the imdazole derivatives; Described toughner is one or more the combination in core-shell particles class toughner, epoxy resin and rubber prepolymer, end epoxy group(ing) rubber and the terminal hydroxy group rubber.
4. the prepreg that a kind of intermediate temperature setting epoxy resin according to claim 1 is body material is characterized in that described strongthener is one or more the combination in thomel, spun glass, aramid fiber, aromatic polyamide fibre, high molecular weight polyethylene fiber and the basalt fibre.
5. the preparation method that a kind of intermediate temperature setting epoxy resin as claimed in claim 1 is the prepreg of body material is characterized in that the preparation method that a kind of intermediate temperature setting epoxy resin is the prepreg of body material accomplishes according to the following steps:
One, with solid-state or semi-solid state epoxy resin exsiccant container internal heating to 50 ℃ ~ 140 ℃; Constant temperature 1 h ~ 12 hours; Get fused epoxy resin, add liquid-state epoxy resin therein, the rotating speed with 1700 commentaries on classics/min ~ 3000 commentaries on classics/min in container stirs; And, obtain epoxy resin composition 50 ℃ ~ 140 ℃ following constant temperature 0.1 h ~ 3 hours; Solid-state or the semi-solid state epoxy resin that wherein adds by mass percentage in the epoxy resin composition is 20% ~ 80%, and the liquid-state epoxy resin of adding is 20% ~ 80%;
Two, with solidifying agent exsiccant container internal heating to 50 ℃ ~ 100 ℃, constant temperature 5 h ~ 20 hours add promotor therein, the rotating speed with 1700 commentaries on classics/min ~ 3000 commentaries on classics/min in container stirs 0.5h ~ 2h, obtains the curative systems mixture; The solidifying agent that adds by mass percentage in this curative systems mixture is 40% ~ 90%, and the promotor of adding is 10% ~ 60%;
Three, epoxy resin composition in toughner, the step 1 and the curative systems mixture in the step 2 are joined in the exsiccant container; Mix; Promptly obtain intermediate temperature setting epoxy resin; The epoxy resin composition that adds by mass percentage in the said composition is 50% ~ 90%, and the curative systems mixture of adding is 6% ~ 30%, and the toughner of adding is 4% ~ 20%.
Four, with the intermediate temperature setting epoxy resin that obtains in the step 3 at 50 ℃ ~ 140 ℃, constant temperature polymerization 10 minutes ~ 200 minutes; With polymeric intermediate temperature setting epoxy resin is that body material and strongthener prepare prepreg with hot melt process.
6. the preparation method that a kind of intermediate temperature setting epoxy resin according to claim 5 is the prepreg of body material is characterized in that solid-state or semi-solid state epoxy resin in the described step 1 is one or more the combination in bisphenol A type epoxy resin, bisphenol-s epoxy resin and the novolac epoxy; Liquid-state epoxy resin in the step 1 is one or more the combination in bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, trifunctional epoxy resin, four-functional group epoxy resin, phenolic resin varnish type epoxy resin and the formaldehyde varnish type epoxy resin.
7. the preparation method that a kind of intermediate temperature setting epoxy resin according to claim 5 is the prepreg of body material is characterized in that the solidifying agent in the described step 2 is Dyhard RU 100 compounds or Dyhard RU 100 compounds modifier; Promotor in the step 2 is one or several the combination in urea compounds, polyureas compound, polyether monoamine compound, the glyoxaline compound; Toughner in the step 3 is one or more the combination in core-shell particles class toughner, epoxy resin and rubber prepolymer, end epoxy group(ing) rubber and the terminal hydroxy group rubber.
8. the preparation method who is the prepreg of body material according to right 5 described a kind of intermediate temperature setting epoxy resin; It is characterized in that hot melt process in the described step 4 prepares the prepreg method for being under 50 ℃ ~ 140 ℃ the condition polymeric intermediate temperature setting epoxy resin to be prepared into glued membrane being coated with film temperature earlier, is to carry out the hot melt preimpregnation under 50 ℃ ~ 140 ℃ the condition in the preimpregnation temperature with the glued membrane for preparing and strongthener again.
9. the preparation method who is the prepreg of body material according to claim 5 or 8 described a kind of intermediate temperature setting epoxy resin is characterized in that described strongthener is one or more the combination in thomel, spun glass, aramid fiber, aromatic polyamide fibre, high molecular weight polyethylene fiber and the basalt fibre.
10. the preparation method who is the prepreg of body material according to claim 5 or 8 described a kind of intermediate temperature setting epoxy resin is characterized in that described strongthener is fibrous braid that obtains through braiding or the fibrous bundle that obtains through unilateral stretching; Wherein, the ratio of the mass area ratio of fortifying fibre cloth and thickness is 300 ~ 1700; The unit of mass area ratio is g/m 2, the unit of thickness is mm; The Tex number of reinforcing fiber bundles is 100 ~ 10000.
CN2012102616080A 2012-07-26 2012-07-26 Prepreg with moderate-temperature cured epoxy resin as substrate material and preparation method thereof Pending CN102746622A (en)

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CN114106515A (en) * 2021-12-31 2022-03-01 广联航空工业股份有限公司 Medium-temperature thermosetting resin mixture with high modulus stability and preparation method thereof
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102300901A (en) * 2009-01-30 2011-12-28 味之素株式会社 Resin composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102300901A (en) * 2009-01-30 2011-12-28 味之素株式会社 Resin composition

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CN105602202A (en) * 2015-12-30 2016-05-25 江苏恒神股份有限公司 Resin composition, prepreg thereof and composite material
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Application publication date: 20121024