CN103467709B - Epoxy resin for polyaryletherketone ex-situ toughening, and preparation method and application thereof - Google Patents
Epoxy resin for polyaryletherketone ex-situ toughening, and preparation method and application thereof Download PDFInfo
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- CN103467709B CN103467709B CN201310477161.5A CN201310477161A CN103467709B CN 103467709 B CN103467709 B CN 103467709B CN 201310477161 A CN201310477161 A CN 201310477161A CN 103467709 B CN103467709 B CN 103467709B
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Abstract
The invention relates to an epoxy resin, particularly an epoxy resin for polyaryletherketone ex-situ toughening, and a preparation method and application thereof. The epoxy resin for polyaryletherketone ex-situ toughening is composed of the following components in parts by mass: 20-50 parts of tetraglycidylamine epoxy resin, 50-80 parts of diglycidyl ether epoxy resin and 35-45 parts of 4,4-diaminodiphenyl sulfone. The preparation method comprises the following steps: prepolymerizing the tetraglycidylamine epoxy resin, diglycidyl ether epoxy resin and 4,4-diaminodiphenyl sulfone; cutting, baiting and spreading the fabric according a predetermined shape, laying a toughener polyaryletherketone film between every two layers of the fabric to form a preformed body, and filling in the mold; according to an epoxy resin curing technique for an RTM technique, injecting, curing, cooling, demolding and trimming to obtain the epoxy resin formed product for polyaryletherketone ex-situ toughening. The epoxy resin for polyaryletherketone ex-situ toughening is applicable to preparing an aviation composite material.
Description
Technical field
The present invention relates to a kind of epoxy resin, especially relate to a kind of polyaryletherketone that is suitable for and to off normal toughness reinforcing epoxy resin and preparation method thereof and application.
Background technology
In the low-cost manufacturing technique of advanced composite material, Resin transfer molding (Resin Transfer Molding, RTM) technique is the main flow of current international field of compound material research and development.The key of RTM forming technique is the resin that will have a low-viscosity long adaptive phase, and in order to meet this characteristic, the RTM of domestic and international main flow is resin dedicated general not toughness reinforcing.In order to solve the contradiction of resin low-viscosity and matrix material high tenacity, first advanced composite material key lab of Beijing Research Inst. of Aeronautic Material at home and abroad proposes and has developed " offing normal " (Ex-situ) composite toughening technology ([1] Yi Xiaosu with the whole independent intellectual property right of China, An Xuefeng, Tang Bangming, Zhang Zilong.A method to significantly improve the composite toughness [P] .Chinese Patent No.ZL01 100981.0 (in Chinese), 2001,3; [2] Yi Xiaosu, An Xuefeng, Tang Bangming, Zhang Ming.A toughened composite laminate and the preparation method [P] .Chinese Patent No.ZL200610099381.9,2006,7).Find through series of studies, composite toughening technology of " offing normal " is not only applicable to prepreg level composite material, and be applicable to the shaping matrix material of RTM ([3] Yi Xiaosu.Challenges and innovation of advanced composite materials technology [J] .Aeronautical Manufacturing Technology, 2004,7,27-33).
Traditional in-situ flexible method can prepare the matrix material that toughness increases substantially, but the viscosity of resin system increases, and cannot be applied to RTM technique.It is toughness reinforcing that toughening technology of " offing normal " then carries out selectivity to the interlayer that matrix material is the weakest, can solve a difficult problem for resin low-viscosity and matrix material high tenacity in RTM technique preferably.Phenolphthalein modified version polyaryletherketone (PAEK-C) applies the most successfully thermoplastic toughening layer resin in current aviation composite field, applies in multiple model aviation composite.In order to meet " offing normal " toughness reinforcing RTM technology condition, need the dissolution process time of toughening layer resin and matrix resin longer, and the dissolving of several epoxy resin conventional in PAEK-C and current aviation composite is too fast, cause the rapid solution of PAEK-C in matrix resin injection process that the viscosity of system resin is suddenlyd change, thus cause resin macro-flow and the wetting property of fibre reinforcement is declined, affect the performance of matrix material.Therefore, on the basis of original processing condition, tooling etc., develop a kind of new epoxy-resin systems most important to adapt to polyaryletherketone toughening technology of " offing normal ".The present invention " a kind of be suitable for polyaryletherketone off normal toughness reinforcing epoxy resin and preparation method thereof and application " is exactly set out based on such thought and the development of a kind of novel epoxy-resin systems that carries out and matrix material thereof, the polyaryletherketone that this epoxy-resin systems can not only be applied to existing aviation composite " is offed normal " toughness reinforcing RTM Technology, and there is excellent mechanical property and thermotolerance, can effectively improve RTM moulding process simultaneously.
Summary of the invention
A kind of polyaryletherketone that is suitable for is the object of the present invention is to provide to off normal toughness reinforcing epoxy resin and preparation method thereof and application.
The described polyaryletherketone that is suitable for is offed normal toughness reinforcing epoxy resin consisting of in mass ratio: epoxy resin is four glycidyl amine epoxy resin (TGDMA) 20 ~ 50; Diglycidyl ether epoxy resin (DGEBF) 50 ~ 80; 4,4-diaminodiphenylsulfone(DDS) (DDS) 35 ~ 45.
The solidifying agent that described 4,4-diaminodiphenylsulfone(DDS)s (DDS) are epoxy resin.
The described polyaryletherketone that is suitable for is offed normal the preparation method of toughness reinforcing epoxy resin, comprises the following steps:
1) by four glycidyl amine epoxy resin (TGDMA), diglycidyl ether epoxy resin (DGEBF) and 4,4-diaminodiphenylsulfone(DDS) (DDS) pre-polymerization;
2) fabric is carried out cutting, blanking, paving by predetermined shape, and toughner polyaryletherketone (PAEK-C) film is laid in fabric interlayer is combined into pre-setting body, die-filling;
3) according to the curing process of RTM technique epoxy resin, carry out injecting glue, solidification, the demoulding after cooling, finishing, namely obtain being suitable for the molding for epoxy resin goods that polyaryletherketone is offed normal toughness reinforcing.
In step 1), the method of described pre-polymerization can be: four glycidyl amine epoxy resin (TGDMA) and diglycidyl ether epoxy resin (DGEBF) are stirred until homogeneous phase at 90 ~ 120 DEG C, then solidifying agent 4 is added, 4-diaminodiphenylsulfone(DDS) (DDS), pre-polymerization 20 ~ 60min.
In step 2) in, described toughner polyaryletherketone (PAEK-C) adopts thermoplastic resin phenolphthalein modified version polyaryletherketone (PAEK-C), and have high thermal resistance, second-order transition temperature is 210.6 DEG C, and its chemical structure skeleton symbol is as follows:
Describedly toughner polyaryletherketone (PAEK-C) film is laid in fabric interlayer is combined into pre-setting body, die-filling method can be: by PAEK-C film and fabric according to predetermined ply stacking-sequence lay in mould, under impressed pressure and vacuum aided, liquid-state epoxy resin good for pre-polymerization is injected mould at 80 DEG C.
In step 3), the method for described solidification can be: be cured according to the curing process of 160 DEG C/2h+180 DEG C/3h+210 DEG C/3h after mold filling to be done.
The described polyaryletherketone toughness reinforcing epoxy resin of offing normal that is suitable for can be applied preparing in aviation composite.
The polyaryletherketone toughness reinforcing epoxy resin of offing normal that is suitable for of the present invention can solve the conventional several epoxy resin of current aviation composite and thermoplastics PA EK-C dissolves too fast well, matrix resin viscosity is caused to increase, be unfavorable for the problem of injecting glue in RTM technological process, and the toughness of matrix material is greatly improved, not only there is good resistance to elevated temperatures and tough, processing performance also be improved significantly.
Accompanying drawing explanation
Fig. 1 is that polyaryletherketone of the present invention is offed normal toughness reinforcing epoxy resin temperature-viscosity curve under the temperature rise rate of 2 DEG C/min.
Fig. 2 is that polyaryletherketone of the present invention is offed normal toughness reinforcing epoxy resin viscosity profile over time under 80 DEG C of constant temperature.
Fig. 3 is one of PAEK-C/EP compound resin casting matrix microscopic appearance (scale is 30 μm).
Fig. 4 is PAEK-C/EP compound resin casting matrix microscopic appearance two (scale is 20 μm).
Fig. 5 is that before and after not toughness reinforcing EP/CF impact injury, matrix material C sweeps figure.In Figure 5, left figure is before impact injury, and right figure is after impact injury.
Fig. 6 is that before and after toughness reinforcing PAEK-C/EP/CF impact injury, matrix material C sweeps figure.In figure 6, left figure is before impact injury, and right figure is after impact injury.
Embodiment
The present invention is set forth further below in conjunction with embodiment and accompanying drawing.
Two kinds of epoxy resin, solidifying agent, toughner and fabrics using in the present invention all obtain by commercially available approach.
Embodiment 1: stir at DGEBF epoxy resin and TGDMA epoxy resin in mass ratio 60: 40 in 100 DEG C until homogeneous phase, then add the DDS that mass ratio is 42, pre-polymerization 50min under 100 DEG C of oil baths, obtains pre-poly epoxy resin.
Fabric is reduced on demand, blanking, and with PAEK-C film according to certain ply stacking-sequence lay, at the uniform velocity fabric is pressed by the even power of the flatirons of about 120 DEG C, after being combined into precast body, die-filling.
Under impressed pressure and vacuum aided, liquid-state epoxy resin good for pre-polymerization is injected mould at 80 DEG C, be cured according to the curing process of 160 DEG C/2h+180 DEG C/3h+210 DEG C/3h after mold filling to be done, the demoulding after cooling, finishing, namely obtain moulded products.
Embodiment 2: stir at DGEBF epoxy resin and TGDMA epoxy resin in mass ratio 70: 30 in 110 DEG C until homogeneous phase, then add the DDS that mass ratio is 41, pre-polymerization 40min under 100 DEG C of oil baths, obtains pre-poly epoxy resin.
Fabric is reduced on demand, blanking, and with PAEK-C film according to certain ply stacking-sequence lay, at the uniform velocity fabric is pressed by the even power of the flatirons of about 120 DEG C, after being combined into precast body, die-filling.
Under impressed pressure and vacuum aided, liquid-state epoxy resin good for pre-polymerization is injected mould at 80 DEG C, be cured according to the curing process of 160 DEG C/2h+180 DEG C/3h+210 DEG C/3h after mold filling to be done, the demoulding after cooling, finishing, namely obtain moulded products.
Embodiment 3: stir at DGEBF epoxy resin and TGDMA epoxy resin in mass ratio 80: 20 in 90 DEG C until homogeneous phase, then add the DDS that mass ratio is 40, pre-polymerization 60min under 100 DEG C of oil baths, obtains pre-poly epoxy resin.
Fabric is reduced on demand, blanking, and with PAEK-C film according to certain ply stacking-sequence lay, at the uniform velocity fabric to be pressed layer by layer by the even power of the flatirons of about 120 DEG C, after being combined into precast body, die-filling.
Under impressed pressure and vacuum aided, liquid-state epoxy resin good for pre-polymerization is injected mould at 80 DEG C, be cured according to the curing process of 160 DEG C/2h+180 DEG C/3h+210 DEG C/3h after mold filling to be done, the demoulding after cooling, finishing, namely obtain moulded products.
The described polyaryletherketone that is suitable for offs normal the viscosity of toughness reinforcing epoxy resin between 70 ~ 180 DEG C lower than 1Pas, and temperature-viscosity curve as shown in Figure 1.The described polyaryletherketone that is suitable for offs normal that constant temperature 6h retention of viscosity is at below 1Pas at 80 DEG C for toughness reinforcing epoxy resin, and at its 80 DEG C, the temperature-viscosity curve of constant temperature as shown in Figure 2.The matrix material interlayer prepared defines PAEK-C/EP two-arch tunnel structure, as shown in Figures 3 and 4.Before and after not toughness reinforcing EP/CF impact injury, matrix material C sweeps figure see Fig. 5, and left figure is before impact injury, and right figure is after impact injury.Before and after toughness reinforcing PAEK-C/EP/CF impact injury, matrix material C sweeps figure see Fig. 6, and left figure is before impact injury, and right figure is after impact injury.
The polyaryletherketone that is suitable for prepared by the present invention is offed normal toughness reinforcing epoxy resin, toughness reinforcing by PAEK-C " offing normal ", compared with not toughness reinforcing laminated wood, and wherein G of the PAEK-C/EP/CF matrix material that certain formula is obtained
iCby toughness reinforcing front 329.6J/m
2bring up to 426.4J/m
2, add 29.4%, G
iICby 1190.5J/m
2be increased to 1927.1J/m
2, improve 61.9%; CAI brings up to 247.4MPa by 196.2MPa, improves 26.1%; Damaged area is by 1348mm
2be reduced to 851mm
2, reduce 36.9%.
Table 1
| System | Not toughness reinforcing EP/CF | Toughness reinforcing PAEK-C/EP/CF |
| Before and after impact injury, C sweeps figure | See Fig. 5 | See Fig. 6 |
| Pit depth (mm) | 0.64 | 0.39 |
| CAI(MPa) | 196.2 | 247.4 |
| Damaged area (mm 2) | 1348 | 851 |
| G IC(J/m 2) | 329.6 | 426.4 |
| G IIC(J/m 2) | 1190.5 | 1927.1 |
Matrix material C mechanical property is as shown in table 1.
Claims (5)
1. be suitable for polyaryletherketone to off normal the preparation method of toughness reinforcing epoxy resin, be suitable for polyaryletherketone described in it is characterized in that and off normal toughness reinforcing epoxy resin consisting of in mass ratio: epoxy resin is four glycidyl amine epoxy resin 20 ~ 50; Diglycidyl ether epoxy resin 50 ~ 80; DDS 35 ~ 45;
Described preparation method, comprises the following steps:
1) by four glycidyl amine epoxy resin, diglycidyl ether epoxy resin and DDS pre-polymerization;
2) fabric is carried out cutting, blanking, paving by predetermined shape, and toughner polyaryletherketone film is laid in fabric interlayer is combined into pre-setting body, die-filling;
3) according to the curing process of RTM technique epoxy resin, carry out injecting glue, solidification, the demoulding after cooling, finishing, namely obtain being suitable for the molding for epoxy resin goods that polyaryletherketone is offed normal toughness reinforcing.
2. be suitable for polyaryletherketone as claimed in claim 1 to off normal the preparation method of toughness reinforcing epoxy resin, it is characterized in that in step 1) in, the method of described pre-polymerization is: four glycidyl amine epoxy resin and diglycidyl ether epoxy resin are stirred until homogeneous phase at 90 ~ 120 DEG C, then solidifying agent 4 is added, 4 '-diaminodiphenylsulfone(DDS), pre-polymerization 20 ~ 60min.
3. be suitable for polyaryletherketone as claimed in claim 1 to off normal the preparation method of toughness reinforcing epoxy resin, it is characterized in that in step 2) in, described toughner polyaryletherketone adopts thermoplastic resin phenolphthalein modified version polyaryletherketone, second-order transition temperature is 210.6 DEG C, and its chemical structure skeleton symbol is as follows:
4. be suitable for polyaryletherketone as claimed in claim 1 to off normal the preparation method of toughness reinforcing epoxy resin, it is characterized in that in step 2) in, described toughner polyaryletherketone film is laid in fabric interlayer and is combined into pre-setting body, die-filling method is: by PAEK-C film and fabric according to predetermined ply stacking-sequence lay in mould, under impressed pressure and vacuum aided, liquid-state epoxy resin good for pre-polymerization is injected mould at 80 DEG C.
5. be suitable for polyaryletherketone as claimed in claim 1 to off normal the preparation method of toughness reinforcing epoxy resin, it is characterized in that in step 3) in, the method for described solidification is: be cured according to the curing process of 160 DEG C/2h+180 DEG C/3h+210 DEG C/3h after mold filling to be done.
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| CN104497478A (en) * | 2014-11-26 | 2015-04-08 | 江西洪都航空工业集团有限责任公司 | Toughened modified thermosetting epoxy resin material and preparation method thereof |
| CN105237958A (en) * | 2015-11-18 | 2016-01-13 | 江西洪都航空工业集团有限责任公司 | Preparation method of high-performance epoxy resin based carbon fiber composite material |
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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 |
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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 |
Non-Patent Citations (2)
| Title |
|---|
| "增韧环氧树脂相结构";张明等;《复合材料学报》;20070228;第24卷(第1期);13-17 * |
| 张明."通用航空环氧树脂的固化和相行为研究".《北京航空材料研究院硕士学位论文》.2009,25-26. * |
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