CN102702684A - Ex-situ toughening tackifier for resin transfer molding and preparation method thereof - Google Patents
Ex-situ toughening tackifier for resin transfer molding and preparation method thereof Download PDFInfo
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- CN102702684A CN102702684A CN2012101817218A CN201210181721A CN102702684A CN 102702684 A CN102702684 A CN 102702684A CN 2012101817218 A CN2012101817218 A CN 2012101817218A CN 201210181721 A CN201210181721 A CN 201210181721A CN 102702684 A CN102702684 A CN 102702684A
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- epoxy resin
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- toughness reinforcing
- offing normal
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Abstract
The invention belongs to the composite manufacturing technology and relates to an ex-situ toughening tackifier for resin transfer molding and a preparation method thereof. The ex-situ toughening tackifier provided by the invention is prepared by prepolymerizing the following components according to the proportion by mass: 50-70 portions of epoxy resin, 20-40 portions of toughening agent and 0-40 portions of curing agent. The ex-situ toughening tackifier provided by the invention is prepared by the following steps of: proportionally weighting the epoxy resin, the toughening agent and the curing agent; firstly prepolymerizing the epoxy resin and the toughening agent at the temperature of 170 DEG C; fully mixing the epoxy resin and the toughening agent for 30 min in a prepolymerizing process, and then lowering the temperature to 140 DEG C; adding the curing agent, and prepolymerizing the epoxy resin, the toughening agent and the curing agent at the temperature of 140 DEG C; and continuously mixing the epoxy resin, the toughening agent and the curing agent for 30 min, and then lowing the temperature to room temperature, so that the ex-situ toughening tackifier is obtained. According to the invention, an ex-situ idea is used for toughening the tackifier, the tackifier can be preformed at certain temperature and pressure, the original shape of a preformed body can be kept at normal temperature, and the preformed body can be stored for a long time.
Description
Technical field
The invention belongs to manufacture technology of composite material, relate to resin transfer moulding with " offing normal " toughness reinforcing setting agent and preparation method thereof.
Background technology
With regard to advanced composite material complex construction integral fabrication technique system, the near clean type of composite element form accuracy and dimensional precision is the important symbol of Modern Manufacturing Technology level, and gordian technique wherein comprises premolding technology and setting agent technology etc.The shaping material that employing is suitable for resin transfer moulding (RTM) technology can carry out premolding to the fabric and the structure thereof of dry state or fluffy attitude, obtains the preform of nearly clean type, premolding that Here it is technology (Preforming Technology).
And the material that is used for this " typing " processing is exactly setting agent (Tackifier).Obviously, setting agent and shaping technology are for the high-quality RTM product of moulding, and particularly large complicated product has very important significance.The development of setting agent can be the matrix material low-cost manufacturing technique, like liquid condition shaping Study on Technology such as RTM, VARTM, RFI, SCRIMP important guarantee is provided.
Setting agent typing fiber or textile preform be a kind of novelty of having developed since early 1990s, be prone to the premolding technology implemented.Through the small amount of solid resin is dispersed in fiber or fabric face, warming and pressurizing, cooling and stripping process and obtain goods dead size preform.Setting agent is preformed in the deficiency that overcomes to a certain extent or remedied braiding premolding technology, and is high to specification of quality, stable performance, and baroque goods are particularly important, are particularly useful for preparing the complicated massive article of structural shape.Guaranteeing quality product, it is significant to shorten production cycle and robotization aspect, is the effective way of cost degradation.
In order further to meet the challenge of advanced composite material high performance-price ratio, the RTM technology had been applied to aerospace and had used advanced composite material in recent years.These matrix materials require heatproof, high damage tolerance and high wet-hot aging performance, need specialize in the corresponding setting agent product of exploitation.
The RTM moulding advanced composite material preform of external development has two kinds of powder or liquid with setting agent.Solution method adopts the solution of the setting agent fabric of finalizing the design, but to environment with healthy harmful, also need handle the equipment of solvent.The RTM matrix material by chemical composition, is divided into modified epoxy class and span class with setting agent.The modified epoxy kind has 80～120 ℃ of premolding to use setting agent, uses setting agent like CYCOM790RTM Preform Binder and 180 ℃ of premolding, like the PT500 of 3M.These setting agents almost do not have influence to second-order transition temperature, interlaminar shear strength and flexural strength/modulus, and it is longer that the disclosed powder sizing agent of Chinese patent CN101613950A is the room temperature storage phase, the Powdered setting agent that does not harden.But above-mentioned disclosed technical scheme is all undesirable to the toughening effect of the matrix material of RTM moulding, and " offing normal " of the present invention toughness reinforcing setting agent has typing preform and the function that improves composite material toughness.
Summary of the invention
The objective of the invention is to propose a kind ofly can improve resin transfer moulding to the composite material toughening effect of RTM moulding with " offing normal " toughness reinforcing setting agent and preparation method thereof.
Technical solution of the present invention is: should be formed by toughner, epoxy resin and three kinds of component pre-polymerizations of solidifying agent by " offing normal " toughness reinforcing setting agent, the mass parts of three kinds of components is: epoxy resin: 50-70 part, toughner: 20-40 part, solidifying agent: 0-40 part.
Said epoxy resin is bisphenol A type epoxy resin or bisphenol f type epoxy resin, or the mixture of two kinds of epoxy resin.
Said toughner is thermoplastic resin, and thermoplastic resin is a kind of in polysulfones ether, polysulfones, poly ether imide, polyketone ether, ppe, polyaryletherketone and the carboxy nitrile rubber or several mixture.
Said solidifying agent is diamino diphenyl sulfone (DDS), diaminodiphenyl-methane (DDM).
Said epoxy resin is that bisphenol A type epoxy resin is E-51, E-54, E-44, E-20, E-12.
Toughness reinforcing setting agent is divided into two types of preparations, and its preparation process is: (1) non-response type setting agent: take by weighing epoxy resin, toughner and solidifying agent in proportion, earlier with epoxy resin and toughner 170 ℃ of following pre-polymerizations; In the time of pre-polymerization, fully stir 30min, be cooled to room temperature naturally, can obtain the toughness reinforcing setting agent of offing normal; (2) response type setting agent: take by weighing epoxy resin, toughner and solidifying agent in proportion, earlier with epoxy resin and toughner 170 ℃ of following pre-polymerizations; In the time of pre-polymerization, fully stir 30min, be cooled to 140 ℃ naturally, add solidifying agent, continue to stir 30min,, be cooled to room temperature naturally, can obtain the toughness reinforcing setting agent of offing normal 140 ℃ of following pre-polymerizations.
Advantage that the present invention has and beneficial effect, this setting agent can premolding under certain temperature and pressure, and preform guarantees original shape at normal temperatures, and have long storage period.Easy to use, the toughness reinforcing setting agent of offing normal is used Powdered use, also can be dissolved in suitable solvent solution shape as required and use.The consistency of setting agent and RTM resin is good, and is less to the negative impact of resin and composite property." offing normal " of the present invention toughness reinforcing setting agent is applied to the toughness reinforcing of setting agent to " offing normal " thought, thereby in typing, improves the toughness of RTM forming composite.
Embodiment
Explain further details in the face of the present invention down.Toughness reinforcing setting agent is by epoxy resin, toughner, solidifying agent pre-polymerization and obtain., toughness reinforcing setting agent is divided into two types, response type setting agent and non-response type setting agent.
Its preparation process is: (1) non-response type setting agent: take by weighing epoxy resin, toughner and solidifying agent in proportion; Earlier with epoxy resin and toughner 170 ℃ of following pre-polymerizations; Make toughner be fused to epoxy resin; Epoxide resin reactive group and the reaction of toughner reactive group, logical as required nitrogen protection; In the time of pre-polymerization, fully stir 30min, be cooled to room temperature naturally, can obtain the non-response type setting agent toughness reinforcing setting agent of offing normal; (2) response type setting agent: take by weighing epoxy resin, toughner and solidifying agent in proportion; Earlier with epoxy resin and toughner 170 ℃ of following pre-polymerizations; Make toughner be fused to epoxy resin, epoxide resin reactive group and the reaction of toughner reactive group, logical as required nitrogen protection; In the time of pre-polymerization, fully stir 30min, be cooled to 140 ℃ naturally, add solidifying agent, continue to stir 30min,, make solidifying agent be fused to epoxy resin, be cooled to room temperature naturally, can obtain the response type toughness reinforcing setting agent of offing normal 140 ℃ of following pre-polymerizations.
During use, solution state or use pulverulence.Setting agent can use solution state by actual needs: be dissolved in suitable solvent to setting agent, be mixed with required concentration, evenly spray or be painted on the fabric, at room temperature dry naturally or in oven dry, obtain the fabric of solution method typing.Setting agent also can use pulverulence: be crushed to 50-100 purpose granularity to the solid block setting agent with disintegrating apparatus.Powder is evenly distributed on single-sided fabric or two-sided, under 100 ℃ temperature, heats 15min, makes the pressed powder fusing, is cooled to room temperature, promptly obtains the fabric of powder sizing.
Embodiment:
1, will take by weighing 20 parts of polyaryletherketones (PEK-C)) and 70 parts of E51 epoxy resin 170 ℃ of following pre-polymerizations, stir 30min, be cooled to room temperature, obtain the non-reacted solid block toughness reinforcing setting agent of offing normal.
2, will take by weighing 30 parts of polyaryletherketones (PEK-C) and 60 parts of E51 epoxy resin 170 ℃ of following pre-polymerizations, stir 30min, be cooled to 140 ℃; Add 20 parts of DDS solidifying agent,, stir 30min 140 ℃ of following pre-polymerizations; Be cooled to room temperature, obtain the hot setting solid block toughness reinforcing setting agent of offing normal.
3, will take by weighing 40 parts of polyaryletherketones (PEK-C) and 50 parts of F46 epoxy resin 170 ℃ of following pre-polymerizations, stir 30min, be cooled to 140 ℃; Add 40 parts of DDM solidifying agent,, stir 30min 140 ℃ of following pre-polymerizations; Be cooled to room temperature, obtain 125 ℃ of intermediate temperature setting solid blocks toughness reinforcing setting agent of offing normal.
4, will take by weighing 35 parts of polyarylsulphone (PSF) and 55 parts of E54 epoxy resin 170 ℃ of following pre-polymerizations, stir 30min, be cooled to room temperature, obtain the non-reacted solid block toughness reinforcing setting agent of offing normal.
5, will take by weighing 25 parts of polyarylsulphone (PSF) and 65 parts of E54 epoxy resin 170 ℃ of following pre-polymerizations, stir 30min, be cooled to 140 ℃; Add, 30 parts of DDS solidifying agent are 140 ℃ of following pre-polymerizations; Stir 30min, be cooled to room temperature, obtain the hot setting solid block toughness reinforcing setting agent of offing normal.
6, will take by weighing 20 parts of polyarylsulphone (PSF) and 60 parts of E54 epoxy resin 170 ℃ of following pre-polymerizations, stir 30min, be cooled to 140 ℃; Add 10 parts of DDM solidifying agent 140 ℃ of following pre-polymerizations; Stir 30min, be cooled to room temperature, obtain 125 ℃ of intermediate temperature setting solid blocks toughness reinforcing setting agent of offing normal.
7, will take by weighing 30 parts of polyethersulfones (PES) and 50 parts of E44 epoxy resin 170 ℃ of following pre-polymerizations, stir 30min, be cooled to room temperature, obtain the non-reacted solid block toughness reinforcing setting agent of offing normal.
8, will take by weighing 40 parts of polyethersulfones (PES) and 50 parts of E44 epoxy resin 170 ℃ of following pre-polymerizations, stir 30min, be cooled to 140 ℃; Add 15 parts of DDS solidifying agent,, stir 30min 140 ℃ of following pre-polymerizations; Be cooled to room temperature, obtain the hot setting solid block toughness reinforcing setting agent of offing normal.
9, will take by weighing 30 parts of polyethersulfones (PES) and 50 parts of E44 epoxy resin 170 ℃ of following pre-polymerizations, stir 30min, be cooled to 140 ℃; Add 10 parts of DDM solidifying agent 140 ℃ of following pre-polymerizations; Stir 30min, be cooled to room temperature, obtain 125 ℃ of intermediate temperature setting solid blocks toughness reinforcing setting agent of offing normal.
10, will take by weighing 30 parts of nbr carboxyl terminals (CTBN) and 60 parts of E12 epoxy resin 170 ℃ of following pre-polymerizations, stir 30min, be cooled to room temperature, obtain the non-reacted solid block toughness reinforcing setting agent of offing normal.
11, will take by weighing 40 parts of nbr carboxyl terminals (CTBN) and 50 parts of E12 epoxy resin 170 ℃ of following pre-polymerizations, stir 30min, be cooled to 140 ℃; Add 30 parts of DDS solidifying agent,, stir 30min 140 ℃ of following pre-polymerizations; Be cooled to room temperature, obtain the hot setting solid block toughness reinforcing setting agent of offing normal.
12, will take by weighing 35 parts of nbr carboxyl terminals (CTBN) and 55 parts of E12 epoxy resin 170 ℃ of following pre-polymerizations; Stir 30min, be cooled to 140 ℃, add 10 parts of DDM solidifying agent 140 ℃ of following pre-polymerizations; Be cooled to room temperature, obtain 125 ℃ of intermediate temperature setting solid blocks toughness reinforcing setting agent of offing normal.
13, will take by weighing 30 parts of nbr carboxyl terminals (CTBN), 20 parts of E12 epoxy resin and 40 parts of E54 epoxy resin 170 ℃ of following pre-polymerizations, stir 30min, be cooled to room temperature, obtain the non-reacted solid block toughness reinforcing setting agent of offing normal.
14, will take by weighing 30 parts of nbr carboxyl terminals (CTBN), 20 parts of E12 epoxy resin and 40 parts of F48 epoxy resin 170 ℃ of following pre-polymerizations; Stir 30min; Be cooled to 140 ℃; Add 30 parts of DDS solidifying agent 140 ℃ of following pre-polymerizations, be cooled to room temperature, obtain the non-reacted solid block toughness reinforcing setting agent of offing normal.
15, will take by weighing 60 parts of 10 parts of nbr carboxyl terminals (CTBN), 20 parts of polyethersulfones (PES) and E12 epoxy resin 170 ℃ of following pre-polymerizations, stir 30min, be cooled to room temperature, obtain the non-reacted solid block toughness reinforcing setting agent of offing normal.
Claims (6)
1. a resin transfer moulding is with " offing normal " toughness reinforcing setting agent; It is characterized in that; Should form by toughner, epoxy resin and three kinds of component pre-polymerizations of solidifying agent by " offing normal " toughness reinforcing setting agent; The mass parts of three kinds of components is: epoxy resin: 50-70 part, toughner: 20-40 part, solidifying agent: 0-40 part.
2. a kind of resin transfer moulding according to claim 1 is characterized in that with " offing normal " toughness reinforcing setting agent said epoxy resin is bisphenol A type epoxy resin or bisphenol f type epoxy resin, or the mixture of two kinds of epoxy resin.
3. a kind of resin transfer moulding according to claim 1 is with " offing normal " toughness reinforcing setting agent; It is characterized in that; Said toughner is thermoplastic resin, and thermoplastic resin is a kind of in polysulfones ether, polysulfones, poly ether imide, polyketone ether, ppe, polyaryletherketone and the carboxy nitrile rubber or several mixture.
4. a kind of resin transfer moulding according to claim 1 is characterized in that with " offing normal " toughness reinforcing setting agent said solidifying agent is a diamino diphenyl sulfone.
5. a kind of resin transfer moulding according to claim 2 is characterized in that with " offing normal " toughness reinforcing setting agent said epoxy resin is that bisphenol A type epoxy resin is E-51, E-54, E-44, E-20, E-12.
6. one kind prepares the method that the described resin transfer moulding of claim 1 is used " offing normal " toughness reinforcing setting agent; It is characterized in that; Toughness reinforcing setting agent is divided into two types of preparations; Its preparation process is: (1) non-response type setting agent: take by weighing epoxy resin, toughner and solidifying agent in proportion, earlier with epoxy resin and toughner 170 ℃ of following pre-polymerizations; In the time of pre-polymerization, fully stir 30min, be cooled to room temperature naturally, can obtain the toughness reinforcing setting agent of offing normal; (2) response type setting agent: take by weighing epoxy resin, toughner and solidifying agent in proportion, earlier with epoxy resin and toughner 170 ℃ of following pre-polymerizations; In the time of pre-polymerization, fully stir 30min, be cooled to 140 ℃ naturally, add solidifying agent, continue to stir 30min,, be cooled to room temperature naturally, can obtain the toughness reinforcing setting agent of offing normal 140 ℃ of following pre-polymerizations.
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| CN201210181721.8A CN102702684B (en) | 2012-06-04 | 2012-06-04 | Ex-situ toughening tackifier for resin transfer molding and preparation method thereof |
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| CN201210181721.8A CN102702684B (en) | 2012-06-04 | 2012-06-04 | Ex-situ toughening tackifier for resin transfer molding and preparation method thereof |
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Cited By (6)
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| CN103819876A (en) * | 2014-03-07 | 2014-05-28 | 南京海拓复合材料有限责任公司 | Sizing glue for widening carbon fibers |
| 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 |
| CN110724365A (en) * | 2019-11-18 | 2020-01-24 | 哈尔滨工程大学 | Low-temperature-resistant epoxy resin and preparation method thereof |
| CN110900883A (en) * | 2018-09-17 | 2020-03-24 | 航天特种材料及工艺技术研究所 | Dry fabric intermediate and preparation device and method thereof |
| CN114875522A (en) * | 2022-05-26 | 2022-08-09 | 上海碳纤维复合材料创新研究院有限公司 | Toughened liquid-molded epoxy resin ternary composite fiber and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819876A (en) * | 2014-03-07 | 2014-05-28 | 南京海拓复合材料有限责任公司 | Sizing glue for widening carbon fibers |
| CN103819876B (en) * | 2014-03-07 | 2016-08-31 | 南京海拓复合材料有限责任公司 | A kind of sizing glue for broadening carbon fiber |
| 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 |
| CN110900883A (en) * | 2018-09-17 | 2020-03-24 | 航天特种材料及工艺技术研究所 | Dry fabric intermediate and preparation device and method thereof |
| CN110900883B (en) * | 2018-09-17 | 2022-08-09 | 航天特种材料及工艺技术研究所 | Dry fabric intermediate and preparation device and method thereof |
| CN110724365A (en) * | 2019-11-18 | 2020-01-24 | 哈尔滨工程大学 | Low-temperature-resistant epoxy resin and preparation method thereof |
| CN114875522A (en) * | 2022-05-26 | 2022-08-09 | 上海碳纤维复合材料创新研究院有限公司 | Toughened liquid-molded epoxy resin ternary composite fiber and preparation method thereof |
| CN114875522B (en) * | 2022-05-26 | 2023-12-12 | 上海碳纤维复合材料创新研究院有限公司 | Toughened liquid-formed epoxy resin ternary composite fiber and preparation method thereof |
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