CN102702684B - 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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- CN102702684B CN102702684B CN201210181721.8A CN201210181721A CN102702684B CN 102702684 B CN102702684 B CN 102702684B CN 201210181721 A CN201210181721 A CN 201210181721A CN 102702684 B CN102702684 B CN 102702684B
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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 " 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 preform technique and setting agent technology etc.The shaping material that employing is suitable for resin transfer moulding (RTM) technique can carry out premolding to the fabric of dry state or fluffy state and structure thereof, obtains the preform of nearly clean type, Here it is preform technique (Preforming Technology).
And be exactly setting agent (Tackifier) for the material that this " sizing " processes.Obviously, setting agent and shaping technology are for shaping high-quality RTM product, and particularly large complicated product has very important significance.The development of setting agent can be matrix material low-cost manufacturing technique, and the research as liquid condition shaping technology such as RTM, VARTM, RFI, SCRIMP provides important guarantee.
Setting agent sizing fiber or fabric prepare a kind of novelty developed since preform is early 1990s, the preform technique easily implemented.By a small amount of solid resin is dispersed in fiber or fabric face, temperature-pressure, cooling and stripping process and obtain goods dead size preform.Setting agent is preformed in the deficiency overcoming or compensate for braiding preform technique to a certain extent, high to specification of quality, stable performance, and baroque goods are particularly important, is particularly useful for the massive article preparing structural shape complexity.Guarantee quality product, shorten the production cycle and automatization aspect significant, be the effective way of cost degradation.
In recent years in order to meet the challenge of advanced composite material high performance-price ratio further, RTM technology had been applied to aerospace advanced composite material.These matrix materials require heatproof, high damage tolerance and high wet-hot aging performance, need to specialize in the corresponding styling aid products of exploitation.
The RTM shaping advanced composite material preform setting agent of external development has powder or liquid two kinds.Solution method adopts the solution of setting agent to carry out pattern bonded fabrics, but is harmful to environment and health, also needs the equipment processing solvent.RTM matrix material by chemical composition, is divided into modified epoxy class and span class with setting agent.Modified epoxy kind has 80 ~ 120 DEG C of premolding setting agents, as CYCOM790RTM Preform Binder and 180 DEG C of premolding setting agent, as the PT500 of 3M.These setting agents are on the almost no impact of second-order transition temperature, interlaminar shear strength and flexural strength/modulus, and it is longer that powder sizing agent disclosed in Chinese patent CN101613950A is the room temperature storage phase, the Powdered setting agent do not hardened.But above-mentioned disclosed technical scheme is all undesirable to the toughening effect of the shaping matrix material of RTM, and " offing normal " of the present invention toughness reinforcing setting agent has sizing preform and improves the function of composite material toughness.
Summary of the invention
The object of the invention is to propose a kind of resin transfer moulding " offing normal " toughness reinforcing setting agent and preparation method thereof that can improve the shaping composite material toughening effect of RTM.
Technical solution of the present invention is: should be formed by the three kinds of component pre-polymerizations of toughner, epoxy resin and 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.
Described epoxy resin is bisphenol A type epoxy resin or bisphenol f type epoxy resin, or the mixture of two kinds of epoxy resin.
Described toughner is thermoplastic resin, and thermoplastic resin is the mixture of one or several in polysulfones ether, polysulfones, poly ether imide, polyketone ether, polyphenylene oxide, polyaryletherketone and carboxy nitrile rubber.
Described solidifying agent is diamino diphenyl sulfone (DDS), diaminodiphenyl-methane (DDM).
Described epoxy resin is bisphenol A type epoxy resin is E-51, E-54, E-44, E-20, E-12.
Toughness reinforcing setting agent is divided into two type preparations, and its preparation process is: (1) non-reactive setting agent: take epoxy resin, toughner and solidifying agent in proportion, the first pre-polymerization at 170 DEG C by epoxy resin and toughner; While pre-polymerization, fully stir 30min, Temperature fall, to room temperature, can obtain toughness reinforcing setting agent of offing normal; (2) response type setting agent: take epoxy resin, toughner and solidifying agent in proportion, the first pre-polymerization at 170 DEG C by epoxy resin and toughner; While pre-polymerization, fully stir 30min, Temperature fall to 140 DEG C, add solidifying agent, continue to stir 30min, pre-polymerization at 140 DEG C, Temperature fall, to room temperature, can obtain toughness reinforcing setting agent of offing normal.
The advantage that the present invention has and beneficial effect, this setting agent can premolding under certain temperature and pressure, and preform ensures original shape at normal temperatures, and has longer storage period.Easy to use, the Powdered use of toughness reinforcing setting agent of offing normal, also can be dissolved in suitable solvent solution shape as required and use.The consistency of setting agent and RTM resin is good, 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 " offing normal " thought, thus improves the toughness of RTM forming composite while sizing.
Embodiment
Below the present invention is described in further details.Toughness reinforcing setting agent is by epoxy resin, toughner, solidifying agent pre-polymerization and obtaining., toughness reinforcing setting agent is divided into two types, response type setting agent and non-reactive setting agent.
Its preparation process is: (1) non-reactive setting agent: take epoxy resin, toughner and solidifying agent in proportion, the first pre-polymerization at 170 DEG C by epoxy resin and toughner, toughner is made to be fused to epoxy resin, epoxide resin reactive group and the reaction of toughner active group, as required logical nitrogen protection; While pre-polymerization, fully stir 30min, Temperature fall, to room temperature, can obtain non-reactive setting agent and to off normal toughness reinforcing setting agent; (2) response type setting agent: take epoxy resin, toughner and solidifying agent in proportion, the first pre-polymerization at 170 DEG C by epoxy resin and toughner, toughner is made to be fused to epoxy resin, epoxide resin reactive group and the reaction of toughner active group, as required logical nitrogen protection; While pre-polymerization, fully stir 30min, Temperature fall to 140 DEG C, add solidifying agent, continue to stir 30min, pre-polymerization at 140 DEG C, makes solidifying agent be fused to epoxy resin, and Temperature fall, to room temperature, can obtain response type and to off normal toughness reinforcing setting agent.
During use, solution state or use pulverulence.Setting agent can use solution state according to actual needs: setting agent is dissolved in suitable solvent, is mixed with required concentration, evenly sprays or is painted on fabric, at room temperature naturally dries or in oven dry, obtains the fabric of solution method sizing.Setting agent also can use pulverulence: with disintegrating apparatus, solid block setting agent is crushed to 50-100 object granularity.Powder is evenly distributed on single-sided fabric or two-sided, heats 15min, pressed powder is melted, is cooled to room temperature, namely obtain the fabric of powder sizing at the temperature of 100 DEG C.
Embodiment:
1,20 parts of polyaryletherketones (PEK-C) will be taken) and 70 parts of E51 epoxy resin pre-polymerizations at 170 DEG C, stir 30min, be cooled to room temperature, obtain non-reacted solid block and to off normal toughness reinforcing setting agent.
2,30 parts of polyaryletherketones (PEK-C) and 60 parts of E51 epoxy resin pre-polymerizations at 170 DEG C will be taken, stir 30min, be cooled to 140 DEG C, add 20 parts of DDS solidifying agent, pre-polymerization at 140 DEG C, stir 30min, be cooled to room temperature, obtain hot setting solid block and to off normal toughness reinforcing setting agent.
3,40 parts of polyaryletherketones (PEK-C) and 50 parts of F46 epoxy resin pre-polymerizations at 170 DEG C will be taken, stir 30min, be cooled to 140 DEG C, add 40 parts of DDM solidifying agent, pre-polymerization at 140 DEG C, stir 30min, be cooled to room temperature, obtain 125 DEG C of intermediate temperature setting solid blocks and to off normal toughness reinforcing setting agent.
4,35 parts of polyarylsulphone (PSF) and 55 parts of E54 epoxy resin pre-polymerizations at 170 DEG C will be taken, stir 30min, be cooled to room temperature, and obtain non-reacted solid block and to off normal toughness reinforcing setting agent.
5,25 parts of polyarylsulphone (PSF) and 65 parts of E54 epoxy resin pre-polymerizations at 170 DEG C will be taken, stir 30min, be cooled to 140 DEG C, add, 30 parts of DDS solidifying agent, pre-polymerization at 140 DEG C, stir 30min, be cooled to room temperature, obtain hot setting solid block and to off normal toughness reinforcing setting agent.
6,20 parts of polyarylsulphone (PSF) and 60 parts of E54 epoxy resin pre-polymerizations at 170 DEG C will be taken, stir 30min, be cooled to 140 DEG C, add 10 parts of DDM solidifying agent pre-polymerizations at 140 DEG C, stir 30min, be cooled to room temperature, obtain 125 DEG C of intermediate temperature setting solid blocks and to off normal toughness reinforcing setting agent.
7,30 parts of polyethersulfones (PES) and 50 parts of E44 epoxy resin pre-polymerizations at 170 DEG C will be taken, stir 30min, be cooled to room temperature, and obtain non-reacted solid block and to off normal toughness reinforcing setting agent.
8,40 parts of polyethersulfones (PES) and 50 parts of E44 epoxy resin pre-polymerizations at 170 DEG C will be taken, stir 30min, be cooled to 140 DEG C, add 15 parts of DDS solidifying agent, pre-polymerization at 140 DEG C, stir 30min, be cooled to room temperature, obtain hot setting solid block and to off normal toughness reinforcing setting agent.
9,30 parts of polyethersulfones (PES) and 50 parts of E44 epoxy resin pre-polymerizations at 170 DEG C will be taken, stir 30min, be cooled to 140 DEG C, add 10 parts of DDM solidifying agent pre-polymerizations at 140 DEG C, stir 30min, be cooled to room temperature, obtain 125 DEG C of intermediate temperature setting solid blocks and to off normal toughness reinforcing setting agent.
10,30 parts of nbr carboxyl terminals (CTBN) and 60 parts of E12 epoxy resin pre-polymerizations at 170 DEG C will be taken, stir 30min, be cooled to room temperature, and obtain non-reacted solid block and to off normal toughness reinforcing setting agent.
11,40 parts of nbr carboxyl terminals (CTBN) and 50 parts of E12 epoxy resin pre-polymerizations at 170 DEG C will be taken, stir 30min, be cooled to 140 DEG C, add 30 parts of DDS solidifying agent, pre-polymerization at 140 DEG C, stir 30min, be cooled to room temperature, obtain hot setting solid block and to off normal toughness reinforcing setting agent.
12,35 parts of nbr carboxyl terminals (CTBN) and 55 parts of E12 epoxy resin pre-polymerizations at 170 DEG C will be taken, stir 30min, be cooled to 140 DEG C, add 10 parts of DDM solidifying agent pre-polymerizations at 140 DEG C, be cooled to room temperature, obtain 125 DEG C of intermediate temperature setting solid blocks and to off normal toughness reinforcing setting agent.
13,30 parts of nbr carboxyl terminals (CTBN), 20 parts of E12 epoxy resin and 40 parts of E54 epoxy resin pre-polymerizations at 170 DEG C will be taken, stir 30min, be cooled to room temperature, and obtain non-reacted solid block and to off normal toughness reinforcing setting agent.
14,30 parts of nbr carboxyl terminals (CTBN), 20 parts of E12 epoxy resin and 40 parts of F48 epoxy resin pre-polymerizations at 170 DEG C will be taken, stir 30min, be cooled to 140 DEG C, add 30 parts of DDS solidifying agent pre-polymerizations at 140 DEG C, be cooled to room temperature, obtain non-reacted solid block and to off normal toughness reinforcing setting agent.
15,10 parts of nbr carboxyl terminals (CTBN), 20 parts of polyethersulfones (PES) 60 parts and the pre-polymerization at 170 DEG C of E12 epoxy resin will be taken, stir 30min, be cooled to room temperature, and obtain non-reacted solid block and to off normal toughness reinforcing setting agent.
Claims (2)
1. resin transfer moulding " an offing normal " toughness reinforcing setting agent, it is characterized in that, should be formed by the three kinds of component pre-polymerizations of toughner, epoxy resin and 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;
Described epoxy resin is bisphenol A type epoxy resin or bisphenol f type epoxy resin, or the mixture of two kinds of epoxy resin;
Described toughner is thermoplastic resin, and thermoplastic resin is the mixture of one or several in polysulfones, poly ether imide, polyketone ether, polyphenylene oxide, polyaryletherketone and carboxy nitrile rubber;
Described solidifying agent is diamino diphenyl sulfone;
Described toughness reinforcing setting agent is divided into two type preparations, and its preparation process is: (1) non-reactive setting agent: take epoxy resin, toughner and solidifying agent in proportion, the first pre-polymerization at 170 DEG C by epoxy resin and toughner; While pre-polymerization, fully stir 30min, Temperature fall, to room temperature, can obtain toughness reinforcing setting agent of offing normal; (2) response type setting agent: take epoxy resin, toughner and solidifying agent in proportion, the first pre-polymerization at 170 DEG C by epoxy resin and toughner; While pre-polymerization, fully stir 30min, Temperature fall to 140 DEG C, add solidifying agent, continue to stir 30min, pre-polymerization at 140 DEG C, Temperature fall, to room temperature, can obtain toughness reinforcing setting agent of offing normal.
2. a kind of resin transfer moulding according to claim 1 " offing normal " toughness reinforcing setting agent, is characterized in that, described epoxy resin is bisphenol A type epoxy resin is E-51, E-54, E-44, E-20, E-12.
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| 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 |
| 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 |
| 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 |
| CN115710408A (en) * | 2022-11-10 | 2023-02-24 | 航天特种材料及工艺技术研究所 | Prepreg containing biphenol polyaryletherketone and high-toughness composite material |
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| CN1923506B (en) * | 2006-07-19 | 2010-08-04 | 中国航空工业第一集团公司北京航空材料研究院 | Toughening composite material lamination board and method for making same |
| CN101760965A (en) * | 2009-12-10 | 2010-06-30 | 中国航空工业集团公司北京航空材料研究院 | Predefinition form agent of toughening function type RTM textile powder and preparing method thereof |
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