CN1155646C - Modified dimaleimide resin capable of being used to transfer molding and its prepn - Google Patents
Modified dimaleimide resin capable of being used to transfer molding and its prepn Download PDFInfo
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- CN1155646C CN1155646C CNB011070129A CN01107012A CN1155646C CN 1155646 C CN1155646 C CN 1155646C CN B011070129 A CNB011070129 A CN B011070129A CN 01107012 A CN01107012 A CN 01107012A CN 1155646 C CN1155646 C CN 1155646C
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- resin
- modified bismaleimide
- bismaleimide resin
- transfer mould
- thinner
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Abstract
The present invention relates to modified bismaleimide resin used for resin transfer moulding shaping and a manufacture method thereof. The modified bismaleimide resin is characterized in that the resin is based on diphenylmethane bismaleimide, reactive diluents and toughening agents are introduced through molecular design under the condition that the heat resistance is not obviously reduced, and the modified bismaleimide resin is prepared. The modified bismaleimide resin has the advantages of high toughness and high temperature resistance, and can be used for the transfer moulding shaping. Structural components prepared by the resin through a transfer moulding shaping process can be widely used for the fields of aviation, astronavigation, navigation, automobiles, electronics and electricity, and the modified bismaleimide resin has obvious economic and social benefits.
Description
One, technical field
The present invention relates to a kind of high-molecular special engineering plastics and forming process thereof.Particularly, the present invention relates to a kind of modified bismaleimide resin that can be used for transfer mould (RTM) and preparation method thereof.
Two, background technology
As a kind of new composite material process planning, the RTM moulding is that low viscosity resin is injected into impregnation of fibers in the mold cavity that fiber preform is housed in advance, heats up and solidifies, and solidifies back cooling depanning.Compare with traditional composite material process planning, this technology has following advantage: the parts of (1) plastic large-scale component and band boss, stiffening web and local thickening; (2) product surface is bright and clean, the dimensional precision height, and mechanical property is outstanding; (3) strongthener that is adopted is of a great variety, and content can strict be controlled in product, and the preparation of fiber preform has good designability; (4) be a kind of closed mould operations, significantly reduce pollution environment; (5) RTM has economy, characteristics fast.But, the RTM moulding requires very harsh to the manufacturability of matrix resin, not only require pressure injection viscosity low, easily flow, the long practical phase is arranged, and can be at a certain temperature curing molding rapidly, in curing molding, do not emit or seldom emit volatility low molecule (Frank C Robertson, British Polymer Journal, 1988,20,417-429).The high-performance matrix resin that is suitable for the RTM technology has Resins, epoxy and bimaleimide resin.The Resins, epoxy use temperature is not high, and wet-hot aging performance is not good enough.Bimaleimide resin has good hydrothermal stability, and weather resistance and reliability all obviously are better than Resins, epoxy, is applicable to make the matrix material that use in the high-performance field.General ditan bismaleimides (BMDPM) is unique realization production domesticization and commercial bismaleimide amine monomers, fusing point height (158-161 ℃), its resin has good and stable electrical insulation capability and mechanical property because of it in wide temperature range, but the BMDPM resin to be made low melting point, low viscosity, easily flow, the RTM molding resin of no volatile matter, must improve its flowability and cured article toughness.
Three, summary of the invention
The objective of the invention is provides a kind of modified bismaleimide resin that can be used for transfer mould and preparation method thereof at the deficiencies in the prior art, be characterized in that the resin viscosity under injection temperature for preparing is low, easily flow, the practical phase is long, under solidification value, can solidify rapidly, and do not emit low-molecular material, cured article has good toughness and thermotolerance.
Purpose of the present invention is realized that by following measure wherein said raw material umber is parts by weight except that specified otherwise:
The recipe ingredient that can be used for the modified bismaleimide resin of transfer mould is:
100 parts of ditan bismaleimidess
N-phenylmaleimide 30-60 part
Thinner (available o, o '-diallyl bisphenol, o, o '-diallyl ether dihydroxyphenyl propane, O-phthalic diene acid
Propyl diester, properties of diallyl isophathalate are or/and vinylbenzene is at least a) 50-110 part
Toughner (liquid acrylonitrile butadiene rubber of available hydroxy-end capped liquid acrylonitrile butadiene rubber, carboxy blocking is or/and liquid propene acid esters rubber is at least a) 10-30 part
Resins, epoxy 60-110 part
The preparation method who can be used for the modified bismaleimide resin of transfer mould:
1. thinner 40-90 part and toughner 10-30 part are carried out pre-polymerization in temperature 120-150 ℃ and make prepolymer I,
2. 100 parts of ditan bismaleimidess, N-phenylmaleimide 30-60 part and all the other thinner 10-20 parts are carried out pre-polymerization in temperature 100-140 ℃ and are made prepolymer II,
3. prepolymer I and II are mixed, be cooled to 100-120 ℃ and add Resins, epoxy 60-110 part, and temperature 100-120 ℃ and vacuum tightness 500-650mmHg reduced pressure treatment 15-25 minute; Make the modified bismaleimide resin that can be used for transfer mould.
The present invention has following advantage:
1. raw material sources are extensive, and producing does not need specific installation, cost low.
2. resin provided by the invention is that modification obtains on the basis of diphenyl methane dimaleimide resin, and the adding of properties-correcting agent has effectively improved the curing action of diphenyl methane dimaleimide, detailed being shown in Table 1.
3. modified bismaleimide resin provided by the invention has good RTM moulding process and good comprehensive mechanical property, detailed being shown in Table 2.
4. this modified bismaleimide resin adopts the RTM moulding process to prepare the high performance composite structural part, and wide application implementation prospect is arranged.
Four, embodiment
Below be the specific descriptions of the present invention being carried out by embodiment.Be necessary to be pointed out that once more that following examples only are used for the present invention is further specified, and can not be interpreted as limiting the scope of the invention.The person skilled in art can make some nonessential improvement and adjustment by foregoing according to the present invention.
1. add o in reactor, liquid fourth dried meat rubber 10 grams of o '-diallyl bisphenol 90 grams and carboxy blocking are warming up to 130 ℃, stir 2 hours, get prepolymer I; Add o in reactor, o '-diallyl bisphenol 30 grams and N-phenylmaleimide 30 restrain, and are warming up to 110 ℃, stir to add ditan bismaleimides 100 grams down, continue to be warming up to 120 ℃, react 20 minutes, get prepolymer II; Prepolymer I is joined among the prepolymer II while hot, add Resins, epoxy 70 grams when being cooled to 110-120 ℃.Being 110 ℃ in temperature is 600mmHg reduced pressure treatment 15 minutes with vacuum tightness, obtains the modified bismaleimide resin product.
2. add o in reactor, o '-diallyl ether dihydroxyphenyl propane 70 grams and hydroxy-end capped liquid acrylonitrile butadiene rubber 20 grams are warming up to 130 ℃, stir 2 hours, get prepolymer I; Add o in reactor, o '-diallyl ether dihydroxyphenyl propane 20 grams and N-phenylmaleimide 40 restrain, and are warming up to 110 ℃, stir to add ditan bismaleimides 100 grams down, continue to be warming up to 120 ℃, react 30 minutes, get prepolymer II; Prepolymer I is joined among the prepolymer II while hot, add Resins, epoxy 60 grams when being cooled to 110-120 ℃.Being 110 ℃ in temperature is 620mmHg reduced pressure treatment 20 minutes with vacuum tightness, obtains the modified bismaleimide resin product.
3. in reactor, add diallyl phthalate 80 grams and liquid propene acid esters rubber 30 grams, be warming up to 130 ℃, stirred 2 hours, get prepolymer I; In reactor, add diallyl phthalate 20 grams and N-phenylmaleimide 60 and restrain, be warming up to 110 ℃, add ditan bismaleimides 100 grams under stirring, continue to be warming up to 120 ℃, reacted 40 minutes, get prepolymer II; Prepolymer I is joined among the prepolymer II while hot, add Resins, epoxy 80 grams when being cooled to 110-120 ℃.Being 110 ℃ in temperature is 580mmHg reduced pressure treatment 25 minutes with vacuum tightness, obtains the modified bismaleimide resin product.
4. adopt the modified bismaleimide resin of this transfer mould moulding, successfully prepared 3-d braided fiber enhanced structural part.With the preheating 60 minutes in 80 ℃ of baking ovens of this 3Kg resin, again resin is changed in the charging basket of RTM equipment and be heated to 90 ℃, reduced pressure treatment 30 minutes is injected resin and has been preheating to 100 ℃ preformed member, stops injection when treating have resin to overflow in the exit.Reduce to room temperature after intensification is solidified and take out product.
The dsc analysis result of table 1 resin
*
Project diphenyl methane dimaleimide RTM modified bismaleimide
The resin resin
Initial solidification value, ℃ 220 150-160
Solidify peak temperature, ℃ 253 175-180
The after fixing temperature, ℃ 300 210-230
*Adopt the Dupont2100 thermal analyzer, heat-up rate is 5 ℃/minute.
The performance of table 2 modified bismaleimide resin
Project testing temperature test value
Viscosity, 90 ℃ of 200-300 of centipoise
Working life, hours 90 ℃＞6
Gel time, minute 195 ℃ of 4-6
Tensile strength, MPa room temperature 50-70
Tensile modulus, GPa room temperature 3.0-3.7
Tension fracture elongation rate, % room temperature 2.0-2.6
Flexural strength, MPa room temperature＞90
Second-order transition temperature (TMA), ℃ 270-300
Claims (5)
1. the modified bismaleimide resin that can be used for transfer mould is characterized in that the recipe ingredient (by weight) of this resin is:
100 parts of ditan bismaleimidess
N-phenylmaleimide 30-60 part
Thinner 50-110 part
Toughner 10-30 part
Resins, epoxy 60-110 part
2. according to the described modified bismaleimide resin that can be used for transfer mould of claim 1, it is characterized in that thinner is o, o '-diallyl bisphenol, o, o '-diallyl ether dihydroxyphenyl propane, diallyl phthalate, properties of diallyl isophathalate are or/and vinylbenzene is at least a.
3. according to the described modified bismaleimide resin that can be used for transfer mould of claim 1, it is characterized in that toughner is that the liquid acrylonitrile butadiene rubber of hydroxy-end capped liquid acrylonitrile butadiene rubber, carboxy blocking is or/and liquid propene acid esters rubber is at least a.
4. according to the described preparation method who can be used for the modified bismaleimide resin of transfer mould of claim 1, it is characterized in that:
A. with thinner 40-90 part and toughner 10-30 part, carry out pre-polymerization in temperature 120-150 ℃, make prepolymer I,
B. with 100 parts of ditan bismaleimidess, N-phenylmaleimide 30-60 part and all the other thinner 10-20 parts, carry out pre-polymerization in temperature 100-140 ℃, make prepolymer II,
C. again prepolymer I and II are mixed, be cooled to 100-120 ℃ and add Resins, epoxy 60-110 part, and, make the transfer mould modified bismaleimide resin temperature 100-120 ℃ and vacuum tightness 500-650mmHg reduced pressure treatment 15-25 minute.
5. according to the described purposes that can be used for the modified bismaleimide resin of transfer mould of claim 1, the plastics that it is characterized in that this resin are used for the composite element of Aeronautics and Astronautics, navigation, electric and auto industry field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011070129A CN1155646C (en) | 2001-01-05 | 2001-01-05 | Modified dimaleimide resin capable of being used to transfer molding and its prepn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011070129A CN1155646C (en) | 2001-01-05 | 2001-01-05 | Modified dimaleimide resin capable of being used to transfer molding and its prepn |
Publications (2)
| Publication Number | Publication Date |
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| CN1362438A CN1362438A (en) | 2002-08-07 |
| CN1155646C true CN1155646C (en) | 2004-06-30 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB011070129A Expired - Fee Related CN1155646C (en) | 2001-01-05 | 2001-01-05 | Modified dimaleimide resin capable of being used to transfer molding and its prepn |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845143B (en) * | 2010-05-19 | 2012-05-02 | 中国科学院化学研究所 | Modified bismaleimide resin as well as preparation method and application thereof |
| CN102199413A (en) * | 2011-03-26 | 2011-09-28 | 舟山维特新材料科技有限公司 | Modified epoxy resin adhesive used for polyimide flexible copper-clad plate |
| CN106280445A (en) * | 2016-08-11 | 2017-01-04 | 江苏恒神股份有限公司 | A kind of liquid molding high tenacity bismaleimide resin and preparation method thereof |
| CN106977717B (en) * | 2017-04-26 | 2019-03-26 | 黑龙江省科学院石油化学研究院 | A kind of ester group compound containing alkenyl and preparation method thereof and the bimaleimide resin being modified using it |
| CN113880986A (en) * | 2020-07-01 | 2022-01-04 | 中国石油化工股份有限公司 | High-temperature high-pressure hydrolysis-resistant bismaleimide resin composition and preparation method and application thereof |
| CN112608597B (en) * | 2020-12-04 | 2022-03-04 | 四川大学 | High-energy-storage-density polymer composite material and preparation method thereof |
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