CN101570600B - Resin matrix for resin transfer molding process, and preparation method thereof - Google Patents
Resin matrix for resin transfer molding process, and preparation method thereof Download PDFInfo
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- CN101570600B CN101570600B CN2009100339700A CN200910033970A CN101570600B CN 101570600 B CN101570600 B CN 101570600B CN 2009100339700 A CN2009100339700 A CN 2009100339700A CN 200910033970 A CN200910033970 A CN 200910033970A CN 101570600 B CN101570600 B CN 101570600B
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Abstract
The invention discloses a resin matrix for resin transfer molding process, and a preparation method thereof. The preparation method comprises the following steps that: by weight, 100 portions of bismaleimide resin and 50 to 90 portions of diallyl phenyl compounds are subjected to pre-polymerization for 30 to 60 minutes at a temperature of between 120 and 140 DEG C, cooled to be between 100 and 120DEG C, added with 20 to 50 portions of cyanate ester resin and then pre-polymerized for 30 to 60 minutes at a temperature of between 100 and 120 DEG C so as to obtain BT resin; 10 to 90 portions of r eactive diluent is added to the BT resin; and the reactive diluent and the BT resin react for 30 to 60 minutes at a temperature of between 80 and 100 DEG C so as to obtain the resin matrix for resin transfer molding process. The resin matrix has excellent comprehensive mechanical properties heat resistance and excellent dielectric properties, and can be used in aerospace, electronic information, transportation and other numerous high-tech fields.
Description
Technical field
The present invention relates to a kind of resin matrix composite material and preparation method thereof, be particularly related to resin matrix that a kind of resin transfer molding (RTM) process uses and preparation method thereof, this matrix material has excellent comprehensive mechanical properties, can be used for high-technology fields such as space flight and aviation, electronic information.
Background technology
Resin transfer moulding (Resin Transfer Moulding is called for short RTM) is to adopt low viscosity resin to inject close die, and resin flows therein, soaks into the good or preformed strongthener of lay rationally, and the processing method of curing molding.This technology can reduce equipment cost, moulding cost effectively without prepreg, autoclave.The RTM moulding process to the requirement of resin is: viscosity is low under (1) injection temperature, and best viscosity is 200～500cp, and resin and strongthener have good wetting property; (2) resin solidification is fast, and no volatile matter is emitted; (3) the resin solidification post-shrinkage ratio is low, to guarantee the dimensional stabilizing of goods.In addition, also require resin matrix itself to have high heat resistance, excellent comprehensive mechanical properties and anti-environmental aging performance in the high request Application Areas.
Cyanate (CE) and bismaleimides (BMI) are the thermosetting resins of two kinds of excellent propertys, CE has excellent mechanical property, dielectric properties (ε ≈ 3.1, tg δ=0.007) and processing performance, BMI has high heat-resisting (340 ℃ of Tg ≈), approach by chemical copolymerization or physical blending combines the two, is the BT resin.The BT resin has been realized the excellent-excellent combination of two kinds of resin properties, has thermotolerance height (Tg=200～340 ℃) and the good advantage of dielectric properties.But BT resin viscosity height needs the processing condition compacted under at comparatively high temps or cryogenic high pressure, and therefore, this matrix material is not suitable for the RTM technological forming.In addition, the toughness of this material is still waiting further raising.
The hyperbranched polymer particular structure makes it to have the different physical and chemical performance of traditional polymer, shows the characteristics that its viscosity is little, solvability is good.In addition, the hyperbranched polymer of a large amount of functional groups that can design surface distribute makes it to have good reactivity.Therefore, hyperbranched polymer has been used for the modification of thermosetting resin, but, how to design hyperbranched polymer and come modification BT resin, make it keeping on excellent dielectric properties of BT resin and the stable on heating basis, acquisition has the more resin system that can be used for the RTM technological forming of high tenacity, and further research and exploration await.
Summary of the invention
To exist toughness not enough in order to overcome the resin described in the background technology, and problem such as processability is relatively poor when the RTM processes, the object of the present invention is to provide a kind ofly not only to have over-all propertieies such as excellent heat resisting, mechanical property, dielectric properties and wet-hot aging performance, and be suitable for resin matrix that RTM technology uses and preparation method thereof.
The technical scheme that realizes the foregoing invention purpose is: a kind of resin transfer molding (RTM) process resin matrix, its composition and proportioning are: by weight, 100 parts of two bismaleimide resins, 50～90 parts of diallyl phenyl compounds, 20～50 parts of cyanate ester resins and 10～90 portions of reactive thinners.
Described bimaleimide resin is 4,4 '-dimaleoyl imino ditane, 4,4 '-dimaleoyl imino phenyl ether, 4, a kind of in 4 '-dimaleoyl imino sulfobenzide and the N-phenyl substituted maleimide amine or their arbitrary combination; Described diallyl phenyl compound is a kind of in diallyl bisphenol, diallyl bisphenol ether and the diallyl bisphenol S or their arbitrary combination; Described cyanate ester resin is a kind of in bisphenol A cyanate ester resin and the dicyclopentadiene type ethylene rhodanate resin or their combination; Described reactive thinner is a hyperbranched polyorganosiloxane.
A kind of resin transfer molding (RTM) process preparation method of resin matrix, its procedure of processing comprises:
A. by weight, with 100 parts of bimaleimide resins and 50～90 parts of diallyl phenyl compound prepolymerization reaction 30～60min under 120～140 ℃ temperature condition;
B. after being cooled to 100～120 ℃, add 20～50 parts of cyanate ester resins, pre-polymerization 30～60min under 100～120 ℃ temperature condition obtains cyanate/bismaleimides copolymer resins;
C. 10～90 portions of reactive thinners are joined in above-mentioned cyanate/bismaleimides copolymer resins, under 80～100 ℃ of temperature condition, react 30～60min, promptly obtain the resin matrix that a kind of resin transfer molding (RTM) process is used.
For on the basis that keeps original BT resin excellent comprehensive performance, significantly improving its manufacturability, should adopt high performance reactive thinner.Therefore, the present invention adopts hyperbranched polyorganosiloxane, and make it to have can with the group of BT resin reaction, as epoxy group(ing), amino, hydroxyl and unsaturated double-bond etc., like this, play the effect of thinner at uncured stage hyperbranched polyorganosiloxane; Under the proper temperature condition, it can participate in curing cross-linking reaction again, thereby has guaranteed that cured article has excellent comprehensive performances.
The beneficial effect that the present invention has is: with the BT resin is essentially consist, by having excellent heat resistance, dielectric properties, humidity resistance and technological hyperbranched polyorganosiloxane is reactive thinner, on the basis that keeps original BT resin excellent comprehensive performance, significantly improve its manufacturability, satisfy the requirement of resin transfer molding (RTM) process moulding high performance composite.Prepared matrix material has excellent comprehensive mechanical properties, thermotolerance and excellent dielectric properties, can be used for numerous high-technology fields such as space flight and aviation, electronic information, communications and transportation.Preparation method of the present invention also has wide, the operating procedure characteristic of simple of suitability.
Description of drawings
The RTM technology that pure BT resin of Fig. 1 and embodiment of the invention technical scheme the provide temperature-viscosity curve comparison diagram of resin matrix;
Among the figure, curve B T is pure BT comparative example resin system; The resin system that curve B T-1 provides for embodiment 1; The resin system that curve B T-2 provides for embodiment 3; The resin system that curve B T-3 provides for embodiment 6; The resin system that curve B T-4 provides for embodiment 7.
Embodiment
Below in conjunction with drawings and Examples the present invention is further described:
Embodiment 1:
Present embodiment technical scheme concrete steps are as follows:
γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane (KH-560) and deionized water were poured in the reaction flask in 1: 1.2 in molar ratio, regulated PH=3, be heated to 60 ℃ of reaction 7hr, dry 4hr obtains hyperbranched polyorganosiloxane in vacuum drying oven.
With 100g 4,4 '-bismaleimides ditane and 86g 0,0 '-diallyl bisphenol add in the reaction flask, obtain performed polymer after being heated to 135 ℃ of prepolymerization reaction 35min.Treat to add the 30g bisphenol A cyanate ester after performed polymer is cooled to 100 ℃,, obtain the BT resin at 100 ℃ of reaction 45min.
Add the 10g hyperbranched polyorganosiloxane in the BT resin, react 60min down at 80 ℃, obtain a kind of RTM technology resin matrix, after tested, its temperature-viscosity curve is seen the curve B T-1 among Fig. 1.
Preparation comparative example BT resin: with 100g 4,4 '-bismaleimides ditane and 86g 0,0 '-diallyl bisphenol adds in the reaction flask, obtains performed polymer after being heated to 135 ℃ of prepolymerization reaction 35min.Treat to add the 30g bisphenol A cyanate ester after performed polymer is cooled to 100 ℃, at 100 ℃ of reaction 45min, obtain the BT resin, after tested, its temperature-viscosity curve is seen the curve B T among Fig. 1.
γ-methacryloxypropyl trimethoxy silane (KH570) and deionized water were poured in the reaction flask in 1: 1.3 in molar ratio, regulated PH=3, be heated to 60 ℃ of reaction 7hr, obtaining hyperbranched polyorganosiloxane behind the dry 4hr in the vacuum drying oven.
With 100g 4,4 '-diphenyl methane dimaleimide, 35g 0,0 '-diallyl bisphenol, 10g diallyl bisphenol ether and 5g diallyl bisphenol S add in the reaction flask, obtain performed polymer after being heated to 140 ℃ of prepolymerization reaction 30min.Treat to add the 20g bisphenol A cyanate ester after performed polymer is cooled to 120 ℃,, obtain the BT resin at 120 ℃ of reaction 30min.After treating that the BT resin is cooled to 100 ℃, add the 10g hyperbranched polyorganosiloxane, react 30min down, obtain a kind of RTM technology resin matrix at 100 ℃.
γ-methacryloxypropyl trimethoxy silane (KH570) and deionized water were poured in the reaction flask in 1: 1.2 in molar ratio, regulated PH=2, be heated to 60 ℃ of reaction 6hr, dry 4hr obtains hyperbranched polyorganosiloxane in vacuum drying oven.
With 100g 4,4 '-bismaleimides ditane and 90g 0,0 '-diallyl bisphenol add in the reaction flask, obtain performed polymer after being heated to 120 ℃ of prepolymerization reaction 40min.Treat to add the 20g bisphenol A cyanate ester after performed polymer is cooled to 100 ℃,, obtain the BT resin at 100 ℃ of reaction 60min.After treating that the BT resin is cooled to 90 ℃, add the 16g hyperbranched polyorganosiloxane, react 40min down at 90 ℃, promptly obtain a kind of RTM technology resin matrix, after tested, its temperature-viscosity curve is seen the curve B T-2 among Fig. 1.
γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane (KH-560) and deionized water were poured in the reaction flask in 1: 1.2 in molar ratio, regulated PH=4, be heated to 60 ℃ of reaction 7hr, dry 4hr obtains hyperbranched polyorganosiloxane in vacuum drying oven.
With 80g 4,4 '-bismaleimides ditane, 10g 4,4 '-dimaleoyl imino phenyl ether, 10g N-phenyl methyl substituted maleimide amine, 70g 0,0 '-diallyl bisphenol and 20g diallyl bisphenol ether add in the reaction flask, obtain performed polymer after being heated to 140 ℃ of prepolymerization reaction 60min.Treat to add 30g bisphenol A cyanate ester and 20g dicyclopentadiene type ethylene rhodanate after performed polymer is cooled to 120 ℃,, obtain the BT resin at 120 ℃ of reaction 60min.After treating that the BT resin is cooled to 100 ℃, add 30g 4 hyperbranched polyorganosiloxanes and 20g 3# hyperbranched polyorganosiloxane, react 60min down, obtain a kind of RTM technology resin matrix at 100 ℃.
Embodiment 5
γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane (KH-560) and deionized water were poured in the reaction flask in 1: 1.1 in molar ratio, regulated PH=3, be heated to 60 ℃ of reaction 7hr, dry 4hr obtains hyperbranched polyorganosiloxane in vacuum drying oven.
With 100g4,4 '-bismaleimides ditane, 30g0,0 '-diallyl bisphenol, 15g diallyl bisphenol ether and 10g diallyl bisphenol S add in the reaction flask, obtain performed polymer after being heated to 130 ℃ of prepolymerization reaction 30min.Treat to add 15g bisphenol A cyanate ester and 10g dicyclopentadiene type ethylene rhodanate after performed polymer is cooled to 120 ℃,, obtain the BT resin at 120 ℃ of reaction 30min.After treating that the BT resin is cooled to 90 ℃, add the 20g hyperbranched polyorganosiloxane, react 40min down, obtain a kind of RTM technology resin matrix at 90 ℃.
Embodiment 6
γ-methacryloxypropyl trimethoxy silane (KH570) and deionized water were poured in the reaction flask in 1: 1.1 in molar ratio, regulated PH=2, be heated to 50 ℃ of reaction 7hr, dry 4hr obtains hyperbranched polyorganosiloxane in vacuum drying oven.
With 100g 4,4 '-bismaleimides ditane and 85g 0,0 '-diallyl bisphenol add in the reaction flask, obtain performed polymer after being heated to 135 ℃ of prepolymerization reaction 40mi n.Treat to add the 24g bisphenol A cyanate ester after performed polymer is cooled to 110 ℃,, obtain the BT resin at 110 ℃ of reaction 40min.After treating that the BT resin is cooled to 85 ℃, add the 19g hyperbranched polyorganosiloxane, react 40min down at 85 ℃, obtain a kind of RTM technology resin matrix, after tested, its temperature-viscosity curve is seen the curve B T-3 among Fig. 1.
Embodiment 7
γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane (KH-560) and deionized water were poured in the reaction flask in 1: 1.1 in molar ratio, regulated PH=4, be heated to 60 ℃ of reaction 7hr, dry 3hr obtains hyperbranched polyorganosiloxane in vacuum drying oven.
With 100g 4,4 '-bismaleimides ditane and 86g 0,0 '-diallyl bisphenol add in the reaction flask, obtain performed polymer after being heated to 135 ℃ of prepolymerization reaction 35min.Treat to add the 25g bisphenol A cyanate ester after performed polymer is cooled to 110 ℃,, obtain the BT resin at 110 ℃ of reaction 45min.After treating that the BT resin is cooled to 90 ℃, add the 90g hyperbranched polyorganosiloxane, react 40min down at 90 ℃, promptly obtain a kind of RTM technology resin matrix, after tested, its temperature-viscosity curve is seen the curve B T-4 among Fig. 1.
Referring to accompanying drawing 1, it is the temperature-viscosity curve comparison diagram of the RTM technology that provides of pure BT resin and embodiment of the invention technical scheme with resin matrix.By curve among the figure as can be seen, the viscosity of the resin matrix that technical solution of the present invention provides significantly is lower than the viscosity of BT resin under the same temperature, and under suitable temperature range, satisfies the requirement of RTM technology to resin viscosity, therefore, be very suitable for resin transfer molding (RTM) process.
Claims (5)
1. resin transfer molding (RTM) process resin matrix, it is characterized in that, its composition and proportioning are: by weight, comprise 100 parts of bimaleimide resins, 50～90 parts of diallyl phenyl compounds, 20～50 parts of cyanate ester resins and 10～90 portions of reactive thinners; Described reactive thinner is a hyperbranched polyorganosiloxane.
2. a kind of resin transfer molding (RTM) process resin matrix according to claim 1, it is characterized in that: described bimaleimide resin is 4,4 '-dimaleoyl imino ditane, 4,4 '-dimaleoyl imino phenyl ether, 4, a kind of in 4 '-dimaleoyl imino sulfobenzide and the N-phenyl substituted maleimide amine or their arbitrary combination.
3. a kind of resin transfer molding (RTM) process resin matrix according to claim 1 is characterized in that: described diallyl phenyl compound is a kind of in diallyl bisphenol, diallyl bisphenol ether and the diallyl bisphenol S or their arbitrary combination.
4. a kind of resin transfer molding (RTM) process resin matrix according to claim 1 is characterized in that: described cyanate ester resin is a kind of in bisphenol A cyanate ester resin and the dicyclopentadiene type ethylene rhodanate resin or their combination.
5. a resin transfer molding (RTM) process is characterized in that procedure of processing comprises with the preparation method of resin matrix:
A. by weight, with 100 parts of bimaleimide resins and 50～90 parts of diallyl phenyl compound prepolymerization reaction 30～60min under 120～140 ℃ temperature condition;
B. after being cooled to 100～120 ℃, add 20～50 parts of cyanate ester resins, pre-polymerization 30～60min under 100～120 ℃ temperature condition obtains cyanate/bismaleimides copolymer resins;
C. 10～90 portions of reactive thinners are joined in above-mentioned cyanate/bismaleimides copolymer resins, under 80～100 ℃ of temperature condition, react 30～60min, promptly obtain the resin matrix that a kind of resin transfer molding (RTM) process is used; Described reactive thinner is a hyperbranched polyorganosiloxane.
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| CN103131008B (en) * | 2013-01-22 | 2016-05-25 | 广东生益科技股份有限公司 | A kind of BMI prepolymer and synthetic method thereof |
| CN103756314B (en) * | 2013-12-17 | 2016-04-20 | 中航复合材料有限责任公司 | For the preparation method of the bimaleimide resin of matrix material liquid condition shaping |
| CN105199297A (en) * | 2015-10-13 | 2015-12-30 | 湖北三江航天江北机械工程有限公司 | Bismaleimide resin premix with good dielectric property as well as preparation method and device of bismaleimide resin premix |
| CN114685988B (en) * | 2020-12-29 | 2024-08-09 | 洛阳尖端技术研究院 | Modified bismaleimide resin and preparation method and application thereof |
| CN118006291B (en) * | 2024-04-10 | 2024-07-02 | 临朐县金迪胶业有限公司 | Moisture-heat resistant silicone structural adhesive suitable for photovoltaic module |
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Granted publication date: 20110525 Termination date: 20140527 |