CN103172862A - Nano-filler bismaleimide resin and preparation method thereof - Google Patents
Nano-filler bismaleimide resin and preparation method thereof Download PDFInfo
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- CN103172862A CN103172862A CN2013101052051A CN201310105205A CN103172862A CN 103172862 A CN103172862 A CN 103172862A CN 2013101052051 A CN2013101052051 A CN 2013101052051A CN 201310105205 A CN201310105205 A CN 201310105205A CN 103172862 A CN103172862 A CN 103172862A
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Abstract
The invention provides a nano-filler bismaleimide resin and a preparation method thereof. According to the adopted preparation method, not only can the technological condition be simplified, but also control is easy, and a special mixing device is not needed in a mixing process. A bismaleimide resin prepolymer prepared by the method disclosed by the invention has good solubleness in organic solvents such as acetone, and is beneficial to the preparation of a high-performance composite material. In addition, compared with other bismaleimide resin, the nano-filler bismaleimide resin prepared by the method disclosed by the invention is small in melting viscosity; and the combination properties such as the solubleness of the solvent, as well as the toughness and heat stability of the obtained cured resin are obviously improved.
Description
Technical field
The present invention relates to field of compound material, be specifically related to a kind ofly have higher toughness, high heat resistance and be used for modified bismaleimide resin of filling nano material and preparation method thereof.
Background technology
Bimaleimide resin (BMI) is because of the advantage such as it has good high temperature resistant, radiation hardness, wet-heat resisting, rate of moisture absorption is low and thermal expansivity is little, become a kind of important composite matrix resin, the application of succeeding in fields such as space flight, aviation and microelectronics.But BMI fragility is larger, and shock resistance is relatively poor and to be used for preparing the manufacturability of matrix material poor, and these shortcomings have seriously hindered the application of BMI at Material Field.In recent decades, BMI is toughness reinforcing improves with preparation technology the important content that always is the performance resins research and development, no matter be that copolymerization is toughness reinforcing, outer chain extension is toughness reinforcing, High performance plastic resin is toughness reinforcing, or rigidity nano-particle toughening, these methods all ubiquity deficiency, be that single solution is toughness reinforcing or improve technique, the resistance to elevated temperatures of even having sacrificed BMI that has.Be the science and technology that satisfies high speed development now and industrial, a kind ofly have excellent manufacturability concurrently, the development of outstanding toughness and stable on heating new type resin system is extremely urgent.
The Chinese patent " nanometer composite double maleimide resin and preparation method thereof " of Beijing Research Inst. of Aeronautic Material application (CN12000015) discloses a kind of nano combined bimaleimide resin that is applicable to and nanometer composite technology and the composite manufacture method thereof of filling nano material in this bimaleimide resin.This patent only relates to the combination of bismaleimides and clay, does not go deep into performance and the technique of BMI.The Chinese patent " hyperbranched polyorganosiloxane modified bismaleimide resin " that the beautiful people of grade of Gu beloved daughter of University Of Suzhou applies for (CN101775139) discloses the preparation method of the hyperbranched modified bismaleimide resin of a kind of use.Although this patent has confirmed hyperbranched polyorganosiloxane and has produced effect aspect toughness reinforcing at thermosetting resin, but the uncontrollability of its siloxanes hydrolysis degree and cause level of response uncontrollable is to the toughness reinforcing defectives such as effect is outstanding, unstable that exist of thermosetting resin.
Summary of the invention
The technical problem that solves
For fear of the deficiencies in the prior art part, the present invention proposes a kind of nano-filled bimaleimide resin and preparation method thereof, provide a kind of outstanding toughness that has, excellent high thermal resistance and good technological nano-filled modified bismaleimide resin and preparation method thereof that is applicable to.
Technical scheme
A kind of nano-filled bimaleimide resin, it is characterized in that material component is counted ratio by weight as follows: 100 parts of bismaleimidess, 25～70 parts of diallyl bisphenols, 0.5～10 part of γ-(quadrol base) propyl group methyl dimethoxysilane and 0.4～5 part of silicon-dioxide.
Described bismaleimides is N, N'-4,4'-diphenyl methane dimaleimide.
Described silicon-dioxide is aerosil, and particle diameter is at 30～50nm.
A kind of method for preparing nano-filled bimaleimide resin is characterized in that step is as follows:
Step 1: bismaleimides, diallyl bisphenol and γ-(quadrol base) propyl group methyl dimethoxysilane is mixed under normal temperature and pressure conditions in proportion, reacted under the environment of room temperature 40～100 minutes;
Step 2: sealing is warming up to 40 ℃～60 ℃, then adds the ethanolic soln of the silicon-dioxide of 20～50 parts, stirs, and reacts 20～40 minutes; The ethanolic soln of described silicon-dioxide is counted: 100 parts of the ethanolic solns of silicon-dioxide and silica 1～10 part by weight;
Step 3: then be warming up to 130 ℃～150 ℃, remain under the condition of stirring and reacted 30～100 minutes, after the vacuum degassing bubble, obtain nano-filled bimaleimide resin.
A kind of method of using described nano-filled bimaleimide resin is characterized in that: nano-filled bimaleimide resin is carried out moulding, solidified 2 hours through 160 ℃, 180 ℃ solidified 2 hours, and 200 ℃ solidified 2 hours, 240 ℃ of lower aftertreatments 4 hours.
Beneficial effect
A kind of nano-filled bimaleimide resin that the present invention proposes and preparation method thereof, the preparation method of employing has not only simplified processing condition, and is easy to control, and mixing process need not special mixing device.Adopt the nano-filled Bismaleimides resin pre-polymer of method preparation of the present invention, have good solvability in acetone and other organic solvent, this is highly beneficial for making high performance composite.In addition, than other bimaleimide resins, the melting viscosity of the prepared nano-filled bimaleimide resin of the present invention is little, solvent solubility, and the over-all propertieies such as the toughness of the cured resin that obtains, thermostability have obvious lifting.
Embodiment
Now the invention will be further described in conjunction with the embodiments:
Embodiment 1:
1, the N of 100g, N'-4, the 4'-diphenyl methane dimaleimide, the diallyl bisphenol of 43g and the γ of 5.75g-(quadrol base) propyl group methyl dimethoxysilane mixes at ambient temperature, and reaction is 90 minutes under room temperature environment; Be warming up to 60 ℃, add the ethanolic soln (wherein 0.42g silicon-dioxide) of 20g silicon-dioxide, stir under enclosed environment, reacted 30 minutes; Be warming up to 140 ℃, under the condition that keeps stirring, reaction is 40 minutes, guarantees that ethanol volatilizees fully, obtains a kind of nano-filled bimaleimide resin after the vacuum stripping bubble is processed.
2, above-mentioned nano-filled bimaleimide resin after the post curing treatment of the curing process of 160 ℃/2h, 180 ℃/2h and 200 ℃/2h and 240 ℃/4h, obtains nano-filled bismaleimides cured resin.
Comparative example: prepare bimaleimide resin example 1 in contrast by as above technique.The N of 100g, N'-4, the diallyl bisphenol of 4'-diphenyl methane dimaleimide and 43g mixes at ambient temperature, and reaction is 90 minutes under room temperature environment; Be warming up to 60 ℃, stir under enclosed environment, reacted 30 minutes; Be warming up to 140 ℃, under the condition that keeps stirring, reaction is 40 minutes, obtains a kind of nano-filled bimaleimide resin after the vacuum stripping bubble is processed.After the post curing treatment of the curing process of 160 ℃/2h, 180 ℃/2h and 200 ℃/2h and 240 ℃/4h, obtain the bismaleimides cured resin.
Testing method according to GB/T2570-1995 and GB/T2571-1995 is tested comparison toughness and intensity to shock strength and the flexural strength of two kinds of resins in above-described embodiment 1 and comparative example; With thermogravimetic analysis (TGA) (TGA) and dynamic mechanically mechanical property (DMA) analysis, the resistance toheat of two kinds of resins in above-described embodiment 1 and comparative example is estimated.
The properties of the bismaleimides cured resin in the resulting nano-filled bismaleimides cured resin of embodiment in the present invention 1 and comparative example is tested comparison, and result is as shown in table 1.
Table 1
According to above-mentioned table 1 data presentation, compare bimaleimide resin, the toughness of nano-filled bimaleimide resin provided by the invention and intensity have obtained significant raising; According to the thermal characteristics data, the thermotolerance of nano-filled bimaleimide resin provided by the invention has obtained obvious lifting.
Embodiment 2:
The N of 100g, N'-4, the 4'-diphenyl methane dimaleimide, the diallyl bisphenol of 60g and the γ of 5.75g-(quadrol base) propyl group methyl dimethoxysilane mixes at ambient temperature, and reaction is 90 minutes under room temperature environment; Be warming up to 60 ℃, add the ethanolic soln (wherein 0.42g silicon-dioxide) of 20g silicon-dioxide, stir under enclosed environment, reacted 30 minutes; Be warming up to 140 ℃, under the condition that keeps stirring, reaction is 40 minutes, guarantees that ethanol volatilizees fully, obtains a kind of nano-filled bimaleimide resin after the vacuum stripping bubble is processed.
This resin obtains nano-filled bismaleimides cured resin after the post curing treatment of the curing process of 160 ℃/2h, 180 ℃/2h and 200 ℃/2h and 240 ℃/4h.
Embodiment 3:
The N of 100g, N'-4, the 4'-diphenyl methane dimaleimide, the diallyl bisphenol of 43g and the γ of 2.87g-(quadrol base) propyl group methyl dimethoxysilane mixes at ambient temperature, and reaction is 90 minutes under room temperature environment; Be warming up to 60 ℃, add the ethanolic soln (wherein 0.42g silicon-dioxide) of 20g silicon-dioxide, stir under enclosed environment, reacted 30 minutes; Be warming up to 140 ℃, under the condition that keeps stirring, reaction is 40 minutes, guarantees that ethanol volatilizees fully, obtains a kind of nano-filled bimaleimide resin after the vacuum stripping bubble is processed.
This resin obtains nano-filled bismaleimides cured resin after the post curing treatment of the curing process of 160 ℃/2h, 180 ℃/2h and 200 ℃/2h and 240 ℃/4h.
Embodiment 4:
The N of 100g, N'-4, the 4'-diphenyl methane dimaleimide, the diallyl bisphenol of 43g and the γ of 8.62g-(quadrol base) propyl group methyl dimethoxysilane mixes at ambient temperature, and reaction is 90 minutes under room temperature environment; Be warming up to 60 ℃, add the ethanolic soln (wherein 0.42g silicon-dioxide) of 20g silicon-dioxide, stir under enclosed environment, reacted 30 minutes; Be warming up to 140 ℃, under the condition that keeps stirring, reaction is 40 minutes, guarantees that ethanol volatilizees fully, obtains a kind of nano-filled bimaleimide resin after the vacuum stripping bubble is processed.
This resin obtains nano-filled bismaleimides cured resin after the post curing treatment of the curing process of 160 ℃/2h, 180 ℃/2h and 200 ℃/2h and 240 ℃/4h.
Embodiment 5:
The N of 100g, N'-4, the 4'-diphenyl methane dimaleimide, the diallyl bisphenol of 43g and the γ of 5.75g-(quadrol base) propyl group methyl dimethoxysilane mixes at ambient temperature, and reaction is 90 minutes under room temperature environment; Be warming up to 60 ℃, add the ethanolic soln (wherein 0.84g silicon-dioxide) of 20g silicon-dioxide, stir under enclosed environment, reacted 30 minutes; Be warming up to 140 ℃, under the condition that keeps stirring, reaction is 40 minutes, guarantees that ethanol volatilizees fully, obtains a kind of nano-filled bimaleimide resin after the vacuum stripping bubble is processed.
This resin obtains nano-filled bismaleimides cured resin after the post curing treatment of the curing process of 160 ℃/2h, 180 ℃/2h and 200 ℃/2h and 240 ℃/4h.
Embodiment 6:
The N of 100g, N'-4, the 4'-diphenyl methane dimaleimide, the diallyl bisphenol of 43g and the γ of 5.75g-(quadrol base) propyl group methyl dimethoxysilane mixes at ambient temperature, and reaction is 90 minutes under room temperature environment; Be warming up to 60 ℃, add the ethanolic soln (wherein 1.68g silicon-dioxide) of 20g silicon-dioxide, stir under enclosed environment, reacted 30 minutes; Be warming up to 140 ℃, under the condition that keeps stirring, reaction is 40 minutes, guarantees that ethanol volatilizees fully, obtains a kind of nano-filled bimaleimide resin after the vacuum stripping bubble is processed.
This resin obtains nano-filled bismaleimides cured resin after the post curing treatment of the curing process of 160 ℃/2h, 180 ℃/2h and 200 ℃/2h and 240 ℃/4h.
Claims (5)
1. nano-filled bimaleimide resin, it is characterized in that material component is counted ratio by weight as follows: 100 parts of bismaleimidess, 25～70 parts of diallyl bisphenols, 0.5～10 part of γ-(quadrol base) propyl group methyl dimethoxysilane and 0.4～5 part of silicon-dioxide.
2. nano-filled bimaleimide resin according to claim 1, it is characterized in that: described bismaleimides is N, N'-4,4'-diphenyl methane dimaleimide.
3. nano-filled bimaleimide resin according to claim 1, it is characterized in that: described silicon-dioxide is aerosil, and particle diameter is at 30～50nm.
4. method for preparing the described nano-filled bimaleimide resin of claim 1～3 any one is characterized in that step is as follows:
Step 1: bismaleimides, diallyl bisphenol and γ-(quadrol base) propyl group methyl dimethoxysilane is mixed under normal temperature and pressure conditions in proportion, reacted under the environment of room temperature 40～100 minutes;
Step 2: sealing is warming up to 40 ℃～60 ℃, then adds the ethanolic soln of the silicon-dioxide of 20～50 parts, stirs, and reacts 20～40 minutes; The ethanolic soln of described silicon-dioxide is counted: 100 parts of the ethanolic solns of silicon-dioxide and silica 1～10 part by weight;
Step 3: then be warming up to 130 ℃～150 ℃, remain under the condition of stirring and reacted 30～100 minutes, after the vacuum degassing bubble, obtain nano-filled bimaleimide resin.
5. a right to use requires the method for 1 described nano-filled bimaleimide resin, it is characterized in that: nano-filled bimaleimide resin is carried out moulding, and through 160 ℃ of curing 2 hours, 180 ℃ solidified 2 hours, 200 ℃ solidified 2 hours, 240 ℃ of lower aftertreatments 4 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106243716A (en) * | 2016-08-22 | 2016-12-21 | 威海光威复合材料股份有限公司 | Nano-ceramic powder modified bismaleimide resin prepares the method for composite |
| CN114561101A (en) * | 2022-04-01 | 2022-05-31 | 焦作市天益科技有限公司 | Diallyl bisphenol A modified bismaleimide resin capable of prolonging shelf life and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1982369A (en) * | 2005-12-16 | 2007-06-20 | 西北工业大学 | Bi-maleimide self-lubricating nano-composite material and its production |
| CN102775605A (en) * | 2012-08-14 | 2012-11-14 | 西北工业大学 | Modified bismaleimide resin and preparation method thereof |
-
2013
- 2013-03-28 CN CN2013101052051A patent/CN103172862A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1982369A (en) * | 2005-12-16 | 2007-06-20 | 西北工业大学 | Bi-maleimide self-lubricating nano-composite material and its production |
| CN102775605A (en) * | 2012-08-14 | 2012-11-14 | 西北工业大学 | Modified bismaleimide resin and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106243716A (en) * | 2016-08-22 | 2016-12-21 | 威海光威复合材料股份有限公司 | Nano-ceramic powder modified bismaleimide resin prepares the method for composite |
| CN114561101A (en) * | 2022-04-01 | 2022-05-31 | 焦作市天益科技有限公司 | Diallyl bisphenol A modified bismaleimide resin capable of prolonging shelf life and preparation method thereof |
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Application publication date: 20130626 |