CN102796373B - Graphene/cyanate ester/bimaleimide composite material and preparation method thereof - Google Patents
Graphene/cyanate ester/bimaleimide composite material and preparation method thereof Download PDFInfo
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- CN102796373B CN102796373B CN201210282778.7A CN201210282778A CN102796373B CN 102796373 B CN102796373 B CN 102796373B CN 201210282778 A CN201210282778 A CN 201210282778A CN 102796373 B CN102796373 B CN 102796373B
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Abstract
The invention relates to a graphene/cyanate ester/bimaleimide composite material and a preparation method thereof, belonging to the technical field of advanced composite material. The invention is characterized by using graphene modified by hyper-branched polysiloxane, and introducing an active epoxide group which can be chemically reacted with resin to the surface of the graphene, wherein the bimaleimide performed polymer used herein contains bisphenol A diallyl ether as an active diluent, has low viscosity, and is beneficial for dispersing graphene. According to the invention, by using 0.1-10 parts of graphene oxide modified by hyper-branched polysiloxane and 10-80 parts of bimaleimide performed polymer containing bisphenol A diallyl ether to carrying out toughening modification on 100 parts of bisphenol A cyanate ester resin, excellent performance can be achieved, and the usage requirements in a plurality of fields of cyanate ester resin are satisfied.
Description
Technical field
The invention belongs to advanced compound materials science domain, be specifically related to a kind of Graphene/cyanate/Bismaleimide composites and preparation method thereof,
Background technology
Graphene is because its main performance index is all quite even better with Graphene, and avoided Graphene to study the difficult problems such as and catalyst impurities separated with the chirality control, metal mold and the semi-conductor type that are difficult to go beyond in application, and cheap, there is important widely using value.But Graphene surface is inert condition, a little less than the interaction of other media, and between graphene film and sheet, there is stronger Van der Waals force, easily produce and assemble, make its dispersion effect poor.At present, in order to improve the dispersiveness of Graphene, researchist has carried out fruitful work.The method of many functionalization of research is non covalent bond functionalization and covalent linkage functionalization at present.Non covalent bond functionalization is mainly to Graphene, to carry out surface-functionalized by non covalent bond effects such as π-π interaction, ionic linkage and hydrogen bonds.Yet, due to the non covalent bond reactive force between Graphene and modifying and decorating group relatively a little less than, join the interface bond strength forming in resin matrix limited.Therefore, by covalent linkage effect, Graphene being carried out to modification is the functional method the most widely of research at present.Research is found, adopts different organic molecules or linear polymer to carry out Graphene covalent modified, can not only improve the dispersiveness of Graphene, and give the function that Graphene is new.Therefore, the present invention utilizes hyperbranched polyorganosiloxane to Graphene modifying surface, with improve the dispersed of Graphene and with the interface binding intensity of resin.
Cyanate ester resin has excellent high heat resistance, good comprehensive mechanical property and extremely low water-intake rate, a kind of functional materials and the structured material that has had potentiality since twentieth century in aviation field, can be used for making the structural part of military affairs, Aeronautics and Astronautics, navigational field, such as wing, ship shell etc., also can be made into foam sandwich construction material conventional in aerospace.Particularly bisphenol A cyanate ester resin is because of its unique molecular structure, there is the extensive favor that more excellent mechanical property, wet-hot aging performance and electrical property are more subject to investigator, but its cured article is more crisp, need to carry out the service requirements that toughening modifying could meet more occasions to it.Bimaleimide resin, with its excellent thermotolerance, electrical insulating property, good mechanical property, is widely used.Research shows, uses bi-maleimide modified cyanate can improve the mechanical property of cyanate ester resin.Therefore the graphene oxide of studying bismaleimides performed polymer and the modification of a kind of hyperbranched polyorganosiloxane carries out toughening modifying to bisphenol A cyanate ester resin, can meet the service requirements of the multiple fields of cyanate ester resin.
Summary of the invention
The technical problem solving
For fear of the deficiencies in the prior art part, the present invention proposes a kind of Graphene/cyanate/Bismaleimide composites and preparation method thereof.
Technical scheme
/ cyanate ester resin/Bismaleimide composites, is characterized in that the massfraction of material component is: 0.1 ~ 10 part of graphene oxide, 5 ~ 100 parts of bismaleimides performed polymer and 100 parts of bisphenol A cyanate ester resin containing bisphenol a diallyl ether that hyperbranched polyorganosiloxane is modified; The structural formula of the chemical substance of the Graphene that described hyperbranched polyorganosiloxane is modified is:
The structural formula of the chemical substance of described bisphenol A cyanate ester resin is:
The percentage of grafting of the Graphene that described hyperbranched polyorganosiloxane is modified is 5 ~ 30%.
Described bimaleimide resin performed polymer is: massfraction is the reactive thinner bisphenol a diallyl ether of 100 parts of ditane type bismaleimidess and 10-100 part; The structural formula of the chemical substance of described ditane type bimaleimide resin is:
The structural formula of the chemical substance of described bisphenol a diallyl ether is:
A method of preparing Graphene/cyanate ester resin/Bismaleimide composites, is characterized in that step is as follows:
Step 1: the graphite oxide of 0.1 ~ 10 part is joined in the tetrahydrofuran solution of 1 ~ 100 part of KH-560, after ultrasonic dispersion 0.5h, drip the HCl aqueous solution that 1 ~ 50mL concentration is 1mol/L, then at 50 ~ 80 ℃, stir after 4 ~ 7h, obtain hyperbranched polyorganosiloxane and modify graphene oxide;
The reactive thinner bisphenol a diallyl ether that by massfraction is 100 parts of ditane type bismaleimidess and 10-100 part obtains bimaleimide resin performed polymer after 80 ~ 160 ℃ of heating and melting pre-polymerization 0.5～3h;
Step 2: the Graphene that 0.1 ~ 10 part of hyperbranched polyorganosiloxane is modified joins in 10 ~ 80 parts of bimaleimide resin performed polymers, ultrasonic dispersion 0.5 ~ 1h under 40 ~ 60 ℃, 50 ~ 70W;
Step 3: add 100 parts of the cyanate ester resins of 80 ℃ of meltings, stir, heat up, pour in mould after 100 ~ 140 ℃ of pre-polymerization 0.5 ~ 2h;
Step 4: in the vacuum chamber of 140 ℃, vacuumize and remove bubble, putting into air dry oven carries out the stage and heat up to solidify, curing process is 160 ℃/2h+180 ℃/2h+200 ℃/2h, then naturally cooling, after the demoulding, then after aftertreatment 2h, obtain Graphene/cyanate ester resin/Bismaleimide composites at 220 ℃.
Beneficial effect
A kind of Graphene/cyanate/Bismaleimide composites that the present invention proposes and preparation method thereof, the graphene oxide of modifying with bismaleimides performed polymer and a kind of hyperbranched polyorganosiloxane carries out toughening modifying to bisphenol A cyanate ester resin, meets the service requirements of the multiple fields of cyanate ester resin.
The present invention is with respect to prior art, its advantage is: the cyanate ester resin of bismaleimides performed polymer modification of take is matrix, wherein contain reactive thinner bisphenol a diallyl ether and at high temperature Claisen rearrangement can occur, form 2,2 '-diallyl bisphenol, can with ditane type bismaleimides polymerization reaction take place; And in wide temperature range, there is lower viscosity, be conducive to the dispersion of Graphene.In addition, the Graphene that hyperbranched polyorganosiloxane is modified, its a large amount of epoxy group(ing) in surface can be reacted with cyanate resin alicyclic monomer, can improve the interface binding intensity of Graphene and resin, thereby obtain the cyanate ester resin composite material of good heat resistance, mechanical property excellence.
Embodiment
Now the invention will be further described in conjunction with the embodiments:
Due to the bad dispersibility of Graphene in resin, and not high with the bonding strength of resin.Therefore, improve the dispersiveness of Graphene in resin, key is to carry out modification to Graphene.The present invention utilizes the low viscosity of hyperbranched polyorganosiloxane, the feature of high reaction activity is carried out modification to Graphene.Then the Graphene of the Hyperbranched polysilane making being modified and cyanate and bismaleimides are mixed to get matrix material according to certain ratio.This matrix material preparing has excellent mechanical property and tribological property.
Concrete grammar is as follows:
The graphite oxide of 0.1 ~ 10 part is joined in the tetrahydrofuran solution of 1 ~ 100 part of KH-560, after ultrasonic dispersion 0.5h, drip the HCl aqueous solution that 1 ~ 50mL concentration is 1mol/L, then at 50 ~ 80 ℃, stir after 4 ~ 7h, obtain hyperbranched polyorganosiloxane and modify graphene oxide;
The Graphene that 0.1 ~ 10 part of hyperbranched polyorganosiloxane is modified joins in 10 ~ 80 parts of bimaleimide resin performed polymers, at 40 ~ 60 ℃, under 50 ~ 70W after ultrasonic dispersion 0.5 ~ 1h, add 100 parts of the cyanate ester resins of 80 ℃ of meltings, stir, heat up, at 100 ~ 140 ℃ of pre-polymerization 0.5 ~ 2h, pour in hot mould, in the vacuum chamber of 140 ℃, vacuumize and remove bubble, putting into air dry oven carries out the stage and heat up to solidify, curing process is 160 ℃/2h+180 ℃/2h+200 ℃/2h, then naturally cooling, after the demoulding, at 220 ℃, aftertreatment 2h obtains Graphene/cyanate ester resin/Bismaleimide composites again
Embodiment 1:
(1) graphite oxide of 0.1 ~ 10 part is joined in the tetrahydrofuran solution of 1 ~ 100 part of KH-560, after ultrasonic dispersion 0.5h, drip the HCl aqueous solution that 1 ~ 50mL concentration is 1mol/L, then at 50 ~ 80 ℃, stir after 4 ~ 7h, obtain hyperbranched polyorganosiloxane and modify graphene oxide;
(2) Graphene of 0.1 part of hyperbranched polyorganosiloxane being modified joins in 10 parts of bimaleimide resin performed polymers, at 40 ~ 60 ℃, under 50 ~ 70W after ultrasonic dispersion 0.5 ~ 1h, add 100 parts of the cyanate ester resins of 80 ℃ of meltings, stir, heat up, at 100 ~ 140 ℃ of pre-polymerization 0.5 ~ 2h, pour in hot mould, in the vacuum chamber of 140 ℃, vacuumize and remove bubble, putting into air dry oven carries out the stage and heat up to solidify, curing process is 160 ℃/2h+180 ℃/2h+200 ℃/2h, then naturally cooling, after the demoulding, at 220 ℃, aftertreatment 2h obtains Graphene/cyanate ester resin/Bismaleimide composites again.
Embodiment 2:
(1) preparation method that hyperbranched polyorganosiloxane is modified graphene oxide is with embodiment 1;
(2) Graphene of 0.5 part of hyperbranched polyorganosiloxane being modified joins in 20 parts of bimaleimide resin performed polymers, at 40 ~ 60 ℃, under 50 ~ 70W after ultrasonic dispersion 0.5 ~ 1h, add 100 parts of the cyanate ester resins of 80 ℃ of meltings, stir, heat up, at 100 ~ 140 ℃ of pre-polymerization 0.5 ~ 2h, pour in hot mould, in the vacuum chamber of 140 ℃, vacuumize and remove bubble, putting into air dry oven carries out the stage and heat up to solidify, curing process is 160 ℃/2h+180 ℃/2h+200 ℃/2h, then naturally cooling, after the demoulding, at 220 ℃, aftertreatment 2h obtains Graphene/cyanate ester resin/Bismaleimide composites again.
Embodiment 3:
(1) preparation method that hyperbranched polyorganosiloxane is modified graphene oxide is with embodiment 1;
(2) Graphene of 1 part of hyperbranched polyorganosiloxane being modified joins in 30 parts of bimaleimide resin performed polymers, at 40 ~ 60 ℃, under 50 ~ 70W after ultrasonic dispersion 0.5 ~ 1h, add 100 parts of the cyanate ester resins of 80 ℃ of meltings, stir, heat up, at 100 ~ 140 ℃ of pre-polymerization 0.5 ~ 2h, pour in hot mould, in the vacuum chamber of 140 ℃, vacuumize and remove bubble, putting into air dry oven carries out the stage and heat up to solidify, curing process is 160 ℃/2h+180 ℃/2h+200 ℃/2h, then naturally cooling, after the demoulding, at 220 ℃, aftertreatment 2h obtains Graphene/cyanate ester resin/Bismaleimide composites again.
Embodiment 4:
(1) preparation method that hyperbranched polyorganosiloxane is modified graphene oxide is with embodiment 1;
(2) Graphene of 2 parts of hyperbranched polyorganosiloxanes being modified joins in 30 parts of bimaleimide resin performed polymers, at 40 ~ 60 ℃, under 50 ~ 70W after ultrasonic dispersion 0.5 ~ 1h, add 100 parts of the cyanate ester resins of 80 ℃ of meltings, stir, heat up, at 100 ~ 140 ℃ of pre-polymerization 0.5 ~ 2h, pour in hot mould, in the vacuum chamber of 140 ℃, vacuumize and remove bubble, putting into air dry oven carries out the stage and heat up to solidify, curing process is 160 ℃/2h+180 ℃/2h+200 ℃/2h, then naturally cooling, after the demoulding, at 220 ℃, aftertreatment 2h obtains Graphene/cyanate ester resin/Bismaleimide composites again.
Embodiment 5:
(1) preparation method that hyperbranched polyorganosiloxane is modified graphene oxide is with embodiment 1;
(2) Graphene of 4 parts of hyperbranched polyorganosiloxanes being modified joins in 40 parts of bimaleimide resin performed polymers, at 40 ~ 60 ℃, under 50 ~ 70W after ultrasonic dispersion 0.5 ~ 1h, add 100 parts of the cyanate ester resins of 80 ℃ of meltings, stir, heat up, at 100 ~ 140 ℃ of pre-polymerization 0.5 ~ 2h, pour in hot mould, in the vacuum chamber of 140 ℃, vacuumize and remove bubble, putting into air dry oven carries out the stage and heat up to solidify, curing process is 160 ℃/2h+180 ℃/2h+200 ℃/2h, then naturally cooling, after the demoulding, at 220 ℃, aftertreatment 2h obtains Graphene/cyanate ester resin/Bismaleimide composites again.
Embodiment 6:
(1) preparation method that hyperbranched polyorganosiloxane is modified graphene oxide is with embodiment 1;
(2) Graphene of 5 parts of hyperbranched polyorganosiloxanes being modified joins in 50 parts of bimaleimide resin performed polymers, at 40 ~ 60 ℃, under 50 ~ 70W after ultrasonic dispersion 0.5 ~ 1h, add 100 parts of the cyanate ester resins of 80 ℃ of meltings, stir, heat up, at 100 ~ 140 ℃ of pre-polymerization 0.5 ~ 2h, pour in hot mould, in the vacuum chamber of 140 ℃, vacuumize and remove bubble, putting into air dry oven carries out the stage and heat up to solidify, curing process is 160 ℃/2h+180 ℃/2h+200 ℃/2h, then naturally cooling, after the demoulding, at 220 ℃, aftertreatment 2h obtains Graphene/cyanate ester resin/Bismaleimide composites again.
Claims (3)
1. Graphene/cyanate ester resin/Bismaleimide composites, is characterized in that the massfraction of material component is: 0.1～10 part of graphene oxide, 5～100 parts of bismaleimides performed polymer and 100 parts of bisphenol A cyanate ester resin containing bisphenol a diallyl ether that hyperbranched polyorganosiloxane is modified; The grapheme modified structural representation of described hyperbranched polyorganosiloxane is as follows:
The structural formula of the chemical substance of described bisphenol A cyanate ester resin is:
Preparation process is as follows:
Step 1: the graphite oxide of 0.1～10 part is joined in the tetrahydrofuran solution of 1～100 part of KH-560, after ultrasonic dispersion 0.5h, drip the HCl aqueous solution that 1～50mL concentration is 1mol/L, then at 50～80 ℃, stir after 4～7h, obtain hyperbranched polyorganosiloxane and modify graphene oxide;
The reactive thinner bisphenol a diallyl ether that by massfraction is 100 parts of ditane type bismaleimidess and 10-100 part obtains bimaleimide resin performed polymer after 80～160 ℃ of heating and melting pre-polymerization 0.5～3h;
Step 2: the Graphene that 0.1～10 part of hyperbranched polyorganosiloxane is modified joins in 10～80 parts of bimaleimide resin performed polymers, ultrasonic dispersion 0.5～1h under 40～60 ℃, 50～70W;
Step 3: add 100 parts of the cyanate ester resins of 80 ℃ of meltings, stir, heat up, pour in mould after 100～140 ℃ of pre-polymerization 0.5～2h;
Step 4: in the vacuum chamber of 140 ℃, vacuumize and remove bubble, putting into air dry oven carries out the stage and heat up to solidify, curing process is 160 ℃/2h+180 ℃/2h+200 ℃/2h, then naturally cooling, after the demoulding, then after aftertreatment 2h, obtain Graphene/cyanate ester resin/Bismaleimide composites at 220 ℃.
2. Graphene/cyanate ester resin/Bismaleimide composites according to claim 1, is characterized in that: the percentage of grafting of the Graphene that described hyperbranched polyorganosiloxane is modified is 5～30%.
3. Graphene/cyanate ester resin/Bismaleimide composites according to claim 1, is characterized in that: described bimaleimide resin performed polymer is: massfraction is the reactive thinner bisphenol a diallyl ether of 100 parts of ditane type bismaleimidess and 10-100 part; The structural formula of the chemical substance of described ditane type bimaleimide resin is:
The structural formula of the chemical substance of described bisphenol a diallyl ether is:
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| CN104231624B (en) * | 2014-08-22 | 2016-05-11 | 南京信息职业技术学院 | A kind of modified cyanic acid ester resin heat-conductive composite material and preparation method thereof |
| CN104558609B (en) * | 2015-01-09 | 2017-01-18 | 西北工业大学 | Oriented graphene/bismaleimide multilevel composite material and preparation method thereof |
| CN106893322B (en) * | 2017-04-01 | 2019-03-08 | 国家纳米科学中心 | A kind of graphene/cyanate composite material and its preparation method and application |
| CN107141794A (en) * | 2017-06-20 | 2017-09-08 | 苏州大学 | A kind of resin base brush and preparation method thereof |
| CN107556750B (en) * | 2017-07-24 | 2020-04-03 | 四川大学 | High-temperature-resistant polyetherimide composite foam material and preparation method thereof |
| CN112518732B (en) * | 2020-12-02 | 2022-06-17 | 哈尔滨工业大学 | Grabbing structure with shape memory function and preparation method thereof |
| CN113913107A (en) * | 2021-08-25 | 2022-01-11 | 浙江儒商科技有限公司 | Preparation method of bismaleimide self-lubricating wear-resistant swash plate |
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| US5780581A (en) * | 1995-10-27 | 1998-07-14 | Hughes Aircraft Company | Plateable structural adhesive for cyanate ester composites |
| CN101456952A (en) * | 2007-12-11 | 2009-06-17 | 同济大学 | Cyanate ester/bimaleimide modified resin and preparation method |
| CN101457021A (en) * | 2007-12-14 | 2009-06-17 | 西北工业大学 | Nano silicon nitride/bimaleimide resin/cyanate ester resin composite material and preparation method thereof |
| CN101824147B (en) * | 2010-04-29 | 2012-08-22 | 苏州大学 | Modified bismaleimide-triazine resin and preparation method thereof |
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