CN102775786A - Graphene oxide/cyanate ester composite material and preparation method thereof - Google Patents
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Abstract
The invention relates to a graphene oxide/cyanate ester composite material and a preparation method of the graphene oxide/cyanate ester composite material, which belongs to the field of advanced composite material technology. The graphene oxide/cyanate ester composite material is prepared by using 0.1-10 parts of hyperbranched polysiloxane-modified graphene oxide, 5-50 parts of epoxy active dilute and 100 parts of bisphenol A cyanate ester prepared by a casting molding method. In order to improve dispersibility of graphene oxide in cyanate ester resin and bonding strength between graphene oxide and cyanate ester resin, hyperbranched polysiloxane is used to modify graphene oxide to introduce active functional group epoxy groups onto the surface of graphene oxide, which can chemically react with the resin. Otherwise, the epoxy active dilute can chemically react with the resin and the epoxy groups on the surface of the graphene. Thus, compatibility and interface adhesion between graphene oxide and the resin are increased on one hand, and low viscosity is helpful to disperse graphene on the other hand. The prepared composite material has excellent performances and can meet the use requirements of cyanate ester resin in various fields.
Description
Technical field
The invention belongs to advanced compound materials science domain, relate to a kind of graphene oxide/cyanate ester resin composite material and preparation method thereof.
Background technology
Graphene oxide is by graphite oxidation and ultra-sonic dispersion; Except having the excellent performance of Graphene; Its surface has the functional group of high reaction activities such as hydroxyl, carboxyl and epoxide group; Can introduce organo-functional group on the Graphene surface through chemical reaction graphene oxide is carried out modification, can not only improve the dispersiveness of graphene oxide, and give graphene oxide new function.For example; Make graphene oxide through sonioation method; Through acyl chloride reaction 4-amino-benzene oxygen phthalonitrile is grafted on the graphene oxide surface then; Make the nitrile modified graphene, and make nano composite material as filler and poly (arylene ether nitrile), find that Young's modulus, tensile strength, the pyrolysis temperature of matrix material all obviously improves with it.And for example, utilize vinyltriethoxysilane that graphene oxide is modified, and be mixed with out nano composite material, found the barrier property of Graphene in polymkeric substance with new LDPE (film grade).
Hyperbranched polyorganosiloxane has LV, high rheological, good solubility, and for the dispersiveness that improves graphene oxide provides favourable condition, particularly its molecular end exists Si-Cl, Si-H, Si-OH, Si-NH
2The isoreactivity group is easy to carry out molecular designing according to different needs.But do not see the report of modifying graphene oxide with hyperbranched polymerization at present as yet.Therefore, the present invention utilizes hyperbranched polyorganosiloxane that modification is carried out on the graphene oxide surface, like this, not only can improve the dispersiveness of graphene oxide, and can improve the interface binding intensity of graphene oxide and resin.
Cyanate ester resin has excellent high heat resistance, good comprehensive mechanical properties and extremely low water-intake rate; Be a kind of functional materials and the structured material that in aviation field, has had potentiality since the twentieth century; Can be used for making the structural part in military affairs, Aeronautics and Astronautics, navigation field; Such as wing, ship shell etc., also can be made into conventional foam sandwich structure material in the aerospace.Particularly bisphenol A cyanate ester resin is because of its distinctive molecular structure; Have more excellent mechanical property, wet-hot aging performance and electrical property and more receive investigator's extensive favor; But its cured article is more crisp, need carry out the request for utilization that toughening modifying could satisfy more occasions to it.
Summary of the invention
The technical problem that solves
Weak point for fear of prior art; The present invention proposes a kind of graphene oxide/cyanate ester resin composite material and preparation method thereof; The oxidation graphene oxide that uses a kind of hyperbranched polyorganosiloxane to modify carries out toughening modifying to bisphenol A cyanate ester resin, satisfies the request for utilization in the multiple field of cyanate ester resin.
Technical scheme
A kind of graphene oxide/cyanate ester resin composite material is characterized in that the massfraction of material component is: 0.1 ~ 10 part of graphene oxide, 5 ~ 50 epoxy active diluents and 100 parts of bisphenol A cyanate ester resin monomer that hyperbranched polyorganosiloxane is modified; The chemical substance structure formula of the graphene oxide that said hyperbranched polyorganosiloxane is modified is:
The monomeric chemical substance structure formula of bisphenol A cyanate ester resin is:
Said epoxy active diluent is E-44 or E-51.
A kind of method for preparing said graphene oxide/cyanate ester resin composite material is characterized in that step is following:
Step 1: 0.1 ~ 10 part graphite oxide is joined in the tetrahydrofuran solution of 1 ~ 100 part of KH-560; Dripping 1 ~ 50mL concentration behind the ultra-sonic dispersion 0.5h is the HCl aqueous solution of 1mol/L; Behind 50 ~ 80 ℃ of stirring 4 ~ 7h, obtain hyperbranched polyorganosiloxane and modify graphene oxide then;
Step 2: 0.1 ~ 10 part of hyperbranched polyorganosiloxane is modified in the epoxy active diluent that graphene oxide joins 5 ~ 50 parts; At ultra-sonic dispersion under the power of 40 ~ 70W after 0.5 ~ 3 hour; Join 100 parts in 80 ℃ of fused bisphenol A cyanate ester resin monomers, at 80 ~ 120 ℃ of following prepolymerization 15 ~ 60min;
Step 3: pour in the good mould of preheating; In 120 ℃ vacuum chamber, vacuumize except that taking out behind the bubble, put into air dry oven then and carry out stage intensification curing; Curing process is 140 ℃/2h+160 ℃/2h+180 ℃/2h; Naturally cooling after the demoulding, obtains graphene oxide/cyanate ester resin composite material at 200 ℃ of following aftertreatment 2h more then.
Beneficial effect
A kind of graphene oxide/cyanate ester resin composite material that the present invention proposes and preparation method thereof; In the cyanate ester resin matrix, containing epoxy active diluent is E-44 or E-51; This epoxy active diluent also can react with the epoxy group(ing) on graphene oxide surface for carrying out chemical reaction with resin.Can increase the consistency and the bonding interface property of graphene oxide and resin like this, on the one hand.Its viscosity is very low on the other hand, helps the dispersion of graphene oxide.In addition; In graphene oxide surface grafting hyperbranched polyorganosiloxane, contain a large amount of active function groups epoxy group(ing); It is dispersed in resin not only can to improve graphene oxide, also can strengthen the interface bond strength of itself and resin, helps improving the mechanical property of matrix material.
Description of drawings
Fig. 1 is graphene oxide/cyanate ester resin composite material preparation technology schema.
Embodiment
Combine embodiment, accompanying drawing that the present invention is further described at present:
Because it is not the bad dispersibility of graphene oxide in resin, and high with the bonding strength of resin.Therefore, improve the dispersiveness of graphene oxide in resin, key is to carry out modification to graphene oxide.One aspect of the present invention utilizes the LV of hyperbranched polyorganosiloxane, the characteristics of high reaction activity that graphene oxide is carried out modification.Utilize the very low epoxy modifying agent of viscosity on the other hand, the dispersion that both can be graphene oxide improves strong condition, again can with the graphene oxide and the resin reaction of modification.Hydride modified graphene oxide, epoxy active diluent and the cyanate resin alicyclic monomer of hyperbranched poly according to certain mixed after, cast molding, the prepared composite material has mechanical property.
Concrete grammar is following:
(1) 0.1 ~ 10 part graphite oxide is joined in the tetrahydrofuran solution of 1 ~ 100 part of KH-560 ultra-sonic dispersion 0.5h.Dripping 1 ~ 50mL concentration then is the HCl aqueous solution of 1mol/L, dropwises the back behind 50 ~ 80 ℃ of stirring 4 ~ 7h, removes the small-molecule substance that generates in the dereaction, promptly gets hyperbranched polyorganosiloxane and modifies graphene oxide.
Above-mentioned graphene oxide is the graphene oxide that hyperbranched polyorganosiloxane is modified.Be that graphene oxide and γ-glycidyl ether oxygen propyl trimethoxy silicane (KH-560) form through hydrolytic condensation; The epoxy group(ing) that its surface is a large amount of; Can react with the cyanate resin alicyclic monomer, improve the dispersed of graphene oxide and with the interface binding intensity of resin.The principle of the graphene oxide that hyperbranched polyorganosiloxane is modified is following:
The oxidation of (2) 0.1 ~ 10 part of hyperbranched polyorganosiloxane being modified joins in 5 ~ 50 parts the epoxy active diluent, at ultra-sonic dispersion under the power of 40 ~ 70W after 0.5 ~ 3 hour, joins 100 parts in 80 ℃ of fused bisphenol A cyanate ester resin monomers; 80 ~ 120 ℃ of following prepolymerization 15 ~ 60min pour in the good mould of preheating, in 120 ℃ vacuum chamber then; Vacuumize and remove bubble; Until there not being bubble to emerge, take out mould, put into air dry oven and carry out stage intensification curing; Curing process is 140 ℃/2h+160 ℃/2h+180 ℃/2h; Naturally cooling after the demoulding, promptly gets graphene oxide/cyanate ester resin composite material at 200 ℃ of following aftertreatment 2h more then.
Embodiment 1:
(1) 0.1 ~ 10 part graphite oxide is joined in the tetrahydrofuran solution of 1 ~ 100 part of KH-560 ultra-sonic dispersion 0.5h.Dripping 1 ~ 50mL concentration then is the HCl aqueous solution of 1mol/L, dropwises the back behind 50 ~ 80 ℃ of stirring 4 ~ 7h, removes the small-molecule substance that generates in the dereaction, promptly gets hyperbranched polyorganosiloxane and modifies graphene oxide.
(2) graphene oxide of 0.1 part of hyperbranched polyorganosiloxane being modified joins among 10 parts the epoxy active diluent E-44, after 0.5 ~ 3 hour, joins 100 parts at ultra-sonic dispersion under the power of 40 ~ 70W in 80 ℃ of fused bisphenol A cyanate ester resin monomers; At 80 ~ 120 ℃ of following prepolymerization 15 ~ 60min, pour into then in the good mould of preheating, in 120 ℃ vacuum chamber; Vacuumize and remove bubble; Until there not being bubble to emerge, take out mould, put into air dry oven and carry out stage intensification curing; Curing process is 140 ℃/2h+160 ℃/2h+180 ℃/2h; Naturally cooling after the demoulding, promptly gets graphene oxide/cyanate ester resin composite material at 200 ℃ of following aftertreatment 2h more then.
Embodiment 2:
(1) preparation method of hyperbranched polyorganosiloxane modification graphene oxide is with embodiment 1.
(2) graphene oxide of 1 part of hyperbranched polyorganosiloxane being modified joins E-51 in 15 parts the epoxy active diluent, after 0.5 ~ 3 hour, joins 100 parts at ultra-sonic dispersion under the power of 40 ~ 70W in 80 ℃ of fused bisphenol A cyanate ester resin monomers; At 80 ~ 120 ℃ of following prepolymerization 15 ~ 60min, pour into then in the good mould of preheating, in 120 ℃ vacuum chamber; Vacuumize and remove bubble; Until there not being bubble to emerge, take out mould, put into air dry oven and carry out stage intensification curing; Curing process is 140 ℃/2h+160 ℃/2h+180 ℃/2h; Naturally cooling after the demoulding, promptly gets graphene oxide/cyanate ester resin composite material at 200 ℃ of following aftertreatment 2h more then.
Embodiment 3:
(1) preparation method of hyperbranched polyorganosiloxane modification graphene oxide is with embodiment 1.
(2) graphene oxide of 3 parts of hyperbranched polyorganosiloxanes being modified joins among 20 parts the epoxy active diluent E-44, after 0.5 ~ 3 hour, joins 100 parts at ultra-sonic dispersion under the power of 40 ~ 70W in 80 ℃ of fused bisphenol A cyanate ester resin monomers; At 80 ~ 120 ℃ of following prepolymerization 15 ~ 60min, pour into then in the good mould of preheating, in 120 ℃ vacuum chamber; Vacuumize and remove bubble; Until there not being bubble to emerge, take out mould, put into air dry oven and carry out stage intensification curing; Curing process is 140 ℃/2h+160 ℃/2h+180 ℃/2h; Naturally cooling after the demoulding, promptly gets graphene oxide/cyanate ester resin composite material at 200 ℃ of following aftertreatment 2h more then.
Embodiment 4:
(1) preparation method of hyperbranched polyorganosiloxane modification graphene oxide is with embodiment 1.
(2) graphene oxide of 5 parts of hyperbranched polyorganosiloxanes being modified joins among 30 parts the epoxy active diluent E-51, after 0.5 ~ 3 hour, joins 100 parts at ultra-sonic dispersion under the power of 40 ~ 70W in 80 ℃ of fused bisphenol A cyanate ester resin monomers; At 80 ~ 120 ℃ of following prepolymerization 15 ~ 60min, pour into then in the good mould of preheating, in 120 ℃ vacuum chamber; Vacuumize and remove bubble; Until there not being bubble to emerge, take out mould, put into air dry oven and carry out stage intensification curing; Curing process is 140 ℃/2h+160 ℃/2h+180 ℃/2h; Naturally cooling after the demoulding, promptly gets graphene oxide/cyanate ester resin composite material at 200 ℃ of following aftertreatment 2h more then.
Claims (3)
1. a graphene oxide/cyanate ester resin composite material is characterized in that the massfraction of material component is: 0.1 ~ 10 part of graphene oxide, 5 ~ 50 epoxy active diluents and 100 parts of bisphenol A cyanate ester resin monomer that hyperbranched polyorganosiloxane is modified; The chemical substance structure formula of the graphene oxide that said hyperbranched polyorganosiloxane is modified is:
The monomeric chemical substance structure formula of bisphenol A cyanate ester resin is:
2. graphene oxide/cyanate ester resin composite material according to claim 1 is characterized in that: said epoxy active diluent is E-44 or E-51.
3. method for preparing claim 1 or 2 said graphene oxide/cyanate ester resin composite materials is characterized in that step is following:
Step 1: 0.1 ~ 10 part graphite oxide is joined in the tetrahydrofuran solution of 1 ~ 100 part of KH-560; Dripping 1 ~ 50mL concentration behind the ultra-sonic dispersion 0.5h is the HCl aqueous solution of 1mol/L; Behind 50 ~ 80 ℃ of stirring 4 ~ 7h, obtain hyperbranched polyorganosiloxane and modify graphene oxide then;
Step 2: 0.1 ~ 10 part of hyperbranched polyorganosiloxane is modified in the epoxy active diluent that graphene oxide joins 5 ~ 50 parts; At ultra-sonic dispersion under the power of 40 ~ 70W after 0.5 ~ 3 hour; Join 100 parts in 80 ℃ of fused bisphenol A cyanate ester resin monomers, at 80 ~ 120 ℃ of following prepolymerization 15 ~ 60min;
Step 3: pour in the good mould of preheating; In 120 ℃ vacuum chamber, vacuumize except that taking out behind the bubble, put into air dry oven then and carry out stage intensification curing; Curing process is 140 ℃/2h+160 ℃/2h+180 ℃/2h; Naturally cooling after the demoulding, obtains graphene oxide/cyanate ester resin composite material at 200 ℃ of following aftertreatment 2h more then.
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