CN114685990A - Modified graphene/bismaleimide resin and preparation method thereof - Google Patents
Modified graphene/bismaleimide resin and preparation method thereof Download PDFInfo
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- CN114685990A CN114685990A CN202011639789.7A CN202011639789A CN114685990A CN 114685990 A CN114685990 A CN 114685990A CN 202011639789 A CN202011639789 A CN 202011639789A CN 114685990 A CN114685990 A CN 114685990A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 185
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 229920003192 poly(bis maleimide) Polymers 0.000 title claims abstract description 130
- 229920005989 resin Polymers 0.000 title claims abstract description 104
- 239000011347 resin Substances 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 48
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 22
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000005576 amination reaction Methods 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 12
- 239000004695 Polyether sulfone Substances 0.000 claims description 8
- -1 allylic phenolic organic compound Chemical class 0.000 claims description 8
- 229920006393 polyether sulfone Polymers 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000005416 organic matter Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000007872 degassing Methods 0.000 claims description 4
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 claims description 4
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical group C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229920006260 polyaryletherketone Polymers 0.000 claims description 3
- 229920001601 polyetherimide Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- 239000004697 Polyetherimide Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- FJKKJQRXSPFNPM-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)-4-methylphenyl]pyrrole-2,5-dione Chemical compound CC1=CC=C(N2C(C=CC2=O)=O)C=C1N1C(=O)C=CC1=O FJKKJQRXSPFNPM-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 30
- 238000003760 magnetic stirring Methods 0.000 description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000000805 composite resin Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000009210 therapy by ultrasound Methods 0.000 description 10
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
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- 230000009467 reduction Effects 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
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- 238000004108 freeze drying Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- 229910021641 deionized water Inorganic materials 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08L79/085—Unsaturated polyimide precursors
Abstract
The invention provides a modified graphene/bismaleimide resin and a preparation method thereof. The preparation method of the modified graphene/bismaleimide resin comprises the following steps: carrying out polymerization reaction on aminated graphene, allyl phenol organic matters, thermoplastic resin and bismaleimide monomer to obtain modified graphene/bismaleimide resin, wherein the weight ratio of the bismaleimide monomer to the aminated graphene to the allyl phenol organic matters to the thermoplastic resin is (50-100): (0.5-7): (35-75): (5-25). The preparation method of the modified graphene/bismaleimide resin prepared by the preparation method has good processability and excellent impact resistance.
Description
Technical Field
The invention relates to the field of organic resin synthesis, and particularly relates to a modified graphene/bismaleimide resin and a preparation method thereof.
Background
The bismaleimide has high strength and modulus, excellent high temperature resistance, humidity and heat resistance, radiation resistance, humidity and heat resistance, low moisture absorption, low thermal expansion coefficient, and the like, and is widely applied to the fields of aerospace, traffic and electronics. However, after the bismaleimide resin is cured, the crosslinking density is high, the molecular chain rigidity is high, and the defects of poor impact resistance, small elongation at break, low fracture toughness and the like are embodied, so that the development and the application of the bismaleimide resin are severely limited. Therefore, improving the molding manufacturability of bismaleimide resin and improving the toughness of cured products become the main research focus of bismaleimide resin.
The graphene is formed by sp carbon atoms2The hybridized and connected monoatomic layer is formed, and the basic structural unit of the hybridized and connected monoatomic layer is the most stable benzene six-membered ring in the organic material. The theoretical thickness of the graphene is 0.35nm, the graphene is the thinnest two-dimensional material discovered at present, and the special structure enables the graphene to show a plurality of excellent physicochemical properties. Researchers have done a great deal of work on the preparation of graphene, the electronic structural properties of graphene, and its application in microelectronic devices. Like most of nano materials, graphene has the problems of poor dispersion in resin, easy agglomeration and poor compatibility with resin when used for preparing resin matrix composite materials.
In view of the above problems, it is desirable to provide a modified graphene/bismaleimide resin capable of satisfying both of graphene modification with good moldability and high impact strength.
Disclosure of Invention
The invention mainly aims to provide a modified graphene/bismaleimide resin and a preparation method thereof, and aims to solve the problem that the existing bismaleimide resin cannot meet the requirements of good formability and high impact resistance at the same time.
In order to achieve the above object, one aspect of the present invention provides a method for preparing a modified graphene/bismaleimide resin, including: carrying out polymerization reaction on aminated graphene, allyl phenol organic matters, aminated graphene, thermoplastic resin and bismaleimide monomer to obtain modified graphene/bismaleimide resin, wherein the weight ratio of the bismaleimide monomer to the allyl phenol organic matters to the thermoplastic resin is (50-100): (0.5-7): (35-75): (5-25).
Further, the weight ratio of the bismaleimide monomer, the aminated graphene, the allyl phenolic organic compound and the thermoplastic resin is 100: (1-4): (50-75): (10-20).
Further, the bismaleimide monomer is selected from one or more of the group consisting of N, N ' -4,4' diphenylmethane bismaleimide, 2-methyl-1, 5, -bismaleimidobenzene and 2,2' -bis [4- (4-bismaleimidophenoxy) phenyl ] propane; the allyl phenol organic matter is selected from one or more of the group consisting of diallyl bisphenol A, diallyl bisphenol A ether, diallyl bisphenol S and allyl phenol; the thermoplastic resin is one or more selected from the group consisting of polyetherimide, polyimide, polyethersulfone and polyaryletherketone.
Further, the polymerization reaction comprises: mixing aminated graphene, allyl phenol organic matters, thermoplastic resin and an organic solvent to obtain a mixed solution; and injecting the mixed solution into a mold, degassing, and curing to obtain the modified graphene/bismaleimide resin.
Further, the curing process is divided into a first curing process, a second curing process and a third curing process, the curing temperature is 130-150 ℃, 170-180 ℃ and 200-220 ℃ in sequence, and the total curing time is 6-8 hours.
Further, the preparation method of the aminated graphite oxide comprises the following steps: carrying out amination reaction on graphene oxide and hydrazine hydrate in the presence of isoamyl nitrite and an alkaline reagent to obtain aminated graphene; preferably, the weight ratio of the graphene oxide to the hydrazine hydrate is 1 (0.5-0.7).
Further, the amination reaction time is 100-120 ℃, and the reaction time is 1-2 h.
Furthermore, the grafting rate of amino groups in the aminated graphene is 3-5 wt%.
The other aspect of the application also provides a modified graphene/bismaleimide resin, and the modified graphene/bismaleimide resin is prepared by the preparation method provided by the application.
Further, the impact strength of the modified graphene/bismaleimide resin is 23.5-32.7 KJ/m2。
By applying the technical scheme of the invention, the interface effect of the bismaleimide resin and the graphene can be greatly improved by carrying out amination modification on the graphene, and meanwhile, the dispersibility of the aminated carbon nanotube in the bismaleimide resin is improved. Meanwhile, the special nano toughening of graphene, the reduction of crosslinking density toughening by allyl phenols and the synergistic toughening effect among thermoplastic resin toughening are utilized, so that the processability of the bismaleimide resin is ensured, and the toughness of the bismaleimide resin is greatly improved. In conclusion, the preparation method of the modified graphene/bismaleimide resin prepared by the preparation method has good processability and excellent impact resistance.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 shows an infrared spectrum of aminated graphene obtained according to a preferred synthetic route of the present invention as shown in fig. 1.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background art, the conventional bismaleimide resin cannot satisfy both of the problems of good moldability and high impact resistance. In order to solve the above technical problems, the present application provides a method for preparing a modified graphene/bismaleimide resin, where the method for preparing the modified graphene/bismaleimide resin includes: carrying out polymerization reaction on aminated graphene, allyl phenol organic matters, thermoplastic resin and bismaleimide monomer to obtain modified graphene/bismaleimide resin, wherein the weight ratio of the bismaleimide monomer to the aminated graphene to the allyl phenol organic matters to the thermoplastic resin is (50-100): (0.5-7): (35-75): (5-25).
In the preparation method, the interface effect of the bismaleimide resin and the graphene can be greatly improved by carrying out amination modification on the graphene, and meanwhile, the dispersibility of the aminated carbon nanotube in the bismaleimide resin is improved. Meanwhile, the special nano toughening of graphene, the reduction of crosslinking density toughening by allyl phenols and the synergistic toughening effect among thermoplastic resin toughening are utilized, so that the toughness of the bismaleimide resin is greatly improved while the manufacturability of the bismaleimide resin is ensured. In conclusion, the preparation method of the modified graphene/bismaleimide resin prepared by the preparation method has good processability and excellent impact resistance.
In a preferred embodiment, the weight ratio of the bismaleimide monomer, the aminated graphene, the allylic phenolic organic compound and the thermoplastic resin is 100: (1-4): (50-75): (10-20). The weight ratio of the bismaleimide monomer, the aminated graphene, the allyl phenol organic matter and the thermoplastic resin can improve the matching performance of the bismaleimide monomer, the aminated graphene, the allyl phenol organic matter and the thermoplastic resin, so that the toughening effect of the three toughening components can be more fully exerted.
The bismaleimide monomer, the allyl phenol organic compound and the thermoplastic resin adopted in the preparation method can be selected from the types commonly used in the field.
In a preferred embodiment, bismaleimide monomers include, but are not limited to, one or more of the group consisting of N, N ' -4,4' diphenylmethane bismaleimide, 2-methyl-1, 5, -bismaleimidobenzene and 2,2' -bis [4- (4-bismaleimidophenoxy) phenyl ] propane. Compared with other bismaleimide monomers, the bismaleimide monomers have more excellent processing performance, so that the adoption of the components is beneficial to further improving the comprehensive performance of the modified graphene/bismaleimide resin.
In a preferred embodiment the allylic phenolic organic includes, but is not limited to, one or more of the group consisting of diallyl bisphenol a, diallyl bisphenol a ether, diallyl bisphenol S and allyl phenol. Compared with other types of allyl phenol organic matters, the allyl phenol organic matters can perform diene addition reaction with the bismaleimide resin, and improve the fluidity and the adhesiveness of the bismaleimide resin, so that the addition of the allyl phenol organic matters is beneficial to further reducing the crosslinking density of the modified graphene/bismaleimide resin, and is further beneficial to further improving the toughness of the modified graphene/bismaleimide resin.
In a preferred embodiment the thermoplastic resin comprises, but is not limited to, one or more of the group consisting of polyetherimides, polyimides, polyethersulphones and polyaryletherketones. Compared with other thermoplastic resins, the thermoplastic resins have better toughness, so that the thermoplastic resins are favorable for further improving the toughness of the modified graphene/bismaleimide resin.
The graphene oxide and the aminated graphene used in the preparation method can be commercially available products or can be prepared by self.
In a preferred embodiment, the graphene oxide is prepared by the following method: under the condition of ice bath, 360ml of concentrated sulfuric acid, 40ml of nitric acid and 3g of graphite powder are added into a flask, 18g of potassium permanganate is slowly added by a small spoon, and then the temperature is raised to 60 ℃ for reaction for 12 hours. Slowly pouring the reacted solution into 400ml of ice water, stirring vigorously for 15min, and then adding hydrogen peroxide until the color of the solution becomes bright yellow. And centrifuging the obtained solution, washing the solution with ethanol, hydrochloric acid and distilled water for three times, and freeze-drying the obtained brown solid to obtain the graphene oxide.
There are many methods for amination of graphene oxide, including but not limited to: carrying out amination reaction on graphene oxide and hydrazine hydrate in the presence of a catalyst and an amination reagent to obtain aminated graphene. Preferably, before the amination reaction, the preparation method of the aminated graphite oxide further comprises: and dispersing graphene oxide in water to prepare graphene oxide suspension with the concentration of 2 mg/ml. Preferably, the catalyst includes, but is not limited to, isoamyl nitrite; amination agents include, but are not limited to, ethylenediamine.
One preferred route for amination of graphene oxide is:
In order to improve the amination degree and reaction rate of the graphene oxide, the weight ratio of the graphene oxide to the hydrazine hydrate is preferably 1 (0.5-0.7), and the dosage ratio of the graphene oxide to the ethylenediamine and the catalyst is preferably 100mg:0.001mol:0.002 mol.
In a preferred embodiment, the temperature of the amination reaction is 100 to 120 ℃, and the reaction time is 1 to 10 hours. The temperature and time of the amination reaction include, but are not limited to, the above range, and the limitation thereof is favorable for reducing the formation of by-products, thereby further improving the yield of the aminated product. In order to further improve the interfacial action between the aminated graphene and the bismaleimide resin and the dispersibility of the aminated graphene in the bismaleimide resin, it is more preferable that the grafting ratio of the amino group in the aminated graphene is 0.5 to 3 wt%.
In a preferred embodiment, the polymerization reaction comprises: mixing aminated graphene, allyl phenol organic matters, thermoplastic resin and an organic solvent to obtain a mixed solution; and injecting the mixed solution into a mold, degassing, and curing to obtain the modified graphene/bismaleimide resin. The degassing treatment (preferably vacuum degassing) can reduce the proportion of pores in the modified graphene/bismaleimide resin prepared after curing, so that the impact resistance of the modified graphene/bismaleimide resin is greatly improved.
In a preferred embodiment, the curing process is divided into a first curing process, a second curing process and a third curing process, the curing temperature is 130-150 ℃, 170-180 ℃ and 200-220 ℃ in sequence, and the total curing time is 6-8 h. The adoption of the staged curing mode is beneficial to improving the curing degree of the modified graphene/bismaleimide resin, so that the comprehensive performance of the modified graphene/bismaleimide resin is further improved.
The other aspect of the application also provides a modified graphene/bismaleimide resin, and the modified graphene/bismaleimide resin is prepared by the preparation method provided by the application.
In the preparation method, the interface effect of the bismaleimide resin and the graphene can be greatly improved by carrying out amination modification on the graphene, and meanwhile, the dispersibility of the aminated carbon nanotube in the bismaleimide resin is improved. Meanwhile, the special nano toughening of graphene, the reduction of crosslinking density toughening by allyl phenols and the synergistic toughening effect among thermoplastic resin toughening are utilized, so that the processability of the bismaleimide resin is ensured, and the toughness of the bismaleimide resin is greatly improved. In conclusion, the preparation method of the modified graphene/bismaleimide resin prepared by the preparation method has good processability and excellent impact resistance.
In order to further improve the comprehensive performance of the modified graphene/bismaleimide resin, the impact strength of the modified graphene/bismaleimide resin is preferably 23.5-32.7 KJ/m2。
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
A preparation method of the modified graphene/bismaleimide resin comprises the following steps:
(1) preparation of graphene oxide
Under the condition of ice bath, 360ml of concentrated sulfuric acid, 40ml of nitric acid and 3g of graphite powder are added into a flask, 18g of potassium permanganate is slowly added by a small spoon, and then the temperature is raised to 60 ℃ for reaction for 12 hours. Slowly pouring the reacted solution into 400ml of ice water, stirring vigorously for 15min, and then adding hydrogen peroxide until the color of the solution becomes bright yellow. And centrifuging the obtained solution, washing the solution with ethanol, hydrochloric acid and distilled water for three times, and freeze-drying the obtained brown solid to obtain the graphene oxide.
(2) Preparation of aminated graphene
And (3) dispersing the graphene oxide obtained in the step (1) in water, wherein the concentration is 2mg/ml, so as to obtain a graphene oxide suspension. According to the proportion of 200mg of graphene oxide solution and 1ml of hydrazine hydrate (50 wt%), after reacting for 1h at 100 ℃, reducing the temperature to 80 ℃, adding 0.002mol of ethylenediamine and 0.004mol of isoamyl nitrite into every 200mg of graphene oxide, after reacting for 10h, reducing the temperature to room temperature, washing with deionized water and tetrahydrofuran, and storing in tetrahydrofuran solution.
(3) Preparation of modified graphene/bismaleimide resin
Adding 75g of diallyl bisphenol A into a modified graphene tetrahydrofuran solution (containing 980mg of modified graphene), carrying out ultrasonic treatment for 1-2 h under an ultrasonic crusher, then carrying out magnetic stirring, adding 20g of thermoplastic resin (polyether sulfone) at 140 ℃, reducing the temperature to 120 ℃ after the thermoplastic resin is completely mixed, adding 100g N, N '-4,4' diphenylmethane bismaleimide under the magnetic stirring, and continuing to carry out magnetic stirring and stirring for 0.5h at 120 ℃ after the solution is clarified. And pouring the mixed liquid into a prepared mould, and vacuumizing a vacuum oven for 15-30 min at the temperature of 150 ℃. Then, curing the mixture according to a curing mode of 150 ℃ for 1h, 180 ℃ for 1h and 200 ℃ for 3h, cooling the mixture to room temperature, taking out the mixture, and demolding the mixture to obtain the modified graphene/bismaleimide resin composite material meeting the requirements, wherein the mass fraction of the graphene in the bismaleimide resin is 0.5 wt%;
example 2
A preparation method of the modified graphene/bismaleimide resin comprises the following steps:
the differences from example 1 are: the modified graphene/bismaleimide resin was prepared as follows:
adding 75g of diallyl bisphenol A into a modified graphene tetrahydrofuran solution (containing 1970mg of modified graphene), carrying out ultrasonic treatment for 1-2 h under an ultrasonic crusher, then carrying out magnetic stirring, adding 20g of thermoplastic resin (polyether sulfone) at 140 ℃, reducing the temperature to 120 ℃ after the thermoplastic resin is completely mixed, adding 100g N, N '-4,4' diphenylmethane bismaleimide under the magnetic stirring, and continuing to carry out magnetic stirring and stirring for 0.5h at 120 ℃ after the solution is clarified. And pouring the mixed liquid into a prepared mould, and vacuumizing a vacuum oven for 15-30 min at the temperature of 150 ℃. And then, curing according to a curing mode of 150 ℃ for 1h, 180 ℃ for 1h and 200 ℃ for 3h, cooling to room temperature, taking out, and demolding to obtain the modified graphene/bismaleimide resin composite material meeting the requirements, wherein the mass fraction of the graphene in the bismaleimide resin is 1 wt%.
Example 3
The differences from example 1 are: the modified graphene/bismaleimide resin was prepared as follows:
adding 75g of diallyl bisphenol A into a modified graphene tetrahydrofuran solution (containing 3980mg of modified graphene), performing ultrasonic treatment for 1-2 h under an ultrasonic crusher, then performing magnetic stirring, adding 20g of thermoplastic resin (polyether sulfone) at 140 ℃, reducing the temperature to 120 ℃ after the thermoplastic resin is completely mixed, adding 100g N, N '-4,4' diphenylmethane bismaleimide under the magnetic stirring, and continuing to perform magnetic stirring and stirring for 0.5h at 120 ℃ after the solution is clarified. And pouring the mixed liquid into a prepared mould, and vacuumizing a vacuum oven for 15-30 min at the temperature of 150 ℃. And then, curing according to a curing mode of 150 ℃ for 1h, 180 ℃ for 1h and 200 ℃ for 3h, cooling to room temperature, taking out, and demolding to obtain the modified graphene/bismaleimide resin composite material meeting the requirements, wherein the mass fraction of the graphene in the bismaleimide resin is 2 wt%.
Example 4
The differences from example 1 are: the modified graphene/bismaleimide resin was prepared as follows:
adding 75g of diallyl bisphenol A into a modified graphene tetrahydrofuran solution (containing 6030mg of modified graphene), carrying out ultrasonic treatment for 1-2 h under an ultrasonic crusher, then carrying out magnetic stirring, adding 20g of thermoplastic resin (polyether sulfone) at 140 ℃, reducing the temperature to 120 ℃ after the thermoplastic resin is completely mixed, adding 100g N, N '-4,4' diphenylmethane bismaleimide under the magnetic stirring, and continuing to stir for 0.5h at 120 ℃ after the solution is clarified. And pouring the mixed liquid into a prepared mould, and vacuumizing a vacuum oven for 15-30 min at the temperature of 150 ℃. And then, curing according to a curing mode of 150 ℃ for 1h, 180 ℃ for 1h and 200 ℃ for 3h, cooling to room temperature, taking out, and demolding to obtain the modified graphene/bismaleimide resin composite material meeting the requirements, wherein the mass fraction of the graphene in the bismaleimide resin is 3 wt%.
Example 5
The differences from example 1 are: the preparation process of the modified graphene/bismaleimide resin is as follows:
adding 35g of diallyl bisphenol A into a modified graphene tetrahydrofuran solution (containing 980mg of modified graphene), carrying out ultrasonic treatment for 1-2 h under an ultrasonic crusher, then carrying out magnetic stirring, adding 20g of thermoplastic resin at 140 ℃, reducing the temperature to 120 ℃ after the thermoplastic resin is completely mixed, adding 100g N, N '-4,4' diphenylmethane bismaleimide under the magnetic stirring, and continuing to carry out magnetic stirring and stirring at 120 ℃ for 0.5h after the solution is clarified. And pouring the mixed liquid into a prepared mould, and vacuumizing a vacuum oven for 15-30 min at the temperature of 150 ℃. And then, curing according to a curing mode of 150 ℃ for 1h, 180 ℃ for 1h and 200 ℃ for 3h, cooling to room temperature, taking out, and demolding to obtain the modified graphene/bismaleimide resin composite material meeting the requirements, wherein the mass fraction of the graphene in the bismaleimide resin is 0.5 wt%.
Example 6
The differences from example 1 are:
adding 35g of diallyl bisphenol A into a modified graphene tetrahydrofuran solution (containing 1616mg of modified graphene), carrying out ultrasonic treatment for 1-2 h under an ultrasonic crusher, then carrying out magnetic stirring, adding 25g of thermoplastic resin (polyether sulfone) at 140 ℃, reducing the temperature to 120 ℃ after the thermoplastic resin is completely mixed, adding 100g N, N '-4,4' diphenylmethane bismaleimide under the magnetic stirring, and continuing to stir for 0.5h at 120 ℃ after the solution is clarified. And pouring the mixed liquid into a prepared mould, and vacuumizing a vacuum oven for 15-30 min at the temperature of 150 ℃. And then, curing according to a curing mode of 150 ℃ for 1h, 180 ℃ for 1h and 200 ℃ for 3h, cooling to room temperature, taking out, and demolding to obtain the modified graphene/bismaleimide resin composite material meeting the requirements, wherein the mass fraction of the graphene in the bismaleimide resin is 1 wt%.
Example 7
The differences from example 1 are:
adding 75g of diallyl bisphenol A into a modified graphene tetrahydrofuran solution (containing 1616mg of modified graphene), performing ultrasonic treatment for 1-2 h under an ultrasonic crusher, then performing magnetic stirring, adding 5g of thermoplastic resin (polyether sulfone) at 140 ℃, reducing the temperature to 120 ℃ after the thermoplastic resin is completely mixed, adding 100g N, N '-4,4' diphenylmethane bismaleimide under the magnetic stirring, and continuing to perform magnetic stirring and stirring for 0.5h at 120 ℃ after the solution is clarified. And pouring the mixed liquid into a prepared mould, and vacuumizing a vacuum oven for 15-30 min at the temperature of 150 ℃. And then, curing according to a curing mode of 150 ℃ for 1h, 180 ℃ for 1h and 200 ℃ for 3h, cooling to room temperature, taking out, and demolding to obtain the modified graphene/bismaleimide resin composite material meeting the requirements, wherein the mass fraction of the graphene in the bismaleimide resin is 1 wt%.
Comparative example 1
The differences from example 3 are: in the preparation process of the modified graphene/bismaleimide resin, the oxidized graphene prepared in the step (1) is used for replacing aminated graphene.
Comparative example 2
The differences from example 3 are: in the preparation process of the modified graphene/bismaleimide resin, no graphene oxide is added, and no aminated graphene is added.
Comparative example 3
The differences from example 3 are: during the preparation of the bismaleimide resin, graphene oxide, aminated graphene, thermoplastic resin and diallyl bisphenol A are not available, namely the conventional bismaleimide resin.
Comparative example 4
The differences from example 1 are: the preparation process of the modified graphene/bismaleimide resin comprises the following steps:
adding 20g of diallyl bisphenol A into a modified graphene tetrahydrofuran solution (containing 980mg of modified graphene), carrying out ultrasonic treatment for 1-2 h under an ultrasonic crusher, then carrying out magnetic stirring, adding 40g of thermoplastic resin at 140 ℃, reducing the temperature to 120 ℃ after the thermoplastic resin is completely mixed, adding 100g N, N '-4,4' diphenylmethane bismaleimide under the magnetic stirring, and continuing to carry out magnetic stirring and stirring for 0.5h at 120 ℃ after the solution is clarified. And pouring the mixed liquid into a prepared mould, and vacuumizing a vacuum oven for 15-30 min at the temperature of 150 ℃. And then, curing according to a curing mode of 150 ℃ for 1h, 180 ℃ for 1h and 200 ℃ for 3h, cooling to room temperature, taking out, and demolding to obtain the modified graphene/bismaleimide resin composite material meeting the requirements, wherein the mass fraction of the graphene in the bismaleimide resin is 0.5 wt%.
Comparative example 5
The differences from example 1 are: the preparation process of the modified graphene/bismaleimide resin is as follows:
adding 75g of diallyl bisphenol A into a modified graphene tetrahydrofuran solution (containing 980mg of modified graphene), carrying out ultrasonic treatment for 1-2 h under an ultrasonic crusher, then carrying out magnetic stirring, adding 2g of thermoplastic resin at 140 ℃, reducing the temperature to 120 ℃ after the thermoplastic resin is completely mixed, adding 100g N, N '-4,4' diphenylmethane bismaleimide under the magnetic stirring, and continuing to carry out magnetic stirring and stirring for 0.5h at 120 ℃ after the solution is clarified. And pouring the mixed liquid into a prepared mould, and vacuumizing a vacuum oven for 15-30 min at the temperature of 150 ℃. And then curing according to a curing mode of 1h at 150 ℃, 1h at 180 ℃ and 3h at 200 ℃, cooling to room temperature, taking out, and demolding to obtain the modified graphene/bismaleimide resin composite material meeting the requirement, wherein the mass fraction of the graphene in the bismaleimide resin is 0.5 wt%.
Comparative example 6
The differences from example 1 are: the preparation process of the modified graphene/bismaleimide resin is as follows:
adding 75g of diallyl bisphenol A into a modified graphene tetrahydrofuran solution (containing 980mg of modified graphene), carrying out ultrasonic treatment for 1-2 h under an ultrasonic crusher, then carrying out magnetic stirring, adding 40g of thermoplastic resin at 140 ℃, reducing the temperature to 120 ℃ after the thermoplastic resin is completely mixed, adding 100g N, N '-4,4' diphenylmethane bismaleimide under the magnetic stirring, and continuing to carry out magnetic stirring and stirring for 0.5h at 120 ℃ after the solution is clarified. And pouring the mixed liquid into a prepared mould, and vacuumizing a vacuum oven for 15-30 min at the temperature of 150 ℃. And then, curing according to a curing mode of 150 ℃ for 1h, 180 ℃ for 1h and 200 ℃ for 3h, cooling to room temperature, taking out, and demolding to obtain the modified graphene/bismaleimide resin composite material meeting the requirements, wherein the mass fraction of the graphene in the bismaleimide resin is 0.5 wt%.
The impact strength of the bismaleimide resins prepared in examples and comparative examples was tested according to GB/T2567. The test results are shown in Table 1.
TABLE 1
| Serial number | Impact strength (KJ/m)2) |
| Example 1 | 23.5 |
| Example 2 | 27.8 |
| Example 3 | 32.7 |
| Example 4 | 31.6 |
| Example 5 | 22.7 |
| Example 6 | 23.2 |
| Example 7 | 22.1 |
| Comparative example 1 | 19.2 |
| Comparative example 2 | 16.2 |
| Comparative example 3 | 9.2 |
| Comparative example 4 | 19.2 |
| Comparative example 5 | 19.1 |
| Comparative example 6 | 22.9 |
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: by carrying out amination modification on graphene, the interface effect of bismaleimide resin and graphene can be greatly improved, and the dispersibility of aminated carbon nanotubes in the bismaleimide resin is improved. Meanwhile, the special nano toughening of graphene, the reduction of crosslinking density toughening by allyl phenols and the synergistic toughening effect among thermoplastic resin toughening are utilized, so that the processability of the bismaleimide resin is ensured, and the toughness of the bismaleimide resin is greatly improved. In conclusion, the preparation method of the modified graphene/bismaleimide resin prepared by the preparation method has good processability and excellent impact resistance.
It is noted that the terms first, second and the like in the description and in the claims of the present application are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments of the application described herein are, for example, capable of operation in sequences other than those described or illustrated herein.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a modified graphene/bismaleimide resin is characterized by comprising the following steps:
carrying out polymerization reaction on aminated graphene, allyl phenol organic matter, thermoplastic resin and bismaleimide monomer to obtain the modified graphene/bismaleimide resin, wherein the weight ratio of the bismaleimide monomer to the aminated graphene to the allyl phenol organic matter to the thermoplastic resin is (50-100): (0.5-7):
(35～75)：(5～25)。
2. the method for preparing the modified graphene/bismaleimide resin according to claim 1, wherein a weight ratio of the bismaleimide monomer, the aminated graphene, the allylic phenolic organic compound, and the thermoplastic resin is 100: (1-4): (50-75): (10-20).
3. The method of preparing a modified graphene/bismaleimide resin according to claim 1 or 2, wherein the bismaleimide monomer is one or more selected from the group consisting of N, N ' -4,4' diphenylmethane bismaleimide, 2-methyl-1, 5-bismaleimidobenzene, and 2,2' -bis [4- (4-bismaleimidophenoxy) phenyl ] propane;
the allyl phenol organic matter is selected from one or more of the group consisting of diallyl bisphenol A, diallyl bisphenol A ether, diallyl bisphenol S and allyl phenol;
the thermoplastic resin is selected from one or more of the group consisting of polyetherimide, polyimide, polyethersulfone and polyaryletherketone.
4. The method of preparing the modified graphene/bismaleimide resin of claim 1, wherein the polymerization reaction comprises:
mixing the aminated graphene, allyl phenol organic matters, thermoplastic resin and an organic solvent to obtain a mixed solution;
and injecting the mixed solution into a mold, degassing, and curing to obtain the modified graphene/bismaleimide resin.
5. The method for preparing the modified graphene/bismaleimide resin according to any one of claims 1 to 4, wherein the curing process is divided into a first curing process, a second curing process and a third curing process, and the curing temperature is 130 to 150 ℃, 170 to 180 ℃ and 200 to 220 ℃ in sequence, and the total curing time is 6 to 8 hours.
6. The method for producing a modified graphene/bismaleimide resin according to any one of claims 1 to 3, wherein the method for producing an aminated graphite oxide comprises:
carrying out amination reaction on graphene oxide and hydrazine hydrate in the presence of isoamyl nitrite and an alkaline reagent to obtain aminated graphene;
preferably, the weight ratio of the graphene oxide to the hydrazine hydrate is 1 (0.5-0.7).
7. The preparation method of the modified graphene/bismaleimide resin according to claim 6, wherein the amination reaction time is 100-120 ℃ and the reaction time is 1-2 hours.
8. The method for preparing the modified graphene/bismaleimide resin according to any one of claims 1 to 3, wherein a grafting ratio of amino groups in the aminated graphene is 3 to 5 wt%.
9. A modified graphene/bismaleimide resin, wherein the modified graphene/bismaleimide resin is prepared by the preparation method of any one of claims 1 to 8.
10. The modified graphene/bismaleimide resin according to claim 9, wherein the impact strength of the modified graphene/bismaleimide resin is 23.5-32.7 KJ/m2。
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