CN104448704A - Preparation method of high-toughness carboxylated graphene-epoxy resin composite material - Google Patents
Preparation method of high-toughness carboxylated graphene-epoxy resin composite material Download PDFInfo
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Abstract
The invention belongs to the technical field of preparation of graphene and epoxy resin, and relates to a preparation method of a high-toughness carboxylated graphene-epoxy resin composite material. The preparation method is characterized by comprising the following preparation steps: preparing carboxylated graphene powder; mutually dissolving epoxy resin and a curing agent; adding carboxylated graphene; adding a promoter; performing vacuum gas pumping; and heating and curing. By adopting the preparation method of the high-toughness carboxylated graphene-epoxy resin composite material disclosed by the invention, the defects that graphene oxide is complex in structure and poor in dispersibility in epoxy resin caused by adopting graphene oxide microspheres as an enhancement phase can be overcome, and the quality and stability of the composite material can be improved.
Description
Technical field
The invention belongs to the preparing technical field of Graphene and epoxy resin, relate to the preparation method of the carboxylated graphene-epoxy resin composite material of a kind of high tenacity.
Background technology
Epoxy resin is a kind of very important thermosetting resin, there is excellent mechanical property, electrical insulation capability, chemical stability, thermotolerance, and low, the easy machine-shaping of shrinking percentage, preferably Stress transmit and the advantage such as with low cost, be widely used in the fields such as aerospace, building machinery, electronic instrument, light industry, electric insulating material, advanced composite material matrix.But too high owing to solidifying rear cross-linking density, pure epoxy resin cured article exists the shortcomings such as internal stress is large, matter is crisp, and fracture toughness property, resistance to cracking are poor, greatly limit its application in engineering.At present, the Research on Toughening of epoxy resin has achieved some achievements, and main toughness reinforcing approach has: add rubber elastomer, thermoplastic resin or thermotropic liquid crystal in the epoxy and carry out toughening modifying; In epoxy networks, toughening modifying is carried out to form Semi-IPN or complete interpenetrating net polymer with thermoplastics etc.; The mobility of molecular network interchain is improved, the toughness of strongthener by the chemical structure changing cross-linked network.Publication number is that the Chinese patent application " a kind of graphene oxide microballoon/epoxy resin composite material and preparation method thereof " of CN103232681A discloses and adopts graphene oxide microballoon to strengthen epoxy resin-base as wild phase, its shortcoming is: graphene oxide complex structure, the a small amount of hydroxyl of load on Graphene, a small amount of epoxy group(ing), a small amount of carboxyl, and only have carboxyl can and polymerization of epoxy resins, therefore graphene oxide makes wild phase bad dispersibility in the epoxy, cause graphene oxide microballoon/epoxy resin composite material unstable properties, of low quality.
Summary of the invention
The object of the invention is: the preparation method proposing the carboxylated graphene-epoxy resin composite material of a kind of high tenacity, to overcome the shortcoming adopting graphene oxide microballoon as the graphene oxide complex structure, the in the epoxy bad dispersibility that produce during wild phase, improve quality and the stability of matrix material.
Technical scheme of the present invention is: the preparation method of the carboxylated graphene-epoxy resin composite material of high tenacity, is characterized in that, the step of preparation is as follows:
1, carboxylated graphene powder is prepared:
1.1, graphene oxide suspension is prepared: by graphene oxide ultrasonication in distilled water, ultrasonic power is 600W ~ 900W, the ultrasonication time is 30min ~ 60min, obtains finely dispersed graphene oxide suspension, and graphene oxide suspension concentration is 1g/L ~ 3g/L;
1.2, prepare Graphene turbid solution: in graphene oxide suspension, add reductive agent hydrazine hydrate, the mass ratio of graphene oxide and hydrazine hydrate is 1:1 ~ 2, and condensing reflux 24h ~ 48h in the oil bath of 85 DEG C ~ 95 DEG C, obtains Graphene turbid solution;
1.3, prepare the presoma turbid solution of carboxylated Graphene: Graphene turbid solution is cooled to 70 DEG C ~ 80 DEG C, add the alcoholic solution of aminophenyl acid and Isopentyl nitrite, aminophenyl acid is aminophenyl formic acid or aminophenyl acetic acid, the concentration of the alcoholic solution of Isopentyl nitrite is 0.2g/ml, alcohol is methyl alcohol or ethanol, aminophenyl acid is 1 ~ 10:10 with the mol ratio of graphene oxide, the mol ratio of Isopentyl nitrite and aminophenyl acid is 1 ~ 2:1, then highly basic is added, highly basic is potassium hydroxide or sodium hydroxide, the mol ratio of potassium hydroxide or sodium hydroxide and aminophenyl acid is 1.2 ~ 1.5:1, condensing reflux 24h ~ 48h in the oil bath of 70 DEG C ~ 80 DEG C, obtain the presoma turbid solution of carboxylated Graphene,
1.4, prepare acidic carboxypolymer functionalized graphene turbid solution: the presoma turbid solution presoma turbid solution strong acid of Graphene adjustment PH to 5 ~ 6 being obtained acidic graphite alkene, strong acid is hydrochloric acid or sulfuric acid;
1.5, moisture carboxylated Graphene is prepared: PH to 6 ~ 7 are filtered in the solid matter deionized water drip washing in acidic carboxypolymer functionalized graphene turbid solution, obtains moisture carboxylated Graphene;
1.6, carboxylated graphene powder is prepared: by moisture carboxylated Graphene lyophilize 5 days ~ 7 days, lyophilize temperature rose to 20 DEG C gradually from-40 DEG C, obtains carboxylated graphene powder;
2, epoxy resin and solidifying agent dissolve each other: epoxy resin and solidifying agent being stirred in a heated condition becomes the body that dissolves each other, epoxy resin is cycloaliphatic epoxy resin, solidifying agent is acid anhydride type curing agent, the mass ratio of epoxy resin and solidifying agent is 1:1.3 ~ 1.4, Heating temperature is 40 DEG C ~ 60 DEG C, and churning time is 0.5h ~ 1.5h;
3, carboxylated Graphene is added: in the body that dissolves each other of epoxy resin and solidifying agent, add carboxylated Graphene, carry out under normal temperature stirring and supersound process, obtain carboxylated Graphene-epoxy resin first mixed solution, the mass ratio of carboxylated Graphene and epoxy resin is 0.5 ~ 3:100, churning time is 10min ~ 20min, and sonication treatment time is 10min ~ 20min;
4, promotor is added: add promotor to carboxylated Graphene-epoxy resin mixed solution, Graphene-epoxy resin second mixed solution is obtained after stirring, promotor is phenol accelerant, and the mass ratio of promotor and epoxy resin is 0.1 ~ 0.5:100, and churning time is 10min ~ 20min;
5, vacuum suction: Graphene-epoxy resin second mixed solution is put into vacuum chamber and carries out vacuum suction, vacuum suction temperature is 30 DEG C ~ 50 DEG C, and the vacuum tightness in vacuum chamber is 0.1MPa, and vacuum pumpdown time is 40min ~ 60min;
6, elevated cure: Graphene-epoxy resin second mixed solution is poured in mould, elevated cure in an oven, temperature-rising method is: be warmed up to 110 DEG C of insulation 2h and carry out Procuring, be warmed up to 140 DEG C of insulation 2h again and carry out first stage solidification, be warmed up to 170 DEG C of insulation 3h again and carry out subordinate phase solidification, be warmed up to 200 DEG C of insulation 2h again and carry out phase III solidification, room temperature cools, and obtains the carboxylated graphene-epoxy resin composite material of high tenacity.
Advantage of the present invention is: the preparation method proposing the carboxylated graphene-epoxy resin composite material of a kind of high tenacity, overcome the shortcoming that graphene oxide microballoon can be adopted as the graphene oxide complex structure, the in the epoxy bad dispersibility that produce during wild phase, improve quality and the stability of matrix material.The present invention adopts carboxylated Graphene as wild phase, carboxyl on carboxylated Graphene and epoxy resin ring-opening polymerization, Graphene is made to be embedded in fine and close epoxy networks with the form of chemical bond, the crack propagation of epoxy resin is played and terminates closed effect, thus form stable, the measured matrix material of matter.
Accompanying drawing explanation
Fig. 1 is the Fracture scan figure in embodiment 1.
Fig. 2 is the Fracture scan figure of embodiment 3.
Fig. 3 is the Fracture scan figure of embodiment 6.
Embodiment
Below the present invention is described in further details.The preparation method of the carboxylated graphene-epoxy resin composite material of high tenacity, is characterized in that, the step of preparation is as follows:
1, carboxylated graphene powder is prepared:
1.1, graphene oxide suspension is prepared: by graphene oxide ultrasonication in distilled water, ultrasonic power is 600W ~ 900W, the ultrasonication time is 30min ~ 60min, obtains finely dispersed graphene oxide suspension, and graphene oxide suspension concentration is 1g/L ~ 3g/L;
1.2, prepare Graphene turbid solution: in graphene oxide suspension, add reductive agent hydrazine hydrate, the mass ratio of graphene oxide and hydrazine hydrate is 1:1 ~ 2, and condensing reflux 24h ~ 48h in the oil bath of 85 DEG C ~ 95 DEG C, obtains Graphene turbid solution;
1.3, prepare the presoma turbid solution of carboxylated Graphene: Graphene turbid solution is cooled to 70 DEG C ~ 80 DEG C, add the alcoholic solution of aminophenyl acid and Isopentyl nitrite, aminophenyl acid is aminophenyl formic acid or aminophenyl acetic acid, the concentration of the alcoholic solution of Isopentyl nitrite is 0.2g/ml, alcohol is methyl alcohol or ethanol, aminophenyl acid is 1 ~ 10:10 with the mol ratio of graphene oxide, the mol ratio of Isopentyl nitrite and aminophenyl acid is 1 ~ 2:1, then highly basic is added, highly basic is potassium hydroxide or sodium hydroxide, the mol ratio of potassium hydroxide or sodium hydroxide and aminophenyl acid is 1.2 ~ 1.5:1, condensing reflux 24h ~ 48h in the oil bath of 70 DEG C ~ 80 DEG C, obtain the presoma turbid solution of carboxylated Graphene,
1.4, prepare acidic carboxypolymer functionalized graphene turbid solution: the presoma turbid solution presoma turbid solution strong acid of Graphene adjustment PH to 5 ~ 6 being obtained acidic graphite alkene, strong acid is hydrochloric acid or sulfuric acid;
1.5, moisture carboxylated Graphene is prepared: PH to 6 ~ 7 are filtered in the solid matter deionized water drip washing in acidic carboxypolymer functionalized graphene turbid solution, obtains moisture carboxylated Graphene;
1.6, carboxylated graphene powder is prepared: by moisture carboxylated Graphene lyophilize 5 days ~ 7 days, lyophilize temperature rose to 20 DEG C gradually from-40 DEG C, obtains carboxylated graphene powder;
2, epoxy resin and solidifying agent dissolve each other: epoxy resin and solidifying agent being stirred in a heated condition becomes the body that dissolves each other, epoxy resin is cycloaliphatic epoxy resin, solidifying agent is acid anhydride type curing agent, the mass ratio of epoxy resin and solidifying agent is 1:1.3 ~ 1.4, Heating temperature is 40 DEG C ~ 60 DEG C, and churning time is 0.5h ~ 1.5h;
3, carboxylated Graphene is added: in the body that dissolves each other of epoxy resin and solidifying agent, add carboxylated Graphene, carry out under normal temperature stirring and supersound process, obtain carboxylated Graphene-epoxy resin first mixed solution, the mass ratio of carboxylated Graphene and epoxy resin is 0.5 ~ 3:100, churning time is 10min ~ 20min, and sonication treatment time is 10min ~ 20min;
4, promotor is added: add promotor to carboxylated Graphene-epoxy resin mixed solution, Graphene-epoxy resin second mixed solution is obtained after stirring, promotor is phenol accelerant, and the mass ratio of promotor and epoxy resin is 0.1 ~ 0.5:100, and churning time is 10min ~ 20min;
5, vacuum suction: Graphene-epoxy resin second mixed solution is put into vacuum chamber and carries out vacuum suction, vacuum suction temperature is 30 DEG C ~ 50 DEG C, and the vacuum tightness in vacuum drying oven is 0.1MPa, and vacuum tightness keeps the pumpdown time of 0.1MPa to be 40min ~ 60min;
6, elevated cure: Graphene-epoxy resin second mixed solution is poured in mould, elevated cure in an oven, temperature-rising method is: be warmed up to 110 DEG C of insulation 2h and carry out Procuring, be warmed up to 140 DEG C of insulation 2h again and carry out first stage solidification, be warmed up to 170 DEG C of insulation 3h again and carry out subordinate phase solidification, be warmed up to 200 DEG C of insulation 2h again and carry out phase III solidification, room temperature cools, and obtains the carboxylated graphene-epoxy resin composite material of high tenacity.
In order to ensure the carboxylated graphene-epoxy resin composite material of the toughness of obtained high-quality, in preparation graphene oxide suspension step, described graphene oxide is prepared by oxidation reduction process, and graphene oxide lamellar spacing is between 0.5nm ~ 2nm.
Embodiment 1
Getting 1L concentration is 1g/L graphene oxide solution, and graphene oxide lamellar spacing is between 0.5nm ~ 2nm, and ultrasonic power is 600W, and the ultrasonication time is 30min, obtains graphene oxide suspension; In graphene oxide suspension, add 1.5g hydrazine hydrate, in 85 DEG C of oil baths, condensing reflux 24h, obtains Graphene turbid solution; Graphene turbid solution is cooled to 70 DEG C, in Graphene turbid solution, add 3g aminophenyl formic acid, the concentration of 12.5mL is the ethanolic soln of 0.2g/mL Isopentyl nitrite, 0.832g sodium hydroxide, at 70 DEG C of condensing reflux 24h, obtain the presoma turbid solution of carboxylated Graphene; Adjusting PH with hydrochloric acid is 5 ~ 6 presoma turbid solutions obtaining acidic graphite alkene; The presoma turbid solution drip washing of acidic graphite alkene filtered, being adjusted to PH is 6 ~ 7; Lyophilize 5 days, obtains carboxylated graphene powder.Take 20g3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexyl manthanoate and 26g 4-methyl hexahydrophthalic anhydride put into beaker, and Heating temperature is 40 DEG C, and churning time is 1.5h, make the two dissolve each other completely.Then the carboxylated graphene powder of 0.1g is added, under normal temperature, churning time is 10min, sonication treatment time is that 20min is to dissolution homogeneity, gained solution is cooled to room temperature, add 0.02g2, 4, 6-tri-(dimethylamino methyl) phenol stirs 10min, be placed in vacuum drying oven, vacuum suction temperature is 30 DEG C, vacuum tightness is 0.1MPa, vacuum tightness keeps the pumpdown time of 0.1MPa to be 60min, then mixed solution is poured in mould, be put in a conventional oven, 110 DEG C of Procuring 2h, 140 DEG C of solidification 2h, 170 DEG C of solidification 3h, 200 DEG C of solidification 2h, then take out from baking oven and be cooled to room temperature, obtain the carboxylated graphene-epoxy resin composite material batten of high tenacity, grinding into specification is 50mm × 8mm × 6mm standard testing batten, do three-point bending mechanical property test.As shown in Figure 1, visible, there is tiny crack in section in the fracture surface sweeping of carboxylated graphene-epoxy resin composite material, is not brittle rupture, illustrates that carboxylated Graphene and epoxy group(ing) form certain chemical bonding.
Embodiment 2:
Getting 1L concentration is 2g/L graphene oxide solution, and graphene oxide lamellar spacing is between 0.5nm ~ 2nm, and ultrasonic power is 700W, and the ultrasonication time is 45min, obtains graphene oxide suspension; In graphene oxide suspension, add 2.0g hydrazine hydrate, in 90 DEG C of oil baths, condensing reflux 36h, obtains Graphene turbid solution; Graphene turbid solution is cooled to 75 DEG C, in Graphene turbid solution, add 2g aminophenyl acetic acid, the concentration of 10mL is the methanol solution of 0.2g/mL Isopentyl nitrite, 1.144g potassium hydroxide, at 75 DEG C of condensing reflux 36h, obtain the presoma turbid solution of carboxylated Graphene; Adjusting PH with hydrochloric acid is 5 ~ 6 presoma turbid solutions obtaining acidic graphite alkene; The presoma turbid solution drip washing of acidic graphite alkene filtered, being adjusted to PH is 6 ~ 7; Lyophilize 7 days, obtains carboxylated graphene powder.Take 20g3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexyl manthanoate and 26g 4-methyl hexahydrophthalic anhydride put into beaker, and Heating temperature is 60 DEG C, and churning time is 0.5h, make the two dissolve each other completely.Then the carboxylated graphene powder of 0.2g is added, under normal temperature, churning time is 20min, sonication treatment time is that 10min is to dissolution homogeneity, gained solution is cooled to room temperature, add 0.02g2, 4, 6-tri-(dimethylamino methyl) phenol stirs 10min, be placed in vacuum drying oven, vacuum suction temperature is 30 DEG C, vacuum tightness is 0.1MPa, vacuum tightness keeps the pumpdown time of 0.1MPa to be 60min, then mixed solution is poured in mould, be put in a conventional oven, 110 DEG C of Procuring 2h, 140 DEG C of solidification 2h, 170 DEG C of solidification 3h, 200 DEG C of solidification 2h, then take out from baking oven and be cooled to room temperature, obtain the carboxylated graphene-epoxy resin composite material batten of high tenacity, grinding into specification is 50mm × 8mm × 6mm standard testing batten, do three-point bending mechanical property test.
Embodiment 3:
Getting 1L concentration is 1g/L graphene oxide solution, and graphene oxide lamellar spacing is between 0.5nm ~ 2nm, and ultrasonic power is 800W, and the ultrasonication time is 60min, obtains graphene oxide suspension; In graphene oxide suspension, add 2.0g hydrazine hydrate, in 95 DEG C of oil baths, condensing reflux 48h, obtains Graphene turbid solution; Graphene turbid solution is cooled to 80 DEG C, in Graphene turbid solution, add 4g aminophenyl acetic acid, the concentration of 22.5mL is the ethanolic soln of 0.2g/mL Isopentyl nitrite, 0.998g sodium hydroxide, at 80 DEG C of condensing reflux 48h, obtain the presoma turbid solution of carboxylated Graphene; Adjusting PH with sulfuric acid is 5 ~ 6 presoma turbid solutions obtaining acidic graphite alkene; The presoma turbid solution drip washing of acidic graphite alkene filtered, being adjusted to PH is 6 ~ 7; Lyophilize 7 days, obtains carboxylated graphene powder.Take 20g3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexyl manthanoate and 27g 4-methyl hexahydrophthalic anhydride put into beaker, and Heating temperature is 50 DEG C, and churning time is 1.0h, make the two dissolve each other completely.Then the carboxylated graphene powder of 0.3g is added, under normal temperature, churning time is 15min, sonication treatment time is that 15min is to dissolution homogeneity, gained solution is cooled to room temperature, add 0.05g2, 4, 6-tri-(dimethylamino methyl) phenol stirs 15min, be placed in vacuum drying oven, vacuum suction temperature is 40 DEG C, vacuum tightness is 0.1MPa, vacuum tightness keeps the pumpdown time of 0.1MPa to be 50min, then mixed solution is poured in mould, be put in a conventional oven, 110 DEG C of Procuring 2h, 140 DEG C of solidification 2h, 170 DEG C of solidification 3h, 200 DEG C of solidification 2h, then take out from baking oven and be cooled to room temperature, obtain the carboxylated graphene-epoxy resin composite material batten of high tenacity, grinding into specification is 50mm × 8mm × 6mm standard testing batten, do three-point bending mechanical property test, its Fracture scan as shown in Figure 2, can find out, surface of fracture roughness increases, texture is more complicated, rupture stress oriented anisotropic, also be attended by increasing toughness tearing face to occur.Embodiment 4:
Getting 1L concentration is 3g/L graphene oxide solution, and graphene oxide lamellar spacing is between 0.5nm ~ 2nm, and ultrasonic power is 900W, and the ultrasonication time is 30min, obtains graphene oxide suspension; In graphene oxide suspension, add 3.5g hydrazine hydrate, in 95 DEG C of oil baths, condensing reflux 36h, obtains Graphene turbid solution; Graphene turbid solution is cooled to 75 DEG C, in Graphene turbid solution, add 6.0g aminophenyl acetic acid, the concentration of 27.5mL is the ethanolic soln of 0.2g/mL Isopentyl nitrite, 2.220g potassium hydroxide, at 75 DEG C of condensing reflux 48h, obtain the presoma turbid solution of carboxylated Graphene; Adjusting PH with sulfuric acid is 5 ~ 6 presoma turbid solutions obtaining acidic graphite alkene; The presoma turbid solution drip washing of acidic graphite alkene filtered, being adjusted to PH is 6 ~ 7; Lyophilize 6 days, obtains carboxylated graphene powder.Take 20g3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexyl manthanoate and 27g 4-methyl hexahydrophthalic anhydride put into beaker, and Heating temperature is 50 DEG C, and churning time is 1.0h, make the two dissolve each other completely.Then the carboxylated graphene powder of 0.4g is added, under normal temperature, churning time is 15min, sonication treatment time is that 15min is to dissolution homogeneity, gained solution is cooled to room temperature, add 0.05g2, 4, 6-tri-(dimethylamino methyl) phenol stirs 15min, be placed in vacuum drying oven, vacuum suction temperature is 40 DEG C, vacuum tightness is 0.1MPa, vacuum tightness keeps the pumpdown time of 0.1MPa to be 50min, then mixed solution is poured in mould, be put in a conventional oven, 110 DEG C of Procuring 2h, 140 DEG C of solidification 2h, 170 DEG C of solidification 3h, 200 DEG C of solidification 2h, then take out from baking oven and be cooled to room temperature, obtain the carboxylated graphene-epoxy resin composite material batten of high tenacity, grinding into specification is 50mm × 8mm × 6mm standard testing batten, do three-point bending mechanical property test.
Embodiment 5:
Getting 1L concentration is 1.5g/L graphene oxide solution, and graphene oxide lamellar spacing is between 0.5nm ~ 2nm, and ultrasonic power is 900W, and the ultrasonication time is 30min, obtains graphene oxide suspension; In graphene oxide suspension, add 2.0g hydrazine hydrate, in 95 DEG C of oil baths, condensing reflux 24h, obtains Graphene turbid solution; Graphene turbid solution is cooled to 80 DEG C, in Graphene turbid solution, add 5.0g aminophenyl acetic acid, the concentration of 30.0mL is the ethanolic soln of 0.2g/mL Isopentyl nitrite, 1.373g sodium hydroxide, at 80 DEG C of condensing reflux 24h, obtain the presoma turbid solution of carboxylated Graphene; Adjusting PH with sulfuric acid is 5 ~ 6 presoma turbid solutions obtaining acidic graphite alkene; The presoma turbid solution drip washing of acidic graphite alkene filtered, being adjusted to PH is 6 ~ 7; Lyophilize 4 days, obtains carboxylated graphene powder.Take 20g3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexyl manthanoate and 28g 4-methyl hexahydrophthalic anhydride put into beaker, and Heating temperature is 60 DEG C, and churning time is 0.5h, make the two dissolve each other completely.Then the carboxylated graphene powder of 0.5g is added, under normal temperature, churning time is 20min, sonication treatment time is that 10min is to dissolution homogeneity, gained solution is cooled to room temperature, add 0.1g2, 4, 6-tri-(dimethylamino methyl) phenol stirs 20min, be placed in vacuum drying oven, vacuum suction temperature is 50 DEG C, vacuum tightness is 0.1MPa, vacuum tightness keeps the pumpdown time of 0.1MPa to be 40min, then mixed solution is poured in mould, be put in a conventional oven, 110 DEG C of Procuring 2h, 140 DEG C of solidification 2h, 170 DEG C of solidification 3h, 200 DEG C of solidification 2h, then take out from baking oven and be cooled to room temperature, obtain the carboxylated graphene-epoxy resin composite material batten of high tenacity, grinding into specification is 50mm × 8mm × 6mm standard testing batten, do three-point bending mechanical property test, do three-point bending mechanical property test.
Embodiment 6:
Getting 1L concentration is 2.5g/L graphene oxide solution, and graphene oxide lamellar spacing is between 0.5nm ~ 2nm, and ultrasonic power is 900W, and the ultrasonication time is 30min, obtains graphene oxide suspension; In graphene oxide suspension, add 3.0g hydrazine hydrate, in 85 DEG C of oil baths, condensing reflux 36h, obtains Graphene turbid solution; Graphene turbid solution is cooled to 80 DEG C, in Graphene turbid solution, add 4.0g aminophenyl acetic acid, the concentration of 22.5mL is the ethanolic soln of 0.2g/mL Isopentyl nitrite, 1.366g potassium hydroxide, at 80 DEG C of condensing reflux 48h, obtain the presoma turbid solution of carboxylated Graphene; Adjusting PH with sulfuric acid is 5 ~ 6 presoma turbid solutions obtaining acidic graphite alkene; The presoma turbid solution drip washing of acidic graphite alkene filtered, being adjusted to PH is 6 ~ 7; Lyophilize 7 days, obtains carboxylated graphene powder.Take 20g3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexyl manthanoate and 28g 4-methyl hexahydrophthalic anhydride put into beaker, and Heating temperature is 60 DEG C, and churning time is 0.5h, make the two dissolve each other completely.Then the carboxylated graphene powder of 0.6g is added, under normal temperature, churning time is 20min, sonication treatment time is that 10min is to dissolution homogeneity, gained solution is cooled to room temperature, add 0.1g2, 4, 6-tri-(dimethylamino methyl) phenol stirs 20min, be placed in vacuum drying oven, vacuum suction temperature is 50 DEG C, vacuum tightness is 0.1MPa, vacuum tightness keeps the pumpdown time of 0.1MPa to be 40min, then mixed solution is poured in mould, be put in a conventional oven, 110 DEG C of Procuring 2h, 140 DEG C of solidification 2h, 170 DEG C of solidification 3h, 200 DEG C of solidification 2h, then take out from baking oven and be cooled to room temperature, obtain the carboxylated graphene-epoxy resin composite material batten of high tenacity, grinding into specification is 50mm × 8mm × 6mm standard testing batten, do three-point bending mechanical property test, do three-point bending mechanical property test, its Fracture scan as shown in Figure 3, obviously visible, fracture apperance big rise and fall, section is more coarse, be attended by extension deformation and tiny crack, fracture mode has obvious ductile rupture characteristic.
Claims (2)
1. the preparation method of the carboxylated graphene-epoxy resin composite material of high tenacity, is characterized in that, the step of preparation is as follows:
1.1, carboxylated graphene powder is prepared:
1.1.1, graphene oxide suspension is prepared: by graphene oxide ultrasonication in distilled water, ultrasonic power is 600W ~ 900W, the ultrasonication time is 30min ~ 60min, obtains finely dispersed graphene oxide suspension, and graphene oxide suspension concentration is 1g/L ~ 3g/L;
1.1.2, prepare Graphene turbid solution: in graphene oxide suspension, add reductive agent hydrazine hydrate, the mass ratio of graphene oxide and hydrazine hydrate is 1:1 ~ 2, and condensing reflux 24h ~ 48h in the oil bath of 85 DEG C ~ 95 DEG C, obtains Graphene turbid solution;
1.1.3, prepare the presoma turbid solution of carboxylated Graphene: Graphene turbid solution is cooled to 70 DEG C ~ 80 DEG C, add the alcoholic solution of aminophenyl acid and Isopentyl nitrite, aminophenyl acid is aminophenyl formic acid or aminophenyl acetic acid, the concentration of the alcoholic solution of Isopentyl nitrite is 0.2g/ml, alcohol is methyl alcohol or ethanol, aminophenyl acid is 1 ~ 10:10 with the mol ratio of graphene oxide, the mol ratio of Isopentyl nitrite and aminophenyl acid is 1 ~ 2:1, then highly basic is added, highly basic is potassium hydroxide or sodium hydroxide, the mol ratio of potassium hydroxide or sodium hydroxide and aminophenyl acid is 1.2 ~ 1.5:1, condensing reflux 24h ~ 48h in the oil bath of 70 DEG C ~ 80 DEG C, obtain the presoma turbid solution of carboxylated Graphene,
1.1.4, prepare acidic carboxypolymer functionalized graphene turbid solution: the presoma turbid solution presoma turbid solution strong acid of Graphene adjustment PH to 5 ~ 6 being obtained acidic graphite alkene, strong acid is hydrochloric acid or sulfuric acid;
1.1.5, moisture carboxylated Graphene is prepared: PH to 6 ~ 7 are filtered in the solid matter deionized water drip washing in acidic carboxypolymer functionalized graphene turbid solution, obtains moisture carboxylated Graphene;
1.1.6, carboxylated graphene powder is prepared: by moisture carboxylated Graphene lyophilize 5 days ~ 7 days, lyophilize temperature rose to 20 DEG C gradually from-40 DEG C, obtains carboxylated graphene powder;
1.2, epoxy resin and solidifying agent dissolve each other: epoxy resin and solidifying agent being stirred in a heated condition becomes the body that dissolves each other, epoxy resin is cycloaliphatic epoxy resin, solidifying agent is acid anhydride type curing agent, the mass ratio of epoxy resin and solidifying agent is 1:1.3 ~ 1.4, Heating temperature is 40 DEG C ~ 60 DEG C, and churning time is 0.5h ~ 1.5h;
1.3, carboxylated Graphene is added: in the body that dissolves each other of epoxy resin and solidifying agent, add carboxylated Graphene, carry out under normal temperature stirring and supersound process, obtain carboxylated Graphene-epoxy resin first mixed solution, the mass ratio of carboxylated Graphene and epoxy resin is 0.5 ~ 3:100, churning time is 10min ~ 20min, and sonication treatment time is 10min ~ 20min;
1.4, promotor is added: add promotor to carboxylated Graphene-epoxy resin mixed solution, Graphene-epoxy resin second mixed solution is obtained after stirring, promotor is phenol accelerant, and the mass ratio of promotor and epoxy resin is 0.1 ~ 0.5:100, and churning time is 10min ~ 20min;
1.5, vacuum suction: Graphene-epoxy resin second mixed solution is put into vacuum chamber and carries out vacuum suction, vacuum suction temperature is 30 DEG C ~ 50 DEG C, and the vacuum tightness in vacuum chamber is 0.1MPa, and vacuum pumpdown time is 40min ~ 60min;
1.6, elevated cure: Graphene-epoxy resin second mixed solution is poured in mould, elevated cure in an oven, temperature-rising method is: be warmed up to 110 DEG C of insulation 2h and carry out Procuring, be warmed up to 140 DEG C of insulation 2h again and carry out first stage solidification, be warmed up to 170 DEG C of insulation 3h again and carry out subordinate phase solidification, be warmed up to 200 DEG C of insulation 2h again and carry out phase III solidification, room temperature cools, and obtains the carboxylated graphene-epoxy resin composite material of high tenacity.
2. preparation method according to claim 1, is characterized in that, in preparation graphene oxide suspension step, described graphene oxide is prepared by oxidation reduction process, and graphene oxide lamellar spacing is between 0.5nm ~ 2nm.
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