CN106966379B - A kind of preparation method of the modification phenolic resin-based carbon foam of graphene/silicon dioxide hybrid material - Google Patents
A kind of preparation method of the modification phenolic resin-based carbon foam of graphene/silicon dioxide hybrid material Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of modification phenolic resin-based carbon foam of graphene/silicon dioxide hybrid material, and this method comprises the following steps: (1) graphene/silicon dioxide hydridization material is mixed with phenolic resin；(2) the modified phenolic resin foam of preparation graphene/silicon dioxide；(3) phenolic resin foam impregnates in acetone；(4) high temperature cabonization；Each raw material dosage is in terms of mass fraction.The method of the present invention can be effectively improved the foam structure of phenolic resin base carbon foam, and so that material is had superior mechanical property, graphene forms conductive path in carbon foam simultaneously, improve the electric conductivity of material, improve the electromagnetic shielding performance of material.
Description
Technical field
The present invention relates to polymeric foamed materials, are changed more particularly, to one kind by graphene/silicon dioxide hybrid material
Property phenolic resin and the foam being further carbonized.
Background technique
Although phenolic resin base carbon foam have very excellent electric conductivity, raw material it is from a wealth of sources, it is cheap,
But phenolic resin base carbon foam has some defects, the foam structure of carbon foam is not visibly homogeneous, this is seriously affected
The mechanical property and electric conductivity of material, for phenol formaldehyde foam base carbon foam in mechanical property, foam structure, in electric conductivity,
Deficiency in electromagnetic shielding performance needs to be modified research to phenolic resin base carbon foam.Currently, inoganic particle modified foam
Plastics are a kind of common method of modifying, and in order to change the foam structure of phenolic resin base carbon foam, phenol is added in inorganic particulate
Foam structure is improved by foaming in urea formaldehyde.
Hybrid material is a kind of novel composite material, obtains tool by the method for physics or chemistry by two kinds of materials
It is this since the interface between component and component is microscopic scale even molecular level there are two types of the excellent characteristic of material
The stress at special reduced performance interface is concentrated, and is given full play to the respective excellent properties of component, is kept the mechanical property of hybrid material obvious
Better than conventional material.Silica is in uniform spheroidal state on the surface of graphene in graphene/silicon dioxide hybrid material, is made
It obtains hybrid material and a kind of three-dimensional structure is presented, considerably increase the specific surface area of material, while silica and phenolic resin tool
There is preferable compatibility, solves the problems, such as that graphene is not easy to disperse in resin, hybrid material is in Foaming of phenolic resin process
It is middle to be used as heterogeneous nucleation agent, improve the foam structure of foam.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, the applicant provides a kind of graphene/silicon dioxide hybrid material
The preparation method of modification phenolic resin-based carbon foam.The method of the present invention can be effectively improved the abscess knot of phenolic resin base carbon foam
Structure, so that material is had superior mechanical property, graphene forms conductive path in carbon foam simultaneously, improves material
Electric conductivity improves the electromagnetic shielding performance of material.
Technical scheme is as follows:
A kind of preparation method of the modification phenolic resin-based carbon foam of graphene/silicon dioxide hybrid material, the method packet
Include following steps: each raw material dosage is in terms of mass fraction；
(1) 1~10 part of graphene/silicon dioxide hybrid material is added in 50-100 parts of phenolic resin, 3000~
1~3min of mechanical stirring under the revolving speed of 5000rpm；
(2) 1~2 part of silicone oil, 10~20 parts of toluenesulfonic acids are added in the resin by step (1) processing, 1500~
After stirring 1~5min under the revolving speed of 2000rpm, 5~7 parts of pentanes are added, foaming 30 in 70~80 DEG C of vacuum drying oven~
The modified phenolic resin foam of graphene/silicon dioxide is made in 60min；
(3) phenolic resin foam made from step (2) is impregnated to 24~32h in 30~50 DEG C of acetone, then foam is set
It is dried in vacuum drying oven；
(4) foam of drying is put into resistance furnace, is carbonized in nitrogen atmosphere high temperature, graphene/silicon dioxide is made
The modification phenolic resin-based carbon foam of hybrid material.
One of model HK1017A, PF-1068, RD-N01, PF2124, PF2127 of the phenolic resin or more
Kind.
The graphene/silicon dioxide hybrid material the preparation method comprises the following steps:
(1) weigh the silica of different-grain diameter respectively, hydroxylating graphene microchip is placed in dry round-bottomed flask, simultaneously
Anhydrous Isosorbide-5-Nitrae-the dioxane solution of 200~300ml or tetrahydrofuran are injected as solvent, by ultrasonic and/or magnetic agitation
Effect, obtains finely dispersed mixed liquor；
(2) poly acryloyl chloride is gradually dropped in dispersion liquid by conduit, while injects triethylamine with syringe, be moved into
In thermostatical oil bath, under nitrogen protection, magnetic agitation reacts 24~48h under 80~100 DEG C of constant temperatures；
(3) reaction product is filtered under diminished pressure, is collected into product and is cleaned multiple times with tetrahydrofuran, then filter to obtain black
Reaction product is placed in freeze-day with constant temperature in 60~80 DEG C of vacuum drying ovens, obtains graphene/silicon dioxide hybrid material.
The partial size of silica described in step (1) is 50~250nm；The silica and hydroxylating graphene microchip
Mass ratio be 1:3~1:1.
The mass ratio of poly acryloyl chloride described in step (2) and silica is 1:10~1:5；The triethylamine and dioxy
The mass ratio of SiClx is 1:20~1:10.
The condition of high temperature cabonization described in step (4) are as follows: the flow velocity of nitrogen is 20~30cm3.min-1；High temperature cabonization process
Divide three phases to carry out, be 1. heated to 350~400 DEG C with the speed of 5~10 DEG C/min, keeps the temperature 20~30min；2. again with 1~2
DEG C/speed of min is heated to 800 DEG C~900 DEG C, keep the temperature 30~60min；3. 1000 are heated to the speed of 1~2 DEG C/min~
1100 DEG C, keep the temperature 60~90min.
The present invention is beneficial to be had the technical effect that
(1) the method for the present invention selects graphene/silicon dioxide hybrid material as modified particle, graphene/silicon dioxide
Hybrid material is made by graphene growth in situ silica, the graphene before handling because Van der Waals force reunite together,
It is easily destroyed the foam structure of foam, spacing increases between graphene sheet layer after handling by growth in situ, Surface Creation two
Silicon oxide particle, therefore hybrid material has biggish specific surface area, and the particle of this large specific surface area is used for phenol formaldehyde foam
Modification in, the nucleating point in foam can be made to increase, so that the abscess quantity to be formed be made to increase, the size of foam becomes more
It is small more evenly, have broad application prospects and commercial value.
(2) the method for the present invention uses the graphene/silicon dioxide hybrid material of different-grain diameter as heterogeneous nucleation agent, different
Hybrid material because the difference of silica partial size passes through control silica partial size have different specific surface areas
Size improves the blasthole structure of phenol formaldehyde foam.
(3) the method for the present invention selects graphene/silicon dioxide hybrid material as additive, and hybrid material is attached to carbon foam
Prism on, form conductive path in the base, improve the electric conductivity of material.
(4) the method for the present invention selects phenolic resin base as the basis material of carbon foam, because of the raw material valence of phenolic resin
The cheap structure simultaneously of lattice is easy to control.
(5) present invention is controlled heating rate, is easy to control the foam structure of carbon foam using the method for segmentation carbonization, is protected
The integrality for holding foam structure is not easily broken the prism of foam, so that carbon foam is kept good mechanical property, while complete
Foam structure can assign the good electric property of carbon foam and electromagnetic shielding performance.
Specific embodiment
Below with reference to embodiment, the present invention is specifically described.
Embodiment 1
A kind of preparation method of the modification phenolic resin-based carbon foam of graphene/silicon dioxide hybrid material, the method packet
Include following steps: each raw material dosage is in terms of mass fraction；
(1) 1 part of graphene/silicon dioxide hybrid material is added in 50 parts of PF2124 phenolic resin, 3000rpm's
Mechanical stirring 1min under revolving speed；
(2) 1 part of silicone oil, 10 parts of toluenesulfonic acids are added in the resin by step (1) processing, in the revolving speed of 1500rpm
After lower stirring 1min, 5 parts of pentanes are added, foam 30min in 70 DEG C of vacuum drying oven, and obtained graphene/silicon dioxide changes
The phenolic resin foam of property；
(3) phenolic resin foam made from step (2) is impregnated for 24 hours in 30 DEG C of acetone, then foam is placed in vacuum and is dried
It is dried in case；
(4) foam of drying is put into resistance furnace, is carbonized in nitrogen atmosphere high temperature, graphene/silicon dioxide is made
The modification phenolic resin-based carbon foam of hybrid material；Wherein, the flow velocity of nitrogen is 20cm3.min-1；Three ranks of high temperature cabonization process point
1. Duan Jinhang is heated to 350 DEG C with the speed of 5 DEG C/min, keep the temperature 20min；2. 800 DEG C are heated to the speed of 1 DEG C/min again,
Keep the temperature 30min；3. being heated to 1000 DEG C with the speed of 1 DEG C/min, 60min is kept the temperature.
The graphene/silicon dioxide hybrid material the preparation method comprises the following steps:
(1) 1 part of partial size is weighed respectively is placed in dry round bottom for the silica of 50nm, 2 parts of hydroxylating graphene microchip
In flask, while injecting the anhydrous Isosorbide-5-Nitrae-dioxane solution of 200ml is that solvent is obtained finely dispersed by the effect of ultrasound
Mixed liquor；
(2) 0.1 part of poly acryloyl chloride is gradually dropped in dispersion liquid by conduit, while injects 0.05 part three with syringe
Ethamine is moved into thermostatical oil bath, and under nitrogen protection, magnetic agitation is reacted for 24 hours under 80 DEG C of constant temperatures；
(3) reaction product is filtered under diminished pressure, is collected into product and is cleaned multiple times with tetrahydrofuran, then filter to obtain black
Reaction product is placed in freeze-day with constant temperature in 60 DEG C of vacuum drying ovens, obtains the graphene/silicon dioxide hybrid material that partial size is 50nm.
Embodiment 2
A kind of preparation method of the modification phenolic resin-based carbon foam of graphene/silicon dioxide hybrid material, the method packet
Include following steps: each raw material dosage is in terms of mass fraction；
(1) 10 parts of graphene/silicon dioxide hybrid materials are added in 100 parts of PF1068 phenolic resin, in 5000rpm
Revolving speed under mechanical stirring 3min；
(2) 2 parts of silicone oil, 20 parts of toluenesulfonic acids are added in the resin by step (1) processing, in the revolving speed of 2000rpm
After lower stirring 5min, 7 parts of pentanes are added, foam 60min in 80 DEG C of vacuum drying oven, and obtained graphene/silicon dioxide changes
The phenolic resin foam of property；
(3) phenolic resin foam made from step (2) is impregnated into 50 DEG C of acetone 32h, then foam is placed in vacuum and is dried
It is dried in case；
(4) foam of drying is put into resistance furnace, is carbonized in nitrogen atmosphere high temperature, graphene/silicon dioxide is made
The modification phenolic resin-based carbon foam of hybrid material；Wherein, the flow velocity of nitrogen is 30cm3.min-1；Three ranks of high temperature cabonization process point
1. Duan Jinhang is heated to 400 DEG C with the speed of 10 DEG C/min, keep the temperature 30min；2. being heated to 900 again with the speed of 2 DEG C/min
DEG C, keep the temperature 60min；3. being heated to 1100 DEG C with the speed of 2 DEG C/min, 90min is kept the temperature.
The graphene/silicon dioxide hybrid material the preparation method comprises the following steps:
(1) silica of 1 part of 250nm is weighed respectively, 3 parts of hydroxylating graphene microchip is placed in dry round-bottomed flask
In, while injecting the anhydrous Isosorbide-5-Nitrae-dioxane solution of 300ml is that solvent is obtained finely dispersed by the effect of magnetic agitation
Mixed liquor；
(2) 0.2 part of poly acryloyl chloride is gradually dropped in dispersion liquid by conduit, while injects 0.1 part three with syringe
Ethamine is moved into thermostatical oil bath, and under nitrogen protection, magnetic agitation reacts 48h under 100 DEG C of constant temperatures；
(3) reaction product is filtered under diminished pressure, is collected into product and is cleaned multiple times with tetrahydrofuran, then filter to obtain black
Reaction product is placed in freeze-day with constant temperature in 80 DEG C of vacuum drying ovens, obtains the graphene/silicon dioxide hybrid material that partial size is 250nm.
Embodiment 3
A kind of preparation method of the modification phenolic resin-based carbon foam of graphene/silicon dioxide hybrid material, the method packet
Include following steps: each raw material dosage is in terms of mass fraction；
(1) 5 parts of graphene/silicon dioxide hybrid materials are added in 80 parts of HK1017A phenolic resin, in 4500rpm
Revolving speed under mechanical stirring 2min；
(2) 1.5 parts of silicone oil, 15 parts of toluenesulfonic acids are added in the resin by step (1) processing, in turning for 1800rpm
After the lower stirring 2.5min of speed, 6 parts of pentanes are added, foam 45min in 75 DEG C of vacuum drying oven, and graphene/titanium dioxide is made
The phenolic resin foam of Si modification；
(3) phenolic resin foam made from step (2) is impregnated into 45 DEG C of acetone 28h, then foam is placed in vacuum and is dried
It is dried in case；
(4) foam of drying is put into resistance furnace, is carbonized in nitrogen atmosphere high temperature, graphene/silicon dioxide is made
The modification phenolic resin-based carbon foam of hybrid material；Wherein, the flow velocity of nitrogen is 25cm3.min-1；Three ranks of high temperature cabonization process point
1. Duan Jinhang is heated to 380 DEG C with the speed of 8 DEG C/min, keep the temperature 25min；2. being heated to 850 again with the speed of 1.5 DEG C/min
DEG C, keep the temperature 45min；3. being heated to 1050 DEG C with the speed of 1.5 DEG C/min, 80min is kept the temperature.
The graphene/silicon dioxide hybrid material the preparation method comprises the following steps:
(1) silica of 1 part of 100nm is weighed respectively, 2 parts of hydroxylating graphene microchip is placed in dry round-bottomed flask
In, while injecting the anhydrous Isosorbide-5-Nitrae-dioxane solution of 250ml is that solvent is dispersed by the effect of ultrasound and magnetic agitation
Uniform mixed liquor；
(2) 0.15 part of poly acryloyl chloride is gradually dropped in dispersion liquid by conduit, while injects 0.075 part with syringe
Triethylamine is moved into thermostatical oil bath, and under nitrogen protection, magnetic agitation reacts 36h under 90 DEG C of constant temperatures；
(3) reaction product is filtered under diminished pressure, is collected into product and is cleaned multiple times with tetrahydrofuran, then filter to obtain black
Reaction product is placed in freeze-day with constant temperature in 75 DEG C of vacuum drying ovens, obtains the graphene/silicon dioxide hybrid material that partial size is 100nm.
Embodiment 4
A kind of preparation method of the modification phenolic resin-based carbon foam of graphene/silicon dioxide hybrid material, the method packet
Include following steps: each raw material dosage is in terms of mass fraction；
(1) 5 parts of graphene/silicon dioxide hybrid materials are added in 80 parts of PF2127 phenolic resin, 5000rpm's
Mechanical stirring 1min under revolving speed；
(2) 2 parts of silicone oil, 15 parts of toluenesulfonic acids are added in the resin by step (1) processing, in the revolving speed of 2000rpm
After lower stirring 2.5min, 7 parts of pentanes are added, foam 60min in 80 DEG C of vacuum drying oven, and graphene/silicon dioxide is made
Modified phenolic resin foam；
(3) phenolic resin foam made from step (2) is impregnated into 30 DEG C of acetone 32h, then foam is placed in vacuum and is dried
It is dried in case；
(4) foam of drying is put into resistance furnace, is carbonized in nitrogen atmosphere high temperature, graphene/silicon dioxide is made
The modification phenolic resin-based carbon foam of hybrid material；Wherein, the flow velocity of nitrogen is 30cm3.min-1；Three ranks of high temperature cabonization process point
1. Duan Jinhang is heated to 400 DEG C with the speed of 5 DEG C/min, keep the temperature 30min；2. 800 DEG C are heated to the speed of 2 DEG C/min again,
Keep the temperature 60min；3. being heated to 1050 DEG C with the speed of 1 DEG C/min, 60min is kept the temperature.
The graphene/silicon dioxide hybrid material the preparation method comprises the following steps:
(1) silica of 1 part of 50nm is weighed respectively, 2 parts of hydroxylating graphene microchip is placed in dry round-bottomed flask
In, while injecting the anhydrous Isosorbide-5-Nitrae-dioxane solution of 250ml is that solvent is dispersed by the effect of ultrasound and magnetic agitation
Uniform mixed liquor；
(2) 0.2 part of poly acryloyl chloride is gradually dropped in dispersion liquid by conduit, while injects 0.1 part three with syringe
Ethamine is moved into thermostatical oil bath, and under nitrogen protection, magnetic agitation reacts 48h under 100 DEG C of constant temperatures；
(3) reaction product is filtered under diminished pressure, is collected into product and is cleaned multiple times with tetrahydrofuran, then filter to obtain black
Reaction product is placed in freeze-day with constant temperature in 80 DEG C of vacuum drying ovens, obtains graphene/silicon dioxide hybrid material.
Comparative example:
A kind of preparation method of the modification phenolic resin-based carbon foam of graphene, described method includes following steps: each raw material
Dosage is in terms of mass fraction；
(1) 5 mass parts graphenes are added in the RD-N01 phenolic resin of 50 mass parts, the machine under the revolving speed of 3000rpm
Tool stirs 1min；
(2) 1 part of silicone oil, 10 parts of toluenesulfonic acids are added in the resin by step (1) processing, in the revolving speed of 1500rpm
After lower stirring 1min, 5 parts of pentanes are added, foam 30min in 70 DEG C of vacuum drying oven, and the modified phenolic aldehyde tree of graphene is made
Fat vacuole foam；
(3) phenolic resin foam made from step (2) is impregnated for 24 hours in 30 DEG C of acetone, then foam is placed in vacuum and is dried
It is dried in case；
(4) foam of drying is put into resistance furnace, is carbonized in air atmosphere high temperature, is heated with the speed of 10 DEG C/min
To 480 DEG C, 60min is kept the temperature, the modification phenolic resin-based carbon foam of graphene is made.
Test case
Examples 1 to 4 and the resulting carbon foam of comparative example are subjected to compression performance test according to ASTM_D1621-2010；
Electromagnetic shielding performance test is carried out in the range of frequency is 8-12GHz using Agilent N-5242A vector network tester；
The electric conductivity of carbon foam is tested using four acusector testers.Test result is as shown in table 1.
Table 1
As can be seen from the data in the table, graphene/silicon dioxide hybrid material can substantially change carbon foam structure and
Performance reduces abscess-size, improves the mechanical property and electromagnetic shielding performance of material, and the increasing of the size with silica
Add, the foam structure of carbon foam reduces, and the electromagnetic shielding performance of carbon foam of electric conductivity improving a lot improves.
Claims (2)
1. a kind of preparation method of the modification phenolic resin-based carbon foam of graphene/silicon dioxide hybrid material, it is characterised in that institute
The method of stating includes the following steps: each raw material dosage in terms of mass fraction；
(1) 1~10 part of graphene/silicon dioxide hybrid material is added in 50~100 parts of phenolic resin, 3000~
1~3min of mechanical stirring under the revolving speed of 5000rpm；
(2) 1~2 part of silicone oil, 10~20 parts of toluenesulfonic acids are added in the resin by step (1) processing, 1500~
After stirring 1~5min under the revolving speed of 2000rpm, 5~7 parts of pentanes are added, foaming 30 in 70~80 DEG C of vacuum drying oven~
The modified phenolic resin foam of graphene/silicon dioxide is made in 60min；
(3) phenolic resin foam made from step (2) is impregnated to 24~32h in 30~50 DEG C of acetone, then foam is placed in very
It is dried in empty baking oven；
(4) foam of drying is put into resistance furnace, is carbonized in nitrogen atmosphere high temperature, graphene/silicon dioxide hydridization is made
Material modification phenolic resin base carbon foam；The condition of the high temperature cabonization are as follows: the flow velocity of nitrogen is 20~30cm3.min-1；High temperature
Carbonisation divides three phases to carry out, and is 1. heated to 350~400 DEG C with the speed of 5~10 DEG C/min, keeps the temperature 20~30min；②
800 DEG C~900 DEG C are heated to the speed of 1~2 DEG C/min again, keeps the temperature 30~60min；3. being heated with the speed of 1~2 DEG C/min
To 1000~1100 DEG C, 60~90min is kept the temperature；
The graphene/silicon dioxide hybrid material the preparation method comprises the following steps:
(1) weigh the silica of different-grain diameter respectively, hydroxylating graphene microchip is placed in dry round-bottomed flask, inject simultaneously
Anhydrous Isosorbide-5-Nitrae-the dioxane solution of 200~300ml or tetrahydrofuran are as solvent, by the effect of ultrasound and/or magnetic agitation,
Obtain finely dispersed mixed liquor；The partial size of the silica is 50~250nm；The silica and hydroxylating graphene
The mass ratio of microplate is 1:3~1；
(2) poly acryloyl chloride is gradually dropped in dispersion liquid by conduit, while injects triethylamine with syringe, be moved into constant temperature
In oil bath pan, under nitrogen protection, magnetic agitation reacts 24~48h under 80~100 DEG C of constant temperatures；The poly acryloyl chloride
Mass ratio with silica is 1:10~1:8；The mass ratio of the triethylamine and silica is 1:15~1:10；
(3) reaction product is filtered under diminished pressure, is collected into product and is cleaned multiple times with tetrahydrofuran, then filter to obtain black reaction
Product is placed in freeze-day with constant temperature in 60~80 DEG C of vacuum drying ovens, obtains graphene/silicon dioxide hybrid material.
2. preparation method according to claim 1, it is characterised in that model HK1017A, PF- of the phenolic resin
1068, one of RD-N01, PF2124, PF2127 or a variety of.
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| CN109535644A (en) * | 2018-11-15 | 2019-03-29 | 苏州宏久航空防热材料科技有限公司 | A kind of carbon foam/carbon nanocoils/silicon carbide nanometer line resin composite materials substrate and preparation method thereof |
| CN112250464B (en) * | 2020-10-26 | 2022-07-15 | 西安工程大学 | Foam carbon composite material for electromagnetic shielding and preparation method thereof |
| CN113959328B (en) * | 2021-10-27 | 2022-07-26 | 江南大学 | In-situ measurement method for internal strain of flexible foam |
| CN113831131B (en) * | 2021-11-11 | 2022-11-04 | 中南大学 | Carbon foam in-situ growth carbon nanotube composite electromagnetic shielding material and preparation method thereof |
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