CN106966379A - 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 PDF

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CN106966379A
CN106966379A CN201710153292.6A CN201710153292A CN106966379A CN 106966379 A CN106966379 A CN 106966379A CN 201710153292 A CN201710153292 A CN 201710153292A CN 106966379 A CN106966379 A CN 106966379A
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graphene
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CN106966379B (en
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俞科静
罗霞
钱坤
张典堂
卢雪峰
孙洁
肖学良
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Jiangnan University
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    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
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    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2006/40—Electric properties
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract

The invention discloses a kind of preparation method of the modification phenolic resin-based carbon foam of graphene/silicon dioxide hybrid material, this method comprises the following steps：(1) graphene/silicon dioxide hydridization material is mixed with phenolic resin；(2) phenolic resin foam that graphene/silicon dioxide is modified is prepared；(3) phenolic resin foam soaks in acetone；(4) high temperature cabonization；Each raw material dosage is in terms of mass fraction.The inventive method can be effectively improved the foam structure of phenolic resin base carbon foam, and material is had more excellent mechanical property, graphene forms conductive path in carbon foam simultaneously, improves the electric conductivity of material, improves the capability of electromagnetic shielding of material.

Description

A kind of system of the modification phenolic resin-based carbon foam of graphene/silicon dioxide hybrid material Preparation Method
Technical field
The present invention relates to polymeric foamed material, changed more particularly, to one kind by graphene/silicon dioxide hybrid material Property phenolic resin and the foam being further carbonized.
Background technology
Although phenolic resin base carbon foam has very excellent electric conductivity, the wide material sources of raw material are cheap, But phenolic resin base carbon foam, there is also some defects, the foam structure of carbon foam is not visibly homogeneous, and this has a strong impact on The mechanical property and electric conductivity of material, for phenol formaldehyde foam base carbon foam in mechanical property, foam structure, in electric conductivity, Deficiency on capability of electromagnetic shielding to phenolic resin base carbon foam, it is necessary to be modified research.At present, inoganic particle modified foam Plastics are a kind of conventional method of modifying, and in order to change the foam structure of phenolic resin base carbon foam, inorganic particulate is added into phenol Improve foam structure by foaming in urea formaldehyde.
Hybrid material is a kind of new composite, and tools are obtained by the method for physics or chemistry by two kinds of materials There is the excellent characteristic of two kinds of materials, it is this because the interface between component and component is microscopic scale even molecular level Characteristic can reduce the stress concentration at interface, give full play to the respective excellent properties of component, make the mechanical property of hybrid material obvious Better than conventional material.Silica is in uniform spheroidal state in graphenic surface in graphene/silicon dioxide hybrid material, is made Obtain 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, solve the problem of graphene is difficult to disperse in resin, hybrid material is in Foaming of phenolic resin process It is middle to be used as heterogeneous nucleation agent, the foam structure of improvement foam.
The content 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 inventive method can be effectively improved the abscess knot of phenolic resin base carbon foam Structure, material is had more excellent mechanical property, graphene forms conductive path in carbon foam simultaneously, improves material Electric conductivity, improves the capability of electromagnetic shielding 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, methods described bag Include following steps：Each raw material dosage is in terms of mass fraction；
(1) in the phenolic resin that 1~10 part of graphene/silicon dioxide hybrid material is added to 50-100 parts, 3000~ 1~3min of mechanical agitation under 5000rpm rotating speed；
(2) 1~2 part of silicone oil, 10~20 parts of toluenesulfonic acids are added in the resin by step (1) processing, 1500~ Stirred under 2000rpm rotating speed after 1~5min, add in 5~7 parts of pentanes, 70~80 DEG C of vacuum drying oven foaming 30~ 60min, is made the phenolic resin foam that graphene/silicon dioxide is modified；
(3) phenolic resin foam made from step (2) is soaked into 24~32h in 30~50 DEG C of acetone, then foam is put Dried in vacuum drying oven；
(4) foam of drying is put into resistance furnace, in the carbonization of nitrogen atmosphere high temperature, graphene/silicon dioxide is made The modification phenolic resin-based carbon foam of hybrid material.
One kind or many in model HK1017A, PF-1068, RD-N01, PF2124, PF2127 of the phenolic resin Kind.
The preparation method of the graphene/silicon dioxide hybrid material is：
(1) weigh the silica of different-grain diameter, hydroxylating graphene microchip respectively to be placed in dry round-bottomed flask, simultaneously Anhydrous Isosorbide-5-Nitrae-the dioxane solutions of 200~300ml or tetrahydrofuran are injected as solvent, pass through ultrasonic and/or magnetic agitation Effect, obtains finely dispersed mixed liquor；
(2) poly acryloyl chloride is gradually dropped in dispersion liquid by conduit, while injecting 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 suction filtration obtains 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 particle diameter 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 and silica described in step (2) 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 is described in step (4)：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 5~10 DEG C/min speed, be incubated 20~30min；2. again with 1~2 DEG C/min speed is heated to 800 DEG C~900 DEG C, is incubated 30~60min；3. 1000 are heated to 1~2 DEG C/min speed~ 1100 DEG C, it is incubated 60~90min.
The present invention is beneficial to be had technical effect that：
(1) the inventive method selection graphene/silicon dioxide hybrid material is used as modified particle, graphene/silicon dioxide Hybrid material is made by graphene growth in situ silica, and the graphene before processing is reunited together because of Van der Waals force, The foam structure of foam is easily destroyed, spacing increases between graphene sheet layer after being handled by growth in situ, Surface Creation two Silicon oxide particle, therefore hybrid material has larger specific surface area, and the big particle of this specific surface area is used for into phenol formaldehyde foam Modification among, can increase the nucleating point in foam, so that the abscess increasing number formed, the size of foam becomes more It is small evenly, have broad application prospects and commercial value.
(2) the inventive method uses the graphene/silicon dioxide hybrid material of different-grain diameter as heterogeneous nucleation agent, difference Hybrid material because silica particle diameter difference with different specific surface areas, by controlling silica particle diameter Size improves the blasthole structure of phenol formaldehyde foam.
(3) the inventive method 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 inventive method selects phenolic resin base as the matrix material of carbon foam, because the raw material valency of phenolic resin The cheap structure simultaneously of lattice is easily controlled.
(5) present invention is controlled heating rate, is easily controlled the foam structure of carbon foam using the method for segmentation carbonization, is protected The integrality of foam structure is held, the prism of foam is not easily broken, carbon foam is kept good mechanical property, while complete Foam structure can assign carbon foam good electric property and capability of electromagnetic shielding.
Embodiment
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, methods described bag Include following steps：Each raw material dosage is in terms of mass fraction；
(1) in the PF2124 phenolic resin that 1 part of graphene/silicon dioxide hybrid material is added to 50 parts, 3000rpm's Mechanical agitation 1min under rotating speed；
(2) 1 part of silicone oil, 10 parts of toluenesulfonic acids are added in the resin by step (1) processing, in 1500rpm rotating speed After lower stirring 1min, the 30min that foamed in 5 parts of pentanes, 70 DEG C of vacuum drying oven is added, obtained graphene/silicon dioxide changes The phenolic resin foam of property；
(3) phenolic resin foam made from step (2) is soaked into 24h in 30 DEG C of acetone, then foam is placed in vacuum and dried Dried in case；
(4) foam of drying is put into resistance furnace, in the carbonization of 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；High temperature cabonization three ranks of process point Duan Jinhang, is 1. heated to 350 DEG C with 5 DEG C/min speed, is incubated 20min；2. 800 DEG C are heated to 1 DEG C/min speed again, It is incubated 30min；3. 1000 DEG C are heated to 1 DEG C/min speed, are incubated 60min.
The preparation method of the graphene/silicon dioxide hybrid material is：
(1) it is that 50nm silica, 2 parts of hydroxylating graphene microchip are placed in dry round bottom to weigh 1 part of particle diameter respectively In flask, while it is solvent to inject the anhydrous Isosorbide-5-Nitrae-dioxane solutions of 200ml, by the effect of ultrasound, obtain finely dispersed Mixed liquor；
(2) 0.1 part of poly acryloyl chloride is gradually dropped in dispersion liquid by conduit, while injecting 0.05 part three with syringe Ethamine, is moved into thermostatical oil bath, and under nitrogen protection, magnetic agitation reacts 24h 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 suction filtration obtains 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 particle diameter is 50nm.
Embodiment 2
A kind of preparation method of the modification phenolic resin-based carbon foam of graphene/silicon dioxide hybrid material, methods described bag Include following steps：Each raw material dosage is in terms of mass fraction；
(1) in the PF1068 phenolic resin that 10 parts of graphene/silicon dioxide hybrid materials are added to 100 parts, in 5000rpm Rotating speed under mechanical agitation 3min；
(2) 2 parts of silicone oil, 20 parts of toluenesulfonic acids are added in the resin by step (1) processing, in 2000rpm rotating speed After lower stirring 5min, the 60min that foamed in 7 parts of pentanes, 80 DEG C of vacuum drying oven is added, obtained graphene/silicon dioxide changes The phenolic resin foam of property；
(3) phenolic resin foam made from step (2) is soaked into 32h in 50 DEG C of acetone, then foam is placed in vacuum and dried Dried in case；
(4) foam of drying is put into resistance furnace, in the carbonization of 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；High temperature cabonization three ranks of process point Duan Jinhang, is 1. heated to 400 DEG C with 10 DEG C/min speed, is incubated 30min；2. 900 are heated to 2 DEG C/min speed again DEG C, it is incubated 60min；3. 1100 DEG C are heated to 2 DEG C/min speed, are incubated 90min.
The preparation method of the graphene/silicon dioxide hybrid material is：
(1) 1 part of 250nm silica, 3 parts of hydroxylating graphene microchip are weighed respectively is placed in dry round-bottomed flask In, while it is solvent to inject the anhydrous Isosorbide-5-Nitrae-dioxane solutions of 300ml, by the effect of magnetic agitation, obtain finely dispersed Mixed liquor；
(2) 0.2 part of poly acryloyl chloride is gradually dropped in dispersion liquid by conduit, while injecting 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 suction filtration obtains 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 particle diameter is 250nm.
Embodiment 3
A kind of preparation method of the modification phenolic resin-based carbon foam of graphene/silicon dioxide hybrid material, methods described bag Include following steps：Each raw material dosage is in terms of mass fraction；
(1) in the HK1017A phenolic resin that 5 parts of graphene/silicon dioxide hybrid materials are added to 80 parts, in 4500rpm Rotating speed under mechanical agitation 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, the 45min that foamed in 6 parts of pentanes, 75 DEG C of vacuum drying oven is added, graphene/titanium dioxide is made The phenolic resin foam of Si modification；
(3) phenolic resin foam made from step (2) is soaked into 28h in 45 DEG C of acetone, then foam is placed in vacuum and dried Dried in case；
(4) foam of drying is put into resistance furnace, in the carbonization of 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；High temperature cabonization three ranks of process point Duan Jinhang, is 1. heated to 380 DEG C with 8 DEG C/min speed, is incubated 25min；2. 850 are heated to 1.5 DEG C/min speed again DEG C, it is incubated 45min；3. 1050 DEG C are heated to 1.5 DEG C/min speed, are incubated 80min.
The preparation method of the graphene/silicon dioxide hybrid material is：
(1) 1 part of 100nm silica, 2 parts of hydroxylating graphene microchip are weighed respectively is placed in dry round-bottomed flask In, while it is solvent to inject the anhydrous Isosorbide-5-Nitrae-dioxane solutions of 250ml, by the effect of ultrasound and magnetic agitation, disperseed Uniform mixed liquor；
(2) 0.15 part of poly acryloyl chloride is gradually dropped in dispersion liquid by conduit, while injecting 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 suction filtration obtains 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 particle diameter is 100nm.
Embodiment 4
A kind of preparation method of the modification phenolic resin-based carbon foam of graphene/silicon dioxide hybrid material, methods described bag Include following steps：Each raw material dosage is in terms of mass fraction；
(1) in the PF2127 phenolic resin that 5 parts of graphene/silicon dioxide hybrid materials are added to 80 parts, 5000rpm's Mechanical agitation 1min under rotating speed；
(2) 2 parts of silicone oil, 15 parts of toluenesulfonic acids are added in the resin by step (1) processing, in 2000rpm rotating speed After lower stirring 2.5min, the 60min that foamed in 7 parts of pentanes, 80 DEG C of vacuum drying oven is added, graphene/silicon dioxide is made Modified phenolic resin foam；
(3) phenolic resin foam made from step (2) is soaked into 32h in 30 DEG C of acetone, then foam is placed in vacuum and dried Dried in case；
(4) foam of drying is put into resistance furnace, in the carbonization of 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；High temperature cabonization three ranks of process point Duan Jinhang, is 1. heated to 400 DEG C with 5 DEG C/min speed, is incubated 30min；2. 800 DEG C are heated to 2 DEG C/min speed again, It is incubated 60min；3. 1050 DEG C are heated to 1 DEG C/min speed, are incubated 60min.
The preparation method of the graphene/silicon dioxide hybrid material is：
(1) 1 part of 50nm silica, 2 parts of hydroxylating graphene microchip are weighed respectively is placed in dry round-bottomed flask In, while it is solvent to inject the anhydrous Isosorbide-5-Nitrae-dioxane solutions of 250ml, by the effect of ultrasound and magnetic agitation, disperseed Uniform mixed liquor；
(2) 0.2 part of poly acryloyl chloride is gradually dropped in dispersion liquid by conduit, while injecting 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 suction filtration obtains 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, methods described comprises the following steps：Each raw material Consumption 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 3000rpm rotating speed Tool stirs 1min；
(2) 1 part of silicone oil, 10 parts of toluenesulfonic acids are added in the resin by step (1) processing, in 1500rpm rotating speed After lower stirring 1min, the 30min that foamed in 5 parts of pentanes, 70 DEG C of vacuum drying oven is added, the phenolic aldehyde tree that graphene is modified is made Fat vacuole foam；
(3) phenolic resin foam made from step (2) is soaked into 24h in 30 DEG C of acetone, then foam is placed in vacuum and dried Dried in case；
(4) foam of drying is put into resistance furnace, in the carbonization of air atmosphere high temperature, heated with 10 DEG C/min speed To 480 DEG C, 60min is incubated, the modification phenolic resin-based carbon foam of graphene is made.
Test case
Carbon foam obtained by embodiment 1~4 and comparative example is compressed performance test according to ASTM_D1621-2010； Using Agilent N-5242A vector networks testers capability of electromagnetic shielding test is carried out in the range of frequency is 8-12GHz； 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 capability of electromagnetic shielding of material, and the increasing of the size with silica Plus, the foam structure of carbon foam reduces, and the improve a lot capability of electromagnetic shielding of carbon foam of electric conductivity is improved.

Claims (6)

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 comprises the following steps：Each raw material dosage is in terms of mass fraction；
(1) in the phenolic resin that 1~10 part of graphene/silicon dioxide hybrid material is added to 50~100 parts, 3000~ 1~3min of mechanical agitation under 5000rpm rotating speed；
(2) 1~2 part of silicone oil, 10~20 parts of toluenesulfonic acids are added in the resin by step (1) processing, 1500~ Stirred under 2000rpm rotating speed after 1~5min, add in 5~7 parts of pentanes, 70~80 DEG C of vacuum drying oven foaming 30~ 60min, is made the phenolic resin foam that graphene/silicon dioxide is modified；
(3) phenolic resin foam made from step (2) is soaked into 24~32h in 30~50 DEG C of acetone, then foam is placed in very Dried in empty baking oven；
(4) foam of drying is put into resistance furnace, in the carbonization of nitrogen atmosphere high temperature, graphene/silicon dioxide hydridization is made Material modification phenolic resin base carbon foam.
2. preparation method according to claim 1, it is characterised in that the preparation of the graphene/silicon dioxide hybrid material Method is：
(1) silica of different-grain diameter, hydroxylating graphene microchip are weighed respectively to be placed in dry round-bottomed flask, are injected simultaneously Anhydrous Isosorbide-5-Nitrae-the dioxane solutions of 200~300ml or tetrahydrofuran are as solvent, by the effect of ultrasound and/or magnetic agitation, Obtain finely dispersed mixed liquor；
(2) poly acryloyl chloride is gradually dropped in dispersion liquid by conduit, while injecting triethylamine with syringe, is moved into constant temperature In oil bath pan, 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 suction filtration obtains 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.
3. preparation method according to claim 2, it is characterised in that the particle diameter of silica described in step (1) is 50~ 250nm；The silica and the mass ratio of hydroxylating graphene microchip are 1:3~1.
4. preparation method according to claim 2, it is characterised in that poly acryloyl chloride and silica described in step (2) Mass ratio be 1:10~1:8；The mass ratio of the triethylamine and silica is 1:15~1：10.
5. preparation method according to claim 1, it is characterised in that model HK1017A, PF- of the phenolic resin 1068th, the one or more in RD-N01, PF2124, PF2127.
6. preparation method according to claim 2, it is characterised in that the condition of high temperature cabonization is described in step (4)：Nitrogen The flow velocity of gas is 20~30cm3.min-1；High temperature cabonization process point three phases are carried out, and are 1. heated with 5~10 DEG C/min speed To 350~400 DEG C, 20~30min is incubated；2. 800 DEG C~900 DEG C are heated to 1~2 DEG C/min speed again, insulation 30~ 60min；3. 1000~1100 DEG C are heated to 1~2 DEG C/min speed, are incubated 60~90min.
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CN112250464A (en) * 2020-10-26 2021-01-22 西安工程大学 Foam carbon composite material for electromagnetic shielding and preparation method thereof
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CN118367132A (en) * 2024-06-19 2024-07-19 上海巴库斯超导新材料有限公司 High-magnification graphene for lithium ion battery and preparation method thereof

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