CN110144107A - Cyanalation redox graphene/poly (arylene ether nitrile) hybrid material and preparation method thereof - Google Patents
Cyanalation redox graphene/poly (arylene ether nitrile) hybrid material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of cyanalation redox graphene/poly (arylene ether nitrile) hybrid materials and preparation method thereof.The hybrid material is the hybrid material of cyanalation redox graphene and phthalonitrile-terminated poly (arylene ether nitrile) composition, is linked together between the two by aryl oxide key resistant to high temperature and phthalocyanine ring, and hybrid material is in film-form.Cyanalation redox graphene/poly (arylene ether nitrile) hybrid material is that self-crosslinking reaction occurs at high temperature by cyanalation redox graphene and phthalonitrile-terminated poly (arylene ether nitrile) to be prepared.By changing the content and high-temperature self-crosslinking reaction temperature, time of cyanalation redox graphene, a series of hybrid materials with high temperature resistant high dielectric property can be obtained.The glass transition temperature of the hybrid material is greater than 360 DEG C, and 5% thermal decomposition temperature is greater than 500 DEG C, and dielectric constant is greater than 15.0 in 1kHz, and dielectric loss is lower than 0.030 in 1kHz.The hybrid material belongs to high temperature polymeric materials manufacturing field, specifically can be used as high temperature resistant dielectric material.
Description
Technical field
The present invention relates to a kind of cyanalation redox graphene/poly (arylene ether nitrile) hybrid materials and preparation method thereof, belong to
High temperature polymeric materials manufacturing field.The hybrid material can be used as high temperature resistant dielectric applied to high temperature energy-storage field.
Background technique
Polyarylether polymer is wide due to its good heat resistance, corrosion resistance, insulating properties and excellent mechanical property
General applies in fields such as electronic material, aerospace, communication, defense military.Poly (arylene ether nitrile) belongs in polyarylether polymer
A member, its main feature is that its side group contains a large amount of functional cyano group.The introducing of highly polar cyano, so that polyarylether
The dielectric constant of nitrile is improved, generally between 3.5~4.5.However, due to the intrinsic glass transition temperature of poly (arylene ether nitrile)
Lower than 250 DEG C, can only be used in the environment of being lower than 250 DEG C.Fortunately, our it has been reported that can pass through parent early periods
Core substitution reaction allows the both ends of poly (arylene ether nitrile) strand to connect phthalonitrile groups, so that it is cross-linking to allow poly (arylene ether nitrile) to have
Property, resistance to hot of the product obtained after crosslinking are obviously improved, its use temperature range is increased.Heat resistance mentions
Height imparts poly (arylene ether nitrile) in the potential application of high-temperature resistant membrane capacitor area.
However, the dielectric constant of poly (arylene ether nitrile) is still relatively low compared to reported high density capacitors.In order to
It solves the problems, such as this, conductive filler or high dielectric filler and poly (arylene ether nitrile) is carried out compound and to improve its dielectric constant be mainstream
Method.Graphene is that a kind of carbon atom passes through sp2The 2D honeycomb structure planar formed after hydridization with Hexagonal array
Two-dimension nano materials have the characteristics such as excellent optics, electricity, mechanics.Therefore graphene and poly (arylene ether nitrile) can be answered
Close and obtain the composite material of high dielectric constant.But the composite material for being directly compounded to form graphene and poly (arylene ether nitrile)
Dielectric constant cannot be effectively improved, and the dielectric loss of the composite material obtained can be made to become larger instead.This is because graphite
Caused by alkene is incompatible with poly (arylene ether nitrile).Therefore, in order to improve the compatibility between graphene and poly (arylene ether nitrile), it is necessary to right
The surface of graphene carries out functionalization.The phthalonitrile that display sealing end poly (arylene ether nitrile) end has been reported can be sent out at high temperature
It is born from cross-linking reaction.It, can be with the neighbour of sealing end poly (arylene ether nitrile) end if connecting phthalonitrile groups on the surface of graphene
Benzene dicarbonitrile one reacts, and hybrid material is formed, so as to improve compatibility between the two.
There are reports at present carries out physics or chemical modification to graphene, then compound with poly (arylene ether nitrile) again, obtains
To the dielectric composite material with high-dielectric and low-loss.However, carefully studying, it can be seen that existing to graphene at present
Learning modification is all first to prepare graphene oxide, then recycles the oxygen-containing groups such as carboxyl, hydroxyl, the epoxy group of surface of graphene oxide
Group forms the linking groups such as ester bond, amido bond, cyanic acid ester bond and connects other function group, to realize modified purpose.But this
The heat resistance of a little linking groups is limited, can decompose at a high temperature of 350 DEG C or more, to influence the energy storage under its high temperature
Energy.Therefore, the high energy storage dielectric material of high temperature resistant is obtained, not only to introduce high dielectric filler, but also to change to filler
Property.In addition to this, the linking group between filler, modified group and the two is required to have characteristic resistant to high temperature, to protect
The high-temperature stability of card system.Phthalonitrile is directly connected to surface of graphene oxide using coupling process and obtains cyano by the present invention
Change graphene oxide, cyanalation redox graphene is then prepared by the method for electronation, is introduced into neighbour
Cyanalation redox graphene/poly (arylene ether nitrile) film composite material is prepared in the poly (arylene ether nitrile) matrix of benzene dicarbonitrile sealing end, most
The film is handled at high temperature afterwards and brings it about self-crosslinking reaction and obtains cyanalation redox graphene/poly (arylene ether nitrile) hydridization
Material is as high temperature resistant dielectric energy storage material.
Summary of the invention
Dielectric constant is not high enough when the purpose of the present invention is overcoming existing poly (arylene ether nitrile) as energy storage dielectric substance, introduces
Dielectric loss can significantly increase and existing modified group or linking group to graphene not technologies such as heatproof after graphene
Deficiency, provide it is a kind of prepare cyanalation redox graphene/poly (arylene ether nitrile) hybrid material method, realize the high energy storage of high temperature resistant
Prepared by the batch of thin dielectric film, solve the problems, such as that energy storage density is low under existing thin dielectric film non-refractory and high temperature, widens
The application range of thin dielectric film.Energy storage thin dielectric film high for high temperature resistant has great meaning in scientific research and application field
Justice.Specifically, first preparing graphene oxide, cyanalation graphene oxide is then prepared by coupling process, utilizes chemical reduction method
It is reduced to cyanalation redox graphene, then by the cyanalation redox graphene and phthalonitrile-terminated
Poly (arylene ether nitrile) is prepared into cyanalation redox graphene/poly (arylene ether nitrile) film composite material by solution film formation, finally will
The film composite material is handled at high temperature to be brought it about self-crosslinking reaction and obtains cyanalation redox graphene/poly (arylene ether nitrile)
Hybrid material is as the high energy storage dielectric material of high temperature resistant.
Described cyanalation redox graphene/poly (arylene ether nitrile) hybrid material and preparation method thereof, it is characterised in that: cyanogen
Base redox graphene/poly (arylene ether nitrile) hybrid material is by cyanalation redox graphene and phthalonitrile-terminated
The hybrid material of poly (arylene ether nitrile) composition, is linked together by phthalocyanine ring resistant to high temperature between the two, and hybrid material is in film-form,
Below preparation methods steps:
(1) preparation of graphene oxide: scale graphite, the concentrated sulfuric acid and concentrated phosphoric acid are added in flask, it is subject to 100~
Potassium permanganate is added into the system in the mechanical stirring of 300r/min, stirring while, adds and continues 10~30min of stirring, it
System is placed in afterwards in 40~80 DEG C of water-bath and 8~20h is stirred to react with the rate of 300~1000r/min, will obtained after reaction
Mixed liquor pour into concentrated sulfuric acid volume than in the deionized water for 1:1, with the mixing speed stirring 3 of 30~100r/min~
30% hydrogen peroxide is added while stirring until mixed liquor becomes golden yellow, by mixed liquor static 10 into system by 10min
Clear liquid above is outwelled after~30h, below turbid solution to repeat to be washed and be centrifuged with deionized water to pH value be 5.5~6.5,
Graphene oxide powder is obtained finally by the method for freeze-drying；Wherein, scale graphite, potassium permanganate, the concentrated sulfuric acid and dense phosphorus
The amount ratio of acid is 1g:(5~10g): (100~200mL): (10~20mL)；
(2) preparation of cyanalation graphene oxide: graphene oxide is distributed in n,N-Dimethylformamide, is made
Amino phthalonitrile, is then added in the dispersion liquid, and lead to by the dispersion liquid and 0.5~2h of ultrasound of 1.0~5.0mg/mL
Enter 5~10min of nitrogen that flow velocity is 0.05~1mL/min, isoamyl nitrite is added in above-mentioned reaction system later, instead
It answers system to react 8~20h at 50~100 DEG C, filters after reaction, filter cake is cleaned with n,N-Dimethylformamide to filtrate
It is colourless, filter cake is finally placed on in 50~100 DEG C of vacuum oven dry 20~50h and obtains cyanalation graphene oxide；Its
In, amino phthalonitrile is 4- (4 '-amino-benzene oxygen) phthalonitrile, 3- (4 '-amino-benzene oxygen) phthalonitrile, 4-
The mass ratio of one or more of amino phthalonitrile, graphene oxide and amino phthalonitrile is 1:(10~30), it is sub-
The volume ratio of isoamyl nitrate and N,N-dimethylformamide is 1:(50~200)；
(3) preparation of cyanalation redox graphene: being distributed to N for the cyanalation graphene oxide that step (2) obtains,
In dinethylformamide, the dispersion liquid and 0.5~2h of ultrasound of 1.0~5.0mg/mL is made, hydrazine hydrate is then added, 80~
At 120 DEG C react 4~12h, filter after reaction, filter cake cleaned with n,N-Dimethylformamide it is colourless to filtrate, finally will
Filter cake is placed in 50~100 DEG C of vacuum oven dry 20~50h and obtains cyanalation redox graphene, wherein cyano
The amount ratio for changing graphene oxide and hydrazine hydrate is 1g:(2~10mL)；
(4) cyanalation redox graphene/poly (arylene ether nitrile) film composite material preparation: step (3) is prepared
Cyanalation redox graphene and phthalonitrile-terminated poly (arylene ether nitrile) be added in N-Methyl pyrrolidone, ultrasound is stirred
It mixes 0.5~2h to be completely dissolved to phthalonitrile-terminated poly (arylene ether nitrile), then mixed system is poured into smooth glass plate
On, and 4~8h is dried in 100~200 DEG C of convection oven, room temperature is naturally cooled to later, takes film off from glass plate
Obtain cyanalation redox graphene/poly (arylene ether nitrile) film composite material；Wherein, cyanalation redox graphene and adjacent benzene
The poly (arylene ether nitrile) mass ratio of dimethoxy nitrile sealing end is 1:(10~100), phthalonitrile-terminated poly (arylene ether nitrile) and N- methylpyrrole
The amount ratio of alkanone is 1g:(10~20mL)；
(5) cyanalation redox graphene/poly (arylene ether nitrile) hybrid material preparation: the cyanogen that step (4) is prepared
Base redox graphene/poly (arylene ether nitrile) film composite material is placed in 2~10h of processing in 280~360 DEG C of high temperature oven,
Then room temperature is naturally cooled to, cyanalation redox graphene/poly (arylene ether nitrile) hybrid material is obtained.
Cyanalation redox graphene/poly (arylene ether nitrile) the hybrid material, it is characterised in that: the cyanalation oxygen reduction
Graphite alkene/poly (arylene ether nitrile) hybrid material glass transition temperature is greater than 360 DEG C or so, and 5% thermal decomposition temperature is greater than 500
DEG C, dielectric constant is greater than 15.0 in 1kHz, and dielectric loss is lower than 0.030 in 1kHz.
Beneficial effects of the present invention: in cyanalation redox graphene/poly (arylene ether nitrile) hybrid material produced by the present invention
Cyanalation redox graphene be uniformly dispersed in poly (arylene ether nitrile) matrix, cyanalation redox graphene and polyarylether
Nitrile is formed with machine-inorganic hybrid material by chemistry key connection, and the chemical bond for connecting the two is aryl oxide key resistant to high temperature and phthalein
Cyanines ring, they have excellent high temperature resistance.Cyanalation redox graphene/poly (arylene ether nitrile) hybrid material glass
Change transition temperature and be greater than 360 DEG C, 5% thermal decomposition temperature is greater than 500 DEG C.The method of the present invention can effectively regulate and control cyanalation reduction
The additional amount of graphene oxide, the dielectric constant of obtained hybrid material are greater than 15.0 in 1kHz, and dielectric loss is in 1kHz
Lower than 0.030, meet the application requirement of the thin film capacitor of resistance to 350 DEG C of high temperature.Cyanalation redox graphene of the invention/
The preparation method of poly (arylene ether nitrile) hybrid material is simple and easy to operate, easily realizes industrialization.
Detailed description of the invention
Fig. 1 is that cyanalation redox graphene prepares schematic diagram
Fig. 2 is cyanalation redox graphene/poly (arylene ether nitrile) hybrid material stereoscan photograph
Fig. 3 is cyanalation redox graphene/poly (arylene ether nitrile) hybrid material DMA figure
Fig. 4 is cyanalation redox graphene/poly (arylene ether nitrile) hybrid material TGA curve
Fig. 5 is cyanalation redox graphene/poly (arylene ether nitrile) hybrid material dielectric constant and dielectric loss figure
Specific embodiment
The embodiment of preparation method of the present invention introduced below, but following embodiment be for illustrating example of the invention, and
Any restriction to the claims in the present invention is not constituted.
Embodiment 1
The schematic diagram for preparing cyanalation redox graphene is as shown in Fig. 1.
(1) 1.5g scale graphite, the 180mL concentrated sulfuric acid and 20mL concentrated phosphoric acid the preparation of graphene oxide: are added to 500mL
Three-necked flask in, be subject to the mechanical stirring of 120r/min, stirring while, 9g potassium permanganate was added into the system, add after
System, is placed in 50 DEG C of water-bath later and is stirred to react 12h with the rate of 600r/min by continuous stirring 30min, will obtain after reaction
To mixed liquor pour into concentrated sulfuric acid volume than in the deionized water for 1:1,5min is stirred with the mixing speed of 60r/min, is stirred
30% hydrogen peroxide is added while mixing into system until mixed liquor becomes golden yellow, will be outwelled after the static 20h of mixed liquor
Clear liquid above, below turbid solution to repeat to be washed and be centrifuged with deionized water to pH value be 5.5~6.5, finally by cold
Dry method is lyophilized and obtains graphene oxide powder；
(2) 0.4g graphene oxide the preparation of cyanalation graphene oxide: is distributed to the N of 100mL, N- dimethyl formyl
In amine, then the 4- of 1.6g (4 '-amino-benzene oxygen) phthalonitrile is added to this point by manufactured dispersion liquid and ultrasound 0.5h
In dispersion liquid, and it is passed through the nitrogen 5min that flow velocity is 1mL/min, the isoamyl nitrite of 1.2mL is added to above-mentioned reaction later
In system, reaction system reacts 12h at 80 DEG C, filters after reaction, and filter cake is cleaned with n,N-Dimethylformamide to filter
Liquid is colourless, and filter cake is finally placed on in 80 DEG C of vacuum oven dry 20h and obtains cyanalation graphene oxide；
(3) product that step (2) obtains the preparation of cyanalation redox graphene: is distributed to N, N- dimethyl formyl
In amine, the dispersion liquid and ultrasound 1h of 2.0mg/mL is made, 80% hydrazine hydrate of 2.5mL is then added, is reacted at 100 DEG C
6h is filtered after reaction, and filter cake is cleaned colourless to filtrate with n,N-Dimethylformamide, and filter cake is finally placed on 80 DEG C true
Dry 20h obtains cyanalation redox graphene in empty drying box；
(4) cyanalation redox graphene/poly (arylene ether nitrile) film composite material preparation: step (3) is prepared
Cyanalation redox graphene 0.1g and phthalonitrile-terminated poly (arylene ether nitrile) 0.9g be added to the N- methyl pyrrole of 15mL
In pyrrolidone, ultrasonic agitation 1h is completely dissolved to phthalonitrile-terminated poly (arylene ether nitrile), is then poured into mixed system flat
On whole glass plate, and 1h is respectively dried in 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C, 180 DEG C and 200 DEG C of convection oven,
Room temperature is naturally cooled to later, and taking film off from glass plate, to obtain cyanalation redox graphene/poly (arylene ether nitrile) film multiple
Condensation material；
(5) cyanalation redox graphene/poly (arylene ether nitrile) hybrid material preparation: the cyanogen that step (4) is prepared
Base redox graphene/poly (arylene ether nitrile) film composite material is placed in 320 DEG C, 340 DEG C and 350 DEG C of high temperature oven respectively
2h is handled, room temperature is then naturally cooled to, obtains cyanalation redox graphene/poly (arylene ether nitrile) hybrid material.
Cyanalation redox graphene/poly (arylene ether nitrile) hybrid material the stereoscan photograph is as shown in Fig. 2, from the figure
It can be seen that cyano carbon nano tube is uniformly dispersed in poly (arylene ether nitrile) matrix, DMA figure as shown in Fig. 3, can from the figure
To find out the glass transition temperature of the hybrid material for 370.5 DEG C, TGA figure as shown in Fig. 4, as can be seen from this figure should
5% thermal decomposition temperature of hybrid material is 530 DEG C, and dielectric constant and dielectric loss are as shown in Fig. 5, as can be seen from this figure
The hybrid material dielectric constant is 19.5 at 1 khz, and dielectric loss is 0.028 at 1 khz.
Embodiment 2
(1) preparation of graphene oxide: consistent with the process in embodiment 1；
(2) preparation of cyanalation graphene oxide: consistent with the process in embodiment 1；
(3) preparation of cyanalation redox graphene: consistent with the process in embodiment 1；
(4) cyanalation redox graphene/poly (arylene ether nitrile) film composite material preparation: step (3) is prepared
Cyanalation redox graphene 0.05g and phthalonitrile-terminated poly (arylene ether nitrile) 0.95g be added to the N- methyl of 15mL
In pyrrolidones, ultrasonic agitation 1h is completely dissolved to phthalonitrile-terminated poly (arylene ether nitrile), is then poured into mixed system
On smooth glass plate, and it is respectively dried in 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C, 180 DEG C and 200 DEG C of convection oven
1h naturally cools to room temperature later, takes film off from glass plate and obtains cyanalation redox graphene/poly (arylene ether nitrile) film
Composite material；
(5) cyanalation redox graphene/poly (arylene ether nitrile) hybrid material preparation: consistent with the process in embodiment 1.
Cyanalation redox graphene uniformly divides in the cyanalation redox graphene/poly (arylene ether nitrile) hybrid material
It being dispersed in poly (arylene ether nitrile) matrix, the glass transition temperature of the hybrid material is 368.0 DEG C, and 5% thermal decomposition temperature is 525 DEG C,
The hybrid material dielectric constant is 12.5 at 1 khz, and dielectric loss is 0.018 at 1 khz.
Embodiment 3
(1) preparation of graphene oxide: consistent with the process in embodiment 1；
(2) preparation of cyanalation graphene oxide: consistent with the process in embodiment 1；
(3) preparation of cyanalation redox graphene: consistent with the process in embodiment 1；
(4) cyanalation redox graphene/poly (arylene ether nitrile) film composite material preparation: step (3) is prepared
Cyanalation redox graphene 0.02g and phthalonitrile-terminated poly (arylene ether nitrile) 0.98g be added to the N- methyl of 15mL
In pyrrolidones, ultrasonic agitation 1h is completely dissolved to phthalonitrile-terminated poly (arylene ether nitrile), is then poured into mixed system
On smooth glass plate, and it is respectively dried in 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C, 180 DEG C and 200 DEG C of convection oven
1h naturally cools to room temperature later, takes film off from glass plate and obtains cyanalation redox graphene/poly (arylene ether nitrile) film
Composite material；
(5) cyanalation redox graphene/poly (arylene ether nitrile) hybrid material preparation: consistent with the process in embodiment 1.
Cyanalation redox graphene in the cyanalation redox graphene/poly (arylene ether nitrile) hybrid material/uniform
It is dispersed in poly (arylene ether nitrile) matrix, the glass transition temperature of the hybrid material is 365.3 DEG C, and 5% thermal decomposition temperature is 522
DEG C, which is 9.5 at 1 khz, and dielectric loss is 0.016 at 1 khz.
Embodiment 4
(1) preparation of graphene oxide: consistent with the process in embodiment 1；
(2) 0.4g graphene oxide the preparation of cyanalation graphene oxide: is distributed to the N of 100mL, N- dimethyl formyl
In amine, then the 3- of 1.6g (4 '-amino-benzene oxygen) phthalonitrile is added to this point by manufactured dispersion liquid and ultrasound 0.5h
In dispersion liquid, and it is passed through the nitrogen 5min that flow velocity is 1mL/min, the isoamyl nitrite of 1.2mL is added to above-mentioned reaction later
In system, reaction system reacts 12h at 80 DEG C, filters after reaction, and filter cake is cleaned with n,N-Dimethylformamide to filter
Liquid is colourless, and filter cake is finally placed on in 80 DEG C of vacuum oven dry 20h and obtains cyanalation graphene oxide；
(3) preparation of cyanalation redox graphene: consistent with the process in embodiment 1；
(4) cyanalation redox graphene/poly (arylene ether nitrile) film composite material preparation: with the process in embodiment 1
Unanimously；
(5) cyanalation redox graphene/poly (arylene ether nitrile) hybrid material preparation: consistent with the process in embodiment 1.
Cyanalation redox graphene uniformly divides in the cyanalation redox graphene/poly (arylene ether nitrile) hybrid material
It being dispersed in poly (arylene ether nitrile) matrix, the glass transition temperature of the hybrid material is 370.1 DEG C, and 5% thermal decomposition temperature is 531 DEG C,
The hybrid material dielectric constant is 20.5 at 1 khz, and dielectric loss is 0.026 at 1 khz.
Embodiment 5
(1) preparation of graphene oxide: consistent with the process in embodiment 1；
(2) 0.4g graphene oxide the preparation of cyanalation graphene oxide: is distributed to the N of 100mL, N- dimethyl formyl
In amine, then the 4 ' of 1.6g-amino phthalonitriles are added in the dispersion liquid by manufactured dispersion liquid and ultrasound 0.5h, and
It is passed through the nitrogen 5min that flow velocity is 1mL/min, the isoamyl nitrite of 1.2mL is added in above-mentioned reaction system later, instead
Answer system to react 12h at 80 DEG C, filter after reaction, filter cake cleaned with n,N-Dimethylformamide it is colourless to filtrate, most
Filter cake is placed on in 80 DEG C of vacuum oven dry 20h afterwards and obtains cyanalation graphene oxide；
(3) preparation of cyanalation redox graphene: consistent with the process in embodiment 1；
(4) cyanalation redox graphene/poly (arylene ether nitrile) film composite material preparation: with the process in embodiment 1
Unanimously；
(5) cyanalation redox graphene/poly (arylene ether nitrile) hybrid material preparation: consistent with the process in embodiment 1.
Cyanalation redox graphene uniformly divides in the cyanalation redox graphene/poly (arylene ether nitrile) hybrid material
It being dispersed in poly (arylene ether nitrile) matrix, the glass transition temperature of the hybrid material is 372.1 DEG C, and 5% thermal decomposition temperature is 533 DEG C,
The hybrid material dielectric constant is 21.4 at 1 khz, and dielectric loss is 0.027 at 1 khz.
Embodiment 6
(1) preparation of graphene oxide: consistent with the process in embodiment 1；
(2) preparation of cyanalation graphene oxide: consistent with the process in embodiment 1；
(3) preparation of cyanalation redox graphene: consistent with the process in embodiment 1；
(4) cyanalation redox graphene/poly (arylene ether nitrile) film composite material preparation: with the process in embodiment 1
Unanimously；
(5) cyanalation redox graphene/poly (arylene ether nitrile) hybrid material preparation: the cyanogen that step (4) is prepared
Base redox graphene/poly (arylene ether nitrile) film composite material is placed in 320 DEG C and 340 DEG C of high temperature oven and handles respectively
Then 2h naturally cools to room temperature, obtain cyanalation redox graphene/poly (arylene ether nitrile) hybrid material.
Cyanalation redox graphene uniformly divides in the cyanalation redox graphene/poly (arylene ether nitrile) hybrid material
It being dispersed in poly (arylene ether nitrile) matrix, the glass transition temperature of the hybrid material is 360.5 DEG C, and 5% thermal decomposition temperature is 513 DEG C,
The hybrid material dielectric constant is 18.4 at 1 khz, and dielectric loss is 0.027 at 1 khz.
Embodiment 7
(1) preparation of graphene oxide: consistent with the process in embodiment 1；
(2) preparation of cyanalation graphene oxide: consistent with the process in embodiment 1；
(3) preparation of cyanalation redox graphene: consistent with the process in embodiment 1；
(4) cyanalation redox graphene/poly (arylene ether nitrile) film composite material preparation: with the process in embodiment 1
Unanimously；
(5) cyanalation redox graphene/poly (arylene ether nitrile) hybrid material preparation: the cyanogen that step (4) is prepared
Base redox graphene/poly (arylene ether nitrile) film composite material is placed in 320 DEG C, 340 DEG C, 340 DEG C and 360 DEG C of high temperature oven
It is middle to handle 2h respectively, room temperature is then naturally cooled to, cyanalation redox graphene/poly (arylene ether nitrile) hybrid material is obtained.
Cyanalation redox graphene uniformly divides in the cyanalation redox graphene/poly (arylene ether nitrile) hybrid material
It being dispersed in poly (arylene ether nitrile) matrix, the glass transition temperature of the hybrid material is 385.5 DEG C, and 5% thermal decomposition temperature is 543 DEG C,
The hybrid material dielectric constant is 20.2 at 1 khz, and dielectric loss is 0.024 at 1 khz.
Claims (2)
1. a kind of cyanalation redox graphene/poly (arylene ether nitrile) hybrid material, it is characterised in that: the hybrid material is cyanalation
The hybrid material of redox graphene and phthalonitrile-terminated poly (arylene ether nitrile) composition, passes through virtue resistant to high temperature between the two
Ehter bond and phthalocyanine ring link together, which is in film-form, and the glass transition temperature of the hybrid material is greater than 360
DEG C, 5% thermal decomposition temperature is greater than 500 DEG C, and dielectric constant is greater than 15.0 in 1kHz, and dielectric loss is lower than 0.030 in 1kHz.
2. cyanalation redox graphene/poly (arylene ether nitrile) hybrid material according to claim 1, it is characterised in that: its
Below preparation method step:
(1) preparation of graphene oxide: scale graphite, the concentrated sulfuric acid and concentrated phosphoric acid are added in flask, 100~300r/ is subject to
Potassium permanganate is added into the system in the mechanical stirring of min, stirring while, adds and continues 10~30min of stirring, later by body
System, which is placed in 40~80 DEG C of water-bath, is stirred to react 8~20h with the rate of 300~1000r/min, the mixing that will be obtained after reaction
Liquid is poured into concentrated sulfuric acid volume than stirring 3~10min with the mixing speed of 30~100r/min, stirring in the deionized water for 1:1
30% hydrogen peroxide is added while mixing into system until mixed liquor becomes golden yellow, after the static 10~30h of mixed liquor
Outwell clear liquid above, below turbid solution to repeat to be washed and be centrifuged with deionized water to pH value be 5.5~6.5, finally lead to
The method for crossing freeze-drying obtains graphene oxide powder；Wherein, the use of scale graphite, potassium permanganate, the concentrated sulfuric acid and concentrated phosphoric acid
Amount is than being 1g:(5~10g): (100~200mL): (10~20mL)；
(2) preparation of cyanalation graphene oxide: graphene oxide is distributed in n,N-Dimethylformamide, it is made 1.0~
Amino phthalonitrile, is then added in the dispersion liquid, and be passed through flow velocity by the dispersion liquid and 0.5~2h of ultrasound of 5.0mg/mL
For 5~10min of nitrogen of 0.05~1mL/min, isoamyl nitrite is added in above-mentioned reaction system later, reaction system
At 50~100 DEG C react 8~20h, filter after reaction, filter cake cleaned with n,N-Dimethylformamide it is colourless to filtrate,
Filter cake is finally placed on in 50~100 DEG C of vacuum oven dry 20~50h and obtains cyanalation graphene oxide；Wherein, ammonia
Base phthalonitrile is 4- (4 '-amino-benzene oxygen) phthalonitrile, 3- (4 '-amino-benzene oxygen) phthalonitrile, 4- amino
The mass ratio of one or more of phthalonitrile, graphene oxide and amino phthalonitrile is 1:(10~30), nitrous acid
The volume ratio of isopentyl ester and N,N-dimethylformamide is 1:(50~200)；
(3) the cyanalation graphene oxide that step (2) obtains the preparation of cyanalation redox graphene: is distributed to N, N- bis-
In methylformamide, the dispersion liquid and 0.5~2h of ultrasound of 1.0~5.0mg/mL is made, hydrazine hydrate is then added, 80~120
At DEG C react 4~12h, filter after reaction, filter cake cleaned with n,N-Dimethylformamide it is colourless to filtrate, finally by filter cake
It is placed in 50~100 DEG C of vacuum oven dry 20~50h and obtains cyanalation redox graphene, wherein cyanalation oxygen
The amount ratio of graphite alkene and hydrazine hydrate is 1g:(2~10mL)；
(4) cyanalation redox graphene/poly (arylene ether nitrile) film composite material preparation: the cyanogen that step (3) is prepared
Base redox graphene and phthalonitrile-terminated poly (arylene ether nitrile) are added in N-Methyl pyrrolidone, are stirred by ultrasonic
0.5~2h is completely dissolved to phthalonitrile-terminated poly (arylene ether nitrile), is then poured into mixed system on smooth glass plate,
And 4~8h is dried in 100~200 DEG C of convection oven, room temperature is naturally cooled to later, is taken film off from glass plate and is obtained
Cyanalation redox graphene/poly (arylene ether nitrile) film composite material；Wherein, cyanalation redox graphene and O-phthalic
The poly (arylene ether nitrile) mass ratio of nitrile sealing end is 1:(10~100), phthalonitrile-terminated poly (arylene ether nitrile) and N-Methyl pyrrolidone
Amount ratio be 1g:(10~20mL)；
(5) cyanalation redox graphene/poly (arylene ether nitrile) hybrid material preparation: step (4) is prepared cyanalation
Redox graphene/poly (arylene ether nitrile) film composite material is placed in 2~10h of processing in 280~360 DEG C of high temperature oven, then
Room temperature is naturally cooled to, cyanalation redox graphene/poly (arylene ether nitrile) hybrid material is obtained.
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| CN113603887A (en) * | 2021-09-02 | 2021-11-05 | 大同共聚(西安)科技有限公司 | Preparation method of barium titanate and polyimide hybrid material |
| CN113604047A (en) * | 2021-09-02 | 2021-11-05 | 大同共聚(西安)科技有限公司 | Preparation method of boron nitride graphene oxide polyimide composite material |
| CN113603887B (en) * | 2021-09-02 | 2023-01-17 | 大同共聚(西安)科技有限公司 | Preparation method of barium titanate and polyimide hybrid material |
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