CN105732917B - A kind of preparation method of redox graphene graft polypropylene nitrile - Google Patents
A kind of preparation method of redox graphene graft polypropylene nitrile Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/26—Cellulose ethers
- C08L1/28—Alkyl ethers
- C08L1/288—Alkyl ethers substituted with nitrogen-containing radicals
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- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/26—Cellulose ethers
- C08J2301/28—Alkyl ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/10—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to inorganic materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Abstract
The present invention relates to a kind of preparation methods of redox graphene graft polypropylene nitrile；Purpose is to provide that a kind of time-consuming is short, energy consumption is low, at low cost and is suitable for industrialized preparing redox graphene graft polypropylene nitrile method.Acrylonitrile monemer is added into water in graphene oxide ultrasonic disperse in high-speed stirred, initiator is added under inert gas shielding and is uniformly mixed, and reaction obtains the washing of graphene oxide graft polypropylene nitrile, drying in microwave reactor；Graphene graft polypropylene nitrile is scattered in solvent, and reducing agent is added and reacts in microwave reactor, washs, be drying to obtain product.Using method of the invention prepare redox graphene graft polypropylene nitrile equipment and operating process it is simple, the period is extremely short, reproducible, at low cost, has practical application value；The composite membrane dielectric properties of preparation are higher, and dielectric loss is lower, can be applied to electronics, motor and cable industry, and also have application prospect in fields such as artificial-muscle, absorbing material and medicament slow releases.
Description
Technical field
The present invention relates to a kind of preparation methods of modified graphene, and in particular to a kind of redox graphene grafting poly- third
The preparation method of alkene nitrile.
Background technique
Graphene (Graphene) is graphite type material, with the basic unit of sp2 hybrid structure and two-dimensional monatomic
Layer, is the most thin two-dimensional material found at present.Due to the excellent electricity of graphene, calorifics, machinery and biocompatibility etc.
Property attracted the concern of more and more scientific research personnel.Just because of graphene, these special and excellent characteristics, make it
As nanoscale elements modify and be doped in polymer, obtain composite material, can effectively improve polymer power, heat, light,
Performance electrically and magnetically etc., so that graphene and its composite material are in energy field, chemical catalysis field, electrotechnical, electronic neck
The fields such as domain, field of biomedicine, aerospace field show wide application prospect.Its main preparation methods is chemical oxygen
Change method: Brodie method, Staudenmaier method, Hummers method and improvement Hummers method, wherein Hummers and improvement
Hummers method is present main stream approach since its reaction process is relatively easy, toxicity is lower.
Grapheme material has excellent performance, but its large specific surface area is easy to happen reunion, and multiple in polymer matrix
Compatibility in condensation material as filler and matrix is poor, this is greatly unfavorable for the application prospect of graphene.Therefore, various countries are ground
Study carefully personnel to fall over each other to study it, it is desirable to be able to find suitable improved method and graphene is made to can be improved compatibility.Have
The study found that carrying out graft modification to graphene surface can be improved its dispersibility or dissolubility in a solvent, also can be improved
The compatibility of redox graphene and matrix.There are research and the report that graft modification is much carried out to graphene in recent years, such as
The patent that Authorization Notice No. is 102040714 B of CN and Authorization Notice No. is CN102586922B discloses a kind of polymer and connects
The preparation method of branch graphene, but traditional polymerization is all used, not only time-consuming, but also it is also big to consume energy, this is also mesh
The maximum restriction that preceding grapheme material industrial applications are subject to.So reducing energy consumption while improving grafting efficiency, shorten anti-
It is a great problem and the challenge of graft polymerization reaction between seasonable.Graphene modification also needs into one the industrial application of graphene
Step research and development and improvement.
Summary of the invention
The purpose of the invention is to provide, a kind of time-consuming is short, energy consumption is low, at low cost and is suitable for industrialized preparation is restored
Graphene oxide graft polypropylene nitrile method.
To achieve the above object, the technical solution adopted by the present invention is that: a kind of redox graphene graft polypropylene nitrile
Preparation method comprising steps of
A. it adds graphene oxide into ultrasonic disperse in water and obtains graphene oxide aqueous dispersions, in above-mentioned dispersion in stirring
Acrylonitrile monemer is added in system, initiator is added under inert gas shielding, is uniformly mixed；
B. mixed system microwave grafting in microwave reactor is put into react to obtain graphene oxide graft polypropylene nitrile
Washing, drying；
C. it disperses the graphene graft polypropylene nitrile that step B is obtained in solvent, reducing agent is added, is placed in microwave reaction
Microwave reduction reacts in device, washs, is drying to obtain product.
Further, the microwave grafting reaction condition is 40-60 DEG C of temperature, reaction time 5-25min, microwave power
For 100-900W；The microwave reduction reaction condition is 80-95 DEG C of temperature, reaction time 1-25min, microwave power 100-
900W。
Further, the mass ratio of the graphene oxide and acrylonitrile monemer is 1:(10-500), initiator and propylene
The molar ratio of nitrile monomer is (3-5): 1000.
Further, the initiator is potassium peroxydisulfate, ammonium persulfate, ammonium ceric nitrate, sodium hydrogensulfite, benzoyl peroxide first
Acyl, azodiisobutyronitrile, any one in azobisisoheptonitrile.
Further, solvent used in the step C be water, n,N-Dimethylformamide, n,N-dimethylacetamide,
The mixing of one or more of N-Methyl pyrrolidone；The dosage of the solvent and the mass ratio of raw material graphene oxide are (1-
1000): 1.
Further, the reducing agent is phenylhydrazine or hydrazine hydrate, and dosage is that reducing agent is added in every milligram of graphene oxide
0.1-10μL.Every graphene oxide that 1mg is added in namely step A, the reducing agent that when reduction uses are 0.1-10 μ L.
Further, the drying process is dry under vacuum condition, and drying temperature is no more than 60 DEG C；The step
Ultrasound condition is the ultrasonic disperse 2h in the ultrasonic cleaning machine of 200W in A.Disperse 2h under the ultrasound condition of 200W.
Above-mentioned redox graphene graft polypropylene nitrile prepares high dielectric nano composite membrane with cyanethyl cellulose
Matrix is configured to solution with casting solution, through casting film-forming system using redox graphene graft polypropylene product as filler
?；The cyanethyl cellulose, redox graphene graft polypropylene product, casting solution mass ratio are as follows: 10:(0.5-
2): (400-500)；The casting solution is N,N-dimethylformamide.That is after solution curtain coating is laid on film plate,
Casting solution volatilizees after drying, finally obtains high dielectric nano composite membrane.
Further, after the nano composite membrane is dry with a thickness of 0.030-0.100mm.
Further, the cyanethyl cellulose degree of substitution is 2.4-2.6, the polyacrylonitrile-grafted modified graphene
Grafting rate be 20%-70%.
Redox graphene graft polypropylene nitrile product and high dielectric nano composite membrane tool are prepared using the method for the present invention
It has the following advantages:
1. the equipment and the operating process that prepare redox graphene graft polypropylene nitrile are simple, the period is extremely short, repeatability
It is good, it is at low cost, there is practical application value.This other similarly suitable a series of vinyl monomers of mode and graphene carry out
It is graft-polymerized, therefore has good application prospect in the covalent modified field of graphene；
2. the present invention prepares redox graphene graft polypropylene nitrile using microwave method, microwave method graft modification has been filled up
The blank of graphene opens the new way of graphene graft modification；Invention further define microwave reaction system raw material proportioning,
Solvent usage, initiator and reducing agent dosage etc. are matched by controlling time, temperature and the power of microwave reaction using described
Modified graphene square then that different grafting rates can be made.
3. the redox graphene graft polypropylene nitrile of preparation has fabulous solubility property and electric conductivity.
4. the flexible high dielectric nano composite membrane of the cyanethyl cellulose being prepared/polyacrylonitrile-grafted modified graphene
Dielectric properties are higher, and dielectric loss is lower, can be applied to electronics, motor and cable industry, and in artificial-muscle, suction wave material
Also there is certain application prospect in the fields such as material and medicament slow release；The cyanethyl cellulose being prepared/polyacrylonitrile-grafted modified
The flexible high dielectric nano composite film surface of graphene is glossy, and good appearance has certain flexibility and good mechanicalness
Energy and hot property.
5. the flexible high dielectric nano composite membrane of the cyanethyl cellulose being prepared/polyacrylonitrile-grafted modified graphene is raw
Method safety is produced, process is simple, and production cost is low, therefore good market prospect.
Specific embodiment
The present invention will be further described combined with specific embodiments below.The embodiment is only preferred implementation of the invention
Example, is not intended to restrict the invention, for those skilled in the art, the present invention can have various changes and change
Change.All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in the present invention
Protection scope within.In embodiment one to five, the dielectric properties of product are surveyed using Agilent 4294A impedance analyzer
Fixed, thermal stability is measured using TG-DTA 6200LAB SYS type thermogravimetric differential thermal synthesis thermal analyzer, ultrasonic in embodiment
Dispersion steps are to disperse 2h under the ultrasound condition of 200W.
Embodiment one
20mg graphene oxide, 200ml water are added in reaction flask, 10g acrylonitrile monemer is added in ultrasonic disperse 30min,
0.43g ammonium persulfate is added under nitrogen atmosphere, is placed in microwave reactor.The microwave setting reaction time is 10min, temperature 60
DEG C, power 600W.Centrifugation, washing, 60 DEG C of vacuum drying.
Above-mentioned products therefrom is dissolved in n,N-Dimethylformamide, 10 μ L phenylhydrazines are added, are placed in microwave reactor,
Be arranged reaction time 25min, 95 DEG C of reaction temperature, microwave power 800W.Precipitating, centrifugation, washing, 60 DEG C of vacuum drying are gone back
Former graphene oxide graft polypropylene nitrile.Grafting rate is 22.4%.
0.6g cyanethyl cellulose is dissolved in 18g DMF, magnetic agitation 2h, is dissolved.Polypropylene made from 0.006g
Nitrile graft modification graphene is dissolved in 6g DMF, stirs 3h, ultrasonic disperse 2h.By dissolved polyacrylonitrile-grafted modified stone
Black alkene is added in the solution of cyanethyl cellulose, obtains mixed solution, magnetic agitation is for 24 hours.Film forming solution is poured on surface plate
It is interior, it is placed in 60 DEG C of dry 48h or so in baking oven, takes off film after cooling, cyanethyl cellulose/polyacrylonitrile-grafted modified can be obtained
The flexible high dielectric nano composite membrane of graphene.Cyanethyl cellulose obtained/polyacrylonitrile-grafted modified graphene flexibility Gao Jie
Electric nano composite membrane finished product component includes: cyanethyl cellulose 0.6g, polyacrylonitrile-grafted modified graphene 0.006g.
With the performance of the high dielectric flexible nano composite membrane of the standby cyanethyl cellulose base of this component and weight in grams numeral system are as follows: be situated between
Electric constant and dielectric loss are respectively 16.9 and 0.234 (100Hz)；First stage thermal decomposition temperature and second stage thermal decomposition temperature
Degree is respectively 267.2 DEG C and 321 DEG C.
Embodiment two
20mg graphene oxide, 200ml water are added in reaction flask, 10g acrylonitrile monemer is added in ultrasonic disperse 30min,
0.43g ammonium persulfate is added under nitrogen atmosphere, is placed in microwave reactor.The microwave setting reaction time is 15min, temperature 60
DEG C, power 600W.Centrifugation, washing, 60 DEG C of vacuum drying.
Above-mentioned products therefrom is dissolved in n,N-Dimethylformamide, 10 μ L phenylhydrazines are added, are placed in microwave reactor,
Be arranged reaction time 15min, 95 DEG C of reaction temperature, microwave power 800W.Precipitating, centrifugation, washing, 60 DEG C of vacuum drying are gone back
Former graphene oxide graft polypropylene nitrile.Grafting rate is 37.3%.
0.6g cyanethyl cellulose is dissolved in 18g DMF, magnetic agitation 2h, is dissolved.Polypropylene made from 0.018g
Nitrile graft modification graphene is dissolved in 12g DMF, stirs 3h, ultrasonic disperse 2h.It will be dissolved polyacrylonitrile-grafted modified
Graphene is added in the solution of cyanethyl cellulose, obtains mixed solution, magnetic agitation is for 24 hours.Film forming solution is poured on surface
In ware, 60 DEG C of dry 48h or so in baking oven are placed in, film is taken off after cooling, cyanethyl cellulose/polyacrylonitrile graft can be obtained and change
Property the flexible high dielectric nano composite membrane of graphene.Cyanethyl cellulose obtained/polyacrylonitrile-grafted modified graphene is flexible high
Dielectric nano composite membrane finished product component includes: cyanethyl cellulose 0.6g, polyacrylonitrile-grafted modified graphene 0.018g.
With the performance of the high dielectric flexible nano composite membrane of the standby cyanethyl cellulose base of this component and weight in grams numeral system are as follows: be situated between
Electric constant and dielectric loss are respectively 18.58 and 0.167 (100Hz)；First stage thermal decomposition temperature and second stage thermal decomposition
Temperature is respectively 265.4 DEG C and 315 DEG C.
Embodiment three
20mg graphene oxide, 200ml water are added in reaction flask, 20g acrylonitrile monemer is added in ultrasonic disperse 30min,
0.43g potassium peroxydisulfate is added under nitrogen atmosphere, is placed in microwave reactor.The microwave setting reaction time is 10min, temperature 60
DEG C, power 600W.Centrifugation, washing, 60 DEG C of vacuum drying.
Above-mentioned products therefrom is dissolved in n,N-dimethylacetamide, 15 μ L phenylhydrazines are added, are placed in microwave reactor,
Be arranged reaction time 25min, 95 DEG C of reaction temperature, microwave power 800W.Precipitating, centrifugation, washing, 60 DEG C of vacuum drying are gone back
Former graphene oxide graft polypropylene nitrile.Grafting rate is 53.6%.
0.6g cyanethyl cellulose is dissolved in 18g DMF, magnetic agitation 2h, is dissolved.Polypropylene made from 0.006g
Nitrile graft modification graphene is dissolved in 12g DMF, stirs 3h, ultrasonic disperse 2h.It will be dissolved polyacrylonitrile-grafted modified
Graphene is added in the solution of cyanethyl cellulose, obtains mixed solution, magnetic agitation is for 24 hours.Film forming solution is poured on surface
In ware, 60 DEG C of dry 48h or so in baking oven are placed in, film is taken off after cooling, cyanethyl cellulose/polyacrylonitrile graft can be obtained and change
Property the flexible high dielectric nano composite membrane of graphene.Cyanethyl cellulose obtained/polyacrylonitrile-grafted modified graphene is flexible high
Dielectric nano composite membrane finished product component includes: cyanethyl cellulose 0.6g, polyacrylonitrile-grafted modified graphene 0.042g.
With the performance of the high dielectric flexible nano composite membrane of the standby cyanethyl cellulose base of this component and weight in grams numeral system are as follows: be situated between
Electric constant and dielectric loss are respectively 20.00 and 0.142 (100Hz)；First stage thermal decomposition temperature and second stage thermal decomposition
Temperature is respectively 266.6 DEG C and 318.6 DEG C.
Example IV
20mg graphene oxide, 200ml water are added in reaction flask, 10g acrylonitrile monemer is added in ultrasonic disperse 30min,
0.43g ammonium persulfate and 0.19g sodium hydrogensulfite are added under nitrogen atmosphere, is placed in microwave reactor.When microwave setting reaction
Between be 10min, temperature 60 C, power 600W.Centrifugation, washing, 60 DEG C of vacuum drying.
Above-mentioned products therefrom is dissolved in n,N-Dimethylformamide, 10 μ L phenylhydrazines are added, are placed in microwave reactor,
Be arranged reaction time 25min, 95 DEG C of reaction temperature, microwave power 800W.Precipitating, centrifugation, washing, 60 DEG C of vacuum drying are gone back
Former graphene oxide graft polypropylene nitrile.Grafting rate is 66.0%.
0.6g cyanethyl cellulose is dissolved in 18g DMF, magnetic agitation 2h, is dissolved.Polypropylene made from 0.006g
Nitrile graft modification graphene is dissolved in 6g DMF, stirs 3h, ultrasonic disperse 2h.By dissolved polyacrylonitrile-grafted modified stone
Black alkene is added in the solution of cyanethyl cellulose, obtains mixed solution, magnetic agitation is for 24 hours.Film forming solution is poured on surface plate
It is interior, it is placed in 60 DEG C of dry 48h or so in baking oven, takes off film after cooling, cyanethyl cellulose/polyacrylonitrile-grafted modified can be obtained
The flexible high dielectric nano composite membrane of graphene.Cyanethyl cellulose obtained/polyacrylonitrile-grafted modified graphene flexibility Gao Jie
Electric nano composite membrane finished product component includes: cyanethyl cellulose 0.6g, polyacrylonitrile-grafted modified graphene 0.006g.
With the performance of the high dielectric flexible nano composite membrane of the standby cyanethyl cellulose base of this component and weight in grams numeral system are as follows: be situated between
Electric constant and dielectric loss are respectively 20.187 and 0.142 (100HZ)；First stage thermal decomposition temperature and second stage thermal decomposition
Temperature is respectively 269.6 DEG C and 312 DEG C.
Embodiment five
20mg graphene oxide is added in reaction flask, 10g acrylonitrile monemer, nitrogen is added in 200mlDMF, ultrasonic disperse 2h
0.06g benzoyl peroxide is added under gas atmosphere, is placed in microwave reactor.The microwave setting reaction time is 10min, temperature 60
DEG C, power 600W.Centrifugation, washing, 60 DEG C of vacuum drying.
Above-mentioned products therefrom is dissolved in N-Methyl pyrrolidone, 10 μ L phenylhydrazines are added, are placed in microwave reactor, if
Set reaction time 25min, 95 DEG C of reaction temperature, microwave power 800W.Precipitating, centrifugation, washing, 60 DEG C of vacuum drying are restored
Graphene oxide graft polypropylene nitrile.Grafting rate is 12%.
0.6g cyanethyl cellulose is dissolved in 18g DMF, magnetic agitation 2h, is dissolved.Polypropylene made from 0.012g
Nitrile graft modification graphene is dissolved in 6g DMF, stirs 3h, ultrasonic disperse 2h.By dissolved polyacrylonitrile-grafted modified stone
Black alkene is added in the solution of cyanethyl cellulose, obtains mixed solution, magnetic agitation is for 24 hours.Film forming solution is poured on surface plate
It is interior, it is placed in 60 DEG C of dry 48h or so in baking oven, takes off film after cooling, cyanethyl cellulose/polyacrylonitrile-grafted modified can be obtained
The flexible high dielectric nano composite membrane of graphene.Cyanethyl cellulose obtained/polyacrylonitrile-grafted modified graphene flexibility Gao Jie
Electric nano composite membrane finished product component includes: cyanethyl cellulose 0.6g, polyacrylonitrile-grafted modified graphene 0.012g.
With the performance of the high dielectric flexible nano composite membrane of the standby cyanethyl cellulose base of this component and weight in grams numeral system are as follows: be situated between
Electric constant and dielectric loss are respectively 22.33 and 0.365 (100HZ)；First stage thermal decomposition temperature and second stage thermal decomposition
Temperature is respectively 271.1 DEG C and 319.2 DEG C.
Claims (8)
1. a kind of preparation method of redox graphene graft polypropylene nitrile, it is characterised in that: comprising steps of
A. it adds graphene oxide into ultrasonic disperse in water and obtains graphene oxide aqueous dispersions, in above-mentioned dispersion in stirring
Middle addition acrylonitrile monemer, is added initiator under inert gas shielding, is uniformly mixed；
B. by mixed system be put into microwave grafting in microwave reactor react to obtain the washing of graphene oxide graft polypropylene nitrile,
It is dry；
C. it disperses the graphene graft polypropylene nitrile that step B is obtained in solvent, reducing agent is added, is placed in microwave reactor
Microwave reduction reaction, washs, is drying to obtain product；
The mass ratio of the graphene oxide and acrylonitrile monemer is 1:(10-500), the molar ratio of initiator and acrylonitrile monemer
For (3-5): 1000；
The microwave grafting reaction condition is 40-60 DEG C of temperature, reaction time 5-25min, microwave power 100-900W；Institute
Stating microwave reduction reaction condition is 80-95 DEG C of temperature, reaction time 1-25min, microwave power 100-900W.
2. the preparation method of redox graphene graft polypropylene nitrile according to claim 1, it is characterised in that: described
Initiator is potassium peroxydisulfate, ammonium persulfate, ammonium ceric nitrate, sodium hydrogensulfite, benzoyl peroxide, azodiisobutyronitrile, azo
Any one in two different heptonitriles.
3. the preparation method of redox graphene graft polypropylene nitrile according to claim 1, it is characterised in that: described
Solvent is the mixing of one or more of water, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone；
The dosage of the solvent and the mass ratio of raw material graphene oxide are (10-1000): 1.
4. the preparation method of redox graphene graft polypropylene nitrile according to claim 1, it is characterised in that: described
Reducing agent is phenylhydrazine or hydrazine hydrate, and dosage is that reducing agent 0.1-10 μ L is added in every milligram of graphene oxide.
5. the preparation method of redox graphene graft polypropylene nitrile according to claim 1, it is characterised in that: described
Drying process is dry under vacuum condition, and drying temperature is no more than 60 DEG C；Ultrasound condition is 200W's in the step A
Ultrasonic disperse 2h in ultrasonic cleaning machine.
6. the high dielectric of the preparation of redox graphene graft polypropylene nitrile described in any one of -5 is received according to claim 1
Rice composite membrane, it is characterised in that: be prepared as follows: using cyanethyl cellulose as matrix, being grafted with redox graphene
Polypropylene product is filler, is configured to solution with casting solution, is made through casting film-forming；
The cyanethyl cellulose, redox graphene graft polypropylene product, casting solution mass ratio are as follows: 10:(0.5-
2): (400-500)；The casting solution N,N-dimethylformamide.
7. high dielectric nano composite membrane according to claim 6, it is characterised in that: the thickness after the nano composite membrane is dry
Degree is 0.030-0.100mm.
8. high dielectric nano composite membrane according to claim 6, it is characterised in that: the cyanethyl cellulose degree of substitution is
2.4-2.6, the grafting rate of the polyacrylonitrile-grafted modified graphene are 20%-75%.
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