CN105732917A - Preparation method of reduced graphene oxide-grafted polyacrylonitrile - Google Patents
Preparation method of reduced graphene oxide-grafted polyacrylonitrile Download PDFInfo
- Publication number
- CN105732917A CN105732917A CN201610274341.7A CN201610274341A CN105732917A CN 105732917 A CN105732917 A CN 105732917A CN 201610274341 A CN201610274341 A CN 201610274341A CN 105732917 A CN105732917 A CN 105732917A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- preparation
- graphene
- graft polypropylene
- microwave
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a preparation method of reduced graphene oxide-grafted polyacrylonitrile. The preparation method of reduced graphene oxide-grafted polyacrylonitrile is small in time consumption and energy consumption, low in cost and suitable for industrialization. The preparation method includes the steps that graphene oxide is ultrasonically dispersed into water, acrylonitrile monomers are added with high-speed stirring, an initiator is added under inert gas shielding and mixed evenly, the mixture is reacted in a microwave reactor to obtain graphene oxide-grafted polyacrylonitrile, and washing and drying are carried out; graphene oxide-grafted polyacrylonitrile is dispersed into a solvent, a reductant is added into the microwave reactor for a reaction, washing and drying are carried out, and the product is obtained. Equipment and an operation process for preparing reduced graphene oxide-grafted polyacrylonitrile with the method are simple, the period is very short, repeatability is good, cost is low, and the method has practical application value; a prepared composite film is high in dielectric property and low in dielectric loss, can be applied to the electronics industry, the motor industry and the cable industry and also has application prospects in the fields of artificial muscles, wave-absorbing materials, drug sustained release and the like.
Description
Technical field
The preparation method that the present invention relates to a kind of modified graphene, the preparation method being specifically related to a kind of redox graphene graft polypropylene nitrile.
Background technology
Graphene (Graphene) is graphite type material, has the elementary cell of sp2 hybrid structure and the monoatomic layer of two dimension, is the thinnest two-dimensional material found at present.Owing to the character of the electricity of Graphene excellence, calorifics, machinery and biocompatibility etc. has attracted the concern of increasing scientific research personnel.Just because of these special and characteristics of excellence of Graphene, it is made to modify as nanoscale elements and be doped in polymer, obtain composite, can effectively improve polymer performance in power, heat, optical, electrical and magnetic etc. so that Graphene and composite thereof demonstrate wide application prospect in fields such as energy field, chemical catalysis field, electrotechnical, electronic field, biomedical sector, aerospace fields.Its main preparation methods is chemical oxidization method: Brodie method, Staudenmaier method, Hummers method and improvement Hummers method, and wherein Hummers and improvement Hummers method are owing to its course of reaction is relatively easy, toxicity is relatively low, therefore are present main stream approach.
Grapheme material has the performance of excellence, but its specific surface area is susceptible to greatly reunite, and the compatibility as filler Yu matrix is poor in polymer matrix composite, and this is greatly unfavorable for the application prospect of Graphene.Therefore, various countries' research worker falls over each other it is studied, it is desirable to be able to find suitable improved method to make Graphene can improve the compatibility.Studies have found that, graphenic surface is carried out graft modification and can improve its dispersibility in a solvent or dissolubility, also can improve the compatibility of redox graphene and matrix.There is a lot of research and report that Graphene is carried out graft modification in recent years, such as the Authorization Notice No. preparation method of a kind of polymer graft Graphene that has been CN102040714B and patent disclosure that Authorization Notice No. is CN102586922B, but all adopt traditional polymerization, not only length consuming time, and it is also big to consume energy, this is also the maximum restriction that current grapheme material industrial applications is subject to.So while improving grafting efficiency, reducing energy consumption, shorten a great problem and challenge that the response time is graft polymerization reaction.The modified commercial Application for Graphene of Graphene also needs to research and develop further and improve.
Summary of the invention
The invention aims to provide a kind of consuming time short, consume energy low, cost is low and is suitable to industrialized prepare redox graphene graft polypropylene nitrile method.
For achieving the above object, the technical solution used in the present invention is: the preparation method of a kind of redox graphene graft polypropylene nitrile includes step:
A. add graphene oxide into ultrasonic disperse in water and obtain graphene oxide aqueous dispersions, stirring adds acrylonitrile monemer in above-mentioned dispersion, adds initiator under inert gas shielding, be uniformly mixed；
B., mixed system is put into microwave grafting in microwave reactor be obtained by reacting the washing of graphene oxide graft polypropylene nitrile, dry；
C. the Graphene graft polypropylene nitrile obtained by step B is scattered in solvent, adds reducing agent, the reaction that is placed in microwave reactor microwave reduction, washs, is drying to obtain product.
Further, described microwave grafting reaction condition is temperature 40-60 DEG C, and the response time is 5-25min, and microwave power is 100-900W；Described microwave reduction reaction condition is temperature 80-95 DEG C, response time 1-25min, and microwave power is 100-900W.
Further, the mass ratio of described graphene oxide and acrylonitrile monemer is 1:(10-500), the mol ratio of initiator and acrylonitrile monemer is (3-5): 1000.
Further, described initiator is any one in potassium peroxydisulfate, Ammonium persulfate., ammonium ceric nitrate, sodium sulfite, benzoyl peroxide, azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile).
Further, the solvent used in described step C is one or more mixing in water, DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone；The mass ratio of the consumption of described solvent and feed oxygen functionalized graphene is (1-1000): 1.
Further, described reducing agent is phenylhydrazine or hydrazine hydrate, and its consumption is that every milligram of graphene oxide adds reducing agent 0.1-10 μ L.Namely often adding the graphene oxide of 1mg in step A, the reducing agent used during reduction is 0.1-10 μ L.
Further, it is dry that described dry run is under vacuum condition, and baking temperature is less than 60 DEG C；In described step A, ultrasound condition is ultrasonic disperse 2h in the ultrasonic cleaner of 200W.Namely under the ultrasound condition of 200W, disperse 2h.
Above-mentioned redox graphene graft polypropylene nitrile prepares high dielectric nano composite membrane with cyanethyl cellulose for matrix, with redox graphene graft polypropylene product for filler, is configured to solution with casting solution, prepares through casting film-forming；Described cyanethyl cellulose, redox graphene graft polypropylene product, casting solution mass ratio be: 10:(0.5-2): (400-500)；Described casting solution is N,N-dimethylformamide.That is, after solution cast flat is layered on masking plate, casting solution volatilization, finally gives high dielectric nano composite membrane after drying.
Further, the dried thickness of described nano composite membrane is 0.030-0.100mm.
Further, described cyanethyl cellulose substitution value is 2.4-2.6, and the percent grafting of described polyacrylonitrile-grafted modified Graphene is 20%-70%.
Adopt the inventive method to prepare redox graphene graft polypropylene nitrile product and high dielectric nano composite membrane has the advantage that
1. equipment and the operating process of preparing redox graphene graft polypropylene nitrile are simple, and the cycle is extremely short, reproducible, and cost is low, has actual application value.Similarly suitable other vinyl monomers a series of of this mode and Graphene carry out glycerol polymerization, therefore have good application prospect in the covalent modified field of Graphene；
2. the present invention adopts microwave method to prepare redox graphene graft polypropylene nitrile, has filled up the blank of microwave method graft modification Graphene, has opened the new way of Graphene graft modification；Invention further defines the proportioning raw materials of microwave reaction system, solvent load, initiator and reducing agent consumption etc., by controlling the time of microwave reaction, temperature and power, utilizes described formula then can prepare the modified graphene of different percent grafting.
3. the redox graphene graft polypropylene nitrile of preparation has fabulous solubility property and electric conductivity.
4. the dielectric properties of the flexible high dielectric nano composite membrane of the cyanethyl cellulose prepared/polyacrylonitrile-grafted modified Graphene are higher, dielectric loss is relatively low, can apply to electronics, motor and cable industry, and also have certain application prospect in fields such as artificial-muscle, absorbing material and medicament slow releases；The flexible high dielectric nano composite film surface of the cyanethyl cellulose prepared/polyacrylonitrile-grafted modified Graphene is glossy, and good looking appearance has certain pliability and good mechanical performance and hot property.
5. the flexible high dielectric nano composite membrane production method safety of the cyanethyl cellulose prepared/polyacrylonitrile-grafted modified Graphene, flow process is simple, and production cost is low, therefore good market prospects.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described.Described embodiment is only the preferred embodiments of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., should be included within protection scope of the present invention.In embodiment one to five, the dielectric properties of product adopt Agilent 4294A electric impedance analyzer to be measured, heat stability adopts TG-DTA6200LABSYS type thermogravimetric differential thermal Thermal Synthetic Analysis instrument to be measured, and in embodiment, ultrasonic disperse step is under the ultrasound condition of 200W and disperses 2h.
Embodiment one
Reaction bulb adds 20mg graphene oxide, 200ml water, ultrasonic disperse 30min, adds 10g acrylonitrile monemer, add 0.43g Ammonium persulfate. under nitrogen atmosphere, be placed in microwave reactor.It is 10min that microwave arranges the response time, temperature 60 C, power 600W.Centrifugal, washing, 60 DEG C of vacuum dryings.
Above-mentioned products therefrom is dissolved in DMF, adds 10 μ L phenylhydrazines, be placed in microwave reactor, response time 25min, reaction temperature 95 DEG C, microwave power 800W are set.Precipitation, centrifugal, washing, 60 DEG C of vacuum dryings obtain redox graphene graft polypropylene nitrile.Percent grafting is 22.4%.
0.6g cyanethyl cellulose is dissolved in 18gDMF, magnetic agitation 2h, dissolves.The polyacrylonitrile-grafted modified Graphene that 0.006g prepares is dissolved in 6gDMF, stirs 3h, ultrasonic disperse 2h.Polyacrylonitrile-grafted modified Graphene after dissolving is joined in the solution of cyanethyl cellulose, obtain mixed solution, magnetic agitation 24h.Film forming solution is poured in surface plate, is placed in baking oven 60 DEG C of dry about 48h, after cooling, take off film, the flexible high dielectric nano composite membrane of cyanethyl cellulose/polyacrylonitrile-grafted modified Graphene can be obtained.The flexible high dielectric nano composite membrane finished product component of the cyanethyl cellulose prepared/polyacrylonitrile-grafted modified Graphene includes: cyanethyl cellulose 0.6g, polyacrylonitrile-grafted modified Graphene 0.006g.
With the performance of the standby cyanethyl cellulose base height dielectric flexible nano composite membrane of this component and weight in grams numeral system for: dielectric constant and dielectric loss be 16.9 and 0.234 (100Hz) respectively；First stage heat decomposition temperature and second stage heat decomposition temperature respectively 267.2 DEG C and 321 DEG C.
Embodiment two
Reaction bulb adds 20mg graphene oxide, 200ml water, ultrasonic disperse 30min, adds 10g acrylonitrile monemer, add 0.43g Ammonium persulfate. under nitrogen atmosphere, be placed in microwave reactor.It is 15min that microwave arranges the response time, temperature 60 C, power 600W.Centrifugal, washing, 60 DEG C of vacuum dryings.
Above-mentioned products therefrom is dissolved in DMF, adds 10 μ L phenylhydrazines, be placed in microwave reactor, response time 15min, reaction temperature 95 DEG C, microwave power 800W are set.Precipitation, centrifugal, washing, 60 DEG C of vacuum dryings obtain redox graphene graft polypropylene nitrile.Percent grafting is 37.3%.
0.6g cyanethyl cellulose is dissolved in 18gDMF, magnetic agitation 2h, dissolves.The polyacrylonitrile-grafted modified Graphene that 0.018g prepares is dissolved in 12gDMF, stirs 3h, ultrasonic disperse 2h.Polyacrylonitrile-grafted modified Graphene after dissolving is joined in the solution of cyanethyl cellulose, obtain mixed solution, magnetic agitation 24h.Film forming solution is poured in surface plate, is placed in baking oven 60 DEG C of dry about 48h, after cooling, take off film, the flexible high dielectric nano composite membrane of cyanethyl cellulose/polyacrylonitrile-grafted modified Graphene can be obtained.The flexible high dielectric nano composite membrane finished product component of the cyanethyl cellulose prepared/polyacrylonitrile-grafted modified Graphene includes: cyanethyl cellulose 0.6g, polyacrylonitrile-grafted modified Graphene 0.018g.
With the performance of the standby cyanethyl cellulose base height dielectric flexible nano composite membrane of this component and weight in grams numeral system for: dielectric constant and dielectric loss be 18.58 and 0.167 (100Hz) respectively；First stage heat decomposition temperature and second stage heat decomposition temperature respectively 265.4 DEG C and 315 DEG C.
Embodiment three
Reaction bulb adds 20mg graphene oxide, 200ml water, ultrasonic disperse 30min, adds 20g acrylonitrile monemer, add 0.43g potassium peroxydisulfate under nitrogen atmosphere, be placed in microwave reactor.It is 10min that microwave arranges the response time, temperature 60 C, power 600W.Centrifugal, washing, 60 DEG C of vacuum dryings.
Above-mentioned products therefrom is dissolved in N,N-dimethylacetamide, adds 15 μ L phenylhydrazines, be placed in microwave reactor, response time 25min, reaction temperature 95 DEG C, microwave power 800W are set.Precipitation, centrifugal, washing, 60 DEG C of vacuum dryings obtain redox graphene graft polypropylene nitrile.Percent grafting is 53.6%.
0.6g cyanethyl cellulose is dissolved in 18gDMF, magnetic agitation 2h, dissolves.The polyacrylonitrile-grafted modified Graphene that 0.006g prepares is dissolved in 12gDMF, stirs 3h, ultrasonic disperse 2h.Polyacrylonitrile-grafted modified Graphene after dissolving is joined in the solution of cyanethyl cellulose, obtain mixed solution, magnetic agitation 24h.Film forming solution is poured in surface plate, is placed in baking oven 60 DEG C of dry about 48h, after cooling, take off film, the flexible high dielectric nano composite membrane of cyanethyl cellulose/polyacrylonitrile-grafted modified Graphene can be obtained.The flexible high dielectric nano composite membrane finished product component of the cyanethyl cellulose prepared/polyacrylonitrile-grafted modified Graphene includes: cyanethyl cellulose 0.6g, polyacrylonitrile-grafted modified Graphene 0.042g.
With the performance of the standby cyanethyl cellulose base height dielectric flexible nano composite membrane of this component and weight in grams numeral system for: dielectric constant and dielectric loss be 20.00 and 0.142 (100Hz) respectively；First stage heat decomposition temperature and second stage heat decomposition temperature respectively 266.6 DEG C and 318.6 DEG C.
Embodiment four
Reaction bulb adds 20mg graphene oxide, 200ml water, ultrasonic disperse 30min, adds 10g acrylonitrile monemer, add 0.43g Ammonium persulfate. and 0.19g sodium sulfite under nitrogen atmosphere, be placed in microwave reactor.It is 10min that microwave arranges the response time, temperature 60 C, power 600W.Centrifugal, washing, 60 DEG C of vacuum dryings.
Above-mentioned products therefrom is dissolved in DMF, adds 10 μ L phenylhydrazines, be placed in microwave reactor, response time 25min, reaction temperature 95 DEG C, microwave power 800W are set.Precipitation, centrifugal, washing, 60 DEG C of vacuum dryings obtain redox graphene graft polypropylene nitrile.Percent grafting is 66.0%.
0.6g cyanethyl cellulose is dissolved in 18gDMF, magnetic agitation 2h, dissolves.The polyacrylonitrile-grafted modified Graphene that 0.006g prepares is dissolved in 6gDMF, stirs 3h, ultrasonic disperse 2h.Polyacrylonitrile-grafted modified Graphene after dissolving is joined in the solution of cyanethyl cellulose, obtain mixed solution, magnetic agitation 24h.Film forming solution is poured in surface plate, is placed in baking oven 60 DEG C of dry about 48h, after cooling, take off film, the flexible high dielectric nano composite membrane of cyanethyl cellulose/polyacrylonitrile-grafted modified Graphene can be obtained.The flexible high dielectric nano composite membrane finished product component of the cyanethyl cellulose prepared/polyacrylonitrile-grafted modified Graphene includes: cyanethyl cellulose 0.6g, polyacrylonitrile-grafted modified Graphene 0.006g.
With the performance of the standby cyanethyl cellulose base height dielectric flexible nano composite membrane of this component and weight in grams numeral system for: dielectric constant and dielectric loss be 20.187 and 0.142 (100H respectivelyZ)；First stage heat decomposition temperature and second stage heat decomposition temperature respectively 269.6 DEG C and 312 DEG C.
Embodiment five
Reaction bulb adds 20mg graphene oxide, 200mlDMF, ultrasonic disperse 2h, adds 10g acrylonitrile monemer, add 0.06g benzoyl peroxide under nitrogen atmosphere, be placed in microwave reactor.It is 10min that microwave arranges the response time, temperature 60 C, power 600W.Centrifugal, washing, 60 DEG C of vacuum dryings.
Above-mentioned products therefrom is dissolved in N-Methyl pyrrolidone, adds 10 μ L phenylhydrazines, be placed in microwave reactor, response time 25min, reaction temperature 95 DEG C, microwave power 800W are set.Precipitation, centrifugal, washing, 60 DEG C of vacuum dryings obtain redox graphene graft polypropylene nitrile.Percent grafting is 12%.
0.6g cyanethyl cellulose is dissolved in 18gDMF, magnetic agitation 2h, dissolves.The polyacrylonitrile-grafted modified Graphene that 0.012g prepares is dissolved in 6gDMF, stirs 3h, ultrasonic disperse 2h.Polyacrylonitrile-grafted modified Graphene after dissolving is joined in the solution of cyanethyl cellulose, obtain mixed solution, magnetic agitation 24h.Film forming solution is poured in surface plate, is placed in baking oven 60 DEG C of dry about 48h, after cooling, take off film, the flexible high dielectric nano composite membrane of cyanethyl cellulose/polyacrylonitrile-grafted modified Graphene can be obtained.The flexible high dielectric nano composite membrane finished product component of the cyanethyl cellulose prepared/polyacrylonitrile-grafted modified Graphene includes: cyanethyl cellulose 0.6g, polyacrylonitrile-grafted modified Graphene 0.012g.
With the performance of the standby cyanethyl cellulose base height dielectric flexible nano composite membrane of this component and weight in grams numeral system for: dielectric constant and dielectric loss be 22.33 and 0.365 (100H respectivelyZ)；First stage heat decomposition temperature and second stage heat decomposition temperature respectively 271.1 DEG C and 319.2 DEG C.
Claims (10)
1. the preparation method of a redox graphene graft polypropylene nitrile, it is characterised in that: include step:
A. add graphene oxide into ultrasonic disperse in water and obtain graphene oxide aqueous dispersions, stirring adds acrylonitrile monemer in above-mentioned dispersion, adds initiator under inert gas shielding, be uniformly mixed；
B., mixed system is put into microwave grafting in microwave reactor be obtained by reacting the washing of graphene oxide graft polypropylene nitrile, dry；
C. the Graphene graft polypropylene nitrile obtained by step B is scattered in solvent, adds reducing agent, the reaction that is placed in microwave reactor microwave reduction, washs, is drying to obtain product.
2. the preparation method of redox graphene graft polypropylene nitrile according to claim 1, described microwave grafting reaction condition is temperature 40-60 DEG C, and the response time is 5-25min, and microwave power is 100-900W；Described microwave reduction reaction condition is temperature 80-95 DEG C, response time 1-25min, and microwave power is 100-900W.
3. the preparation method of redox graphene graft polypropylene nitrile according to claim 1, it is characterized in that: the mass ratio of described graphene oxide and acrylonitrile monemer is 1:(10-500), the mol ratio of initiator and acrylonitrile monemer is (3-5): 1000.
4. the preparation method of redox graphene graft polypropylene nitrile according to claim 1, it is characterised in that: described initiator is any one in potassium peroxydisulfate, Ammonium persulfate., ammonium ceric nitrate, sodium sulfite, benzoyl peroxide, azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile).
5. the preparation method of redox graphene graft polypropylene nitrile according to claim 1, it is characterised in that: described solvent is one or more mixing in water, DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone；The mass ratio of the consumption of described solvent and feed oxygen functionalized graphene is (10-1000): 1.
6. 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 its consumption is that every milligram of graphene oxide adds reducing agent 0.1-10 μ L.
7. the preparation method of redox graphene graft polypropylene nitrile according to claim 1, it is characterised in that: it is dry that described dry run is under vacuum condition, and baking temperature is less than 60 DEG C；In described step A, ultrasound condition is ultrasonic disperse 2h in the ultrasonic cleaner of 200W.
8. the high dielectric nano composite membrane that prepared by the redox graphene graft polypropylene nitrile according to claim 1-7, it is characterized in that: be prepared as follows: with cyanethyl cellulose for matrix, with redox graphene graft polypropylene product for filler, it is configured to solution with casting solution, prepares through casting film-forming；
Described cyanethyl cellulose, redox graphene graft polypropylene product, casting solution mass ratio be: 10:(0.5-2): (400-500)；Described casting solution N,N-dimethylformamide.
9. high dielectric nano composite membrane according to claim 8, it is characterised in that: the dried thickness of described nano composite membrane is 0.030-0.100mm.
10. high dielectric nano composite membrane according to claim 8, it is characterised in that: described cyanethyl cellulose substitution value is 2.4-2.6, and the percent grafting of described polyacrylonitrile-grafted modified Graphene is 20%-75%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610274341.7A CN105732917B (en) | 2016-04-28 | 2016-04-28 | A kind of preparation method of redox graphene graft polypropylene nitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610274341.7A CN105732917B (en) | 2016-04-28 | 2016-04-28 | A kind of preparation method of redox graphene graft polypropylene nitrile |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105732917A true CN105732917A (en) | 2016-07-06 |
| CN105732917B CN105732917B (en) | 2018-12-28 |
Family
ID=56288576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610274341.7A Expired - Fee Related CN105732917B (en) | 2016-04-28 | 2016-04-28 | A kind of preparation method of redox graphene graft polypropylene nitrile |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105732917B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106893052A (en) * | 2017-03-13 | 2017-06-27 | 东北大学秦皇岛分校 | A kind of preparation method of graphene oxide/polyacrylamide composite aquogel |
| CN110117004A (en) * | 2018-02-05 | 2019-08-13 | 庄鹏宇 | A kind of preparation method of redox graphene group compound film |
| CN110772659A (en) * | 2019-06-28 | 2020-02-11 | 复向医药科技(上海)有限公司 | Preparation method of chitosan graphene nano medical dressing for resisting bacteria and promoting wound healing |
| CN111454409A (en) * | 2020-04-30 | 2020-07-28 | 宁波锋成纳米科技有限公司 | Polymer grafted graphene material and preparation method and application thereof |
| CN111484644A (en) * | 2020-04-17 | 2020-08-04 | 东华理工大学 | Method for preparing, separating and enriching uranium from polyamidoxime/graphene nanoribbon composite aerogel |
| CN113943982A (en) * | 2021-11-03 | 2022-01-18 | 绍兴绿地针织有限公司 | Volcanic rock thermal fiber and thermal socks |
| CN114797503A (en) * | 2022-06-28 | 2022-07-29 | 南通纳爱斯环保科技有限公司 | Graphene-quaternary ammonium salt modified polyacrylonitrile composite fiber filtering membrane and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008133672A2 (en) * | 2006-12-22 | 2008-11-06 | Drexel University | Nanowires and coatings of self-assembled nanoparticles |
| CN102560746A (en) * | 2011-12-29 | 2012-07-11 | 中国科学院宁波材料技术与工程研究所 | Preparation method of polyacrylonitrile/graphene composite-based carbon fiber |
| CN102586951A (en) * | 2012-01-18 | 2012-07-18 | 浙江大学 | Preparation method for composite carbon fiber based on graphene/ polyacrylonitrile |
| CN102586922A (en) * | 2012-01-18 | 2012-07-18 | 浙江大学 | Preparation method for macroscopic fiber of polyacrylonitrile grafted graphene |
| CN103113625A (en) * | 2013-03-20 | 2013-05-22 | 北京理工大学 | Cyano-containing cellulose derivative and graphene composite material and preparation method thereof |
| CN103408880A (en) * | 2013-06-27 | 2013-11-27 | 复旦大学 | Method for preparing polyacrylonitrile/graphene composite material |
-
2016
- 2016-04-28 CN CN201610274341.7A patent/CN105732917B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008133672A2 (en) * | 2006-12-22 | 2008-11-06 | Drexel University | Nanowires and coatings of self-assembled nanoparticles |
| CN102560746A (en) * | 2011-12-29 | 2012-07-11 | 中国科学院宁波材料技术与工程研究所 | Preparation method of polyacrylonitrile/graphene composite-based carbon fiber |
| CN102586951A (en) * | 2012-01-18 | 2012-07-18 | 浙江大学 | Preparation method for composite carbon fiber based on graphene/ polyacrylonitrile |
| CN102586922A (en) * | 2012-01-18 | 2012-07-18 | 浙江大学 | Preparation method for macroscopic fiber of polyacrylonitrile grafted graphene |
| CN103113625A (en) * | 2013-03-20 | 2013-05-22 | 北京理工大学 | Cyano-containing cellulose derivative and graphene composite material and preparation method thereof |
| CN103408880A (en) * | 2013-06-27 | 2013-11-27 | 复旦大学 | Method for preparing polyacrylonitrile/graphene composite material |
Non-Patent Citations (3)
| Title |
|---|
| GOUTAM PRASANNA: "Tailoring the interface of an immiscible polymer blend by a mutually miscible homopolymer grafted onto graphene oxide:outstanding mechanical properties", 《ROYAL SOCIETY OF CHEMISTRY》 * |
| LIJUN MA，等: "Synthesis and characterization of polymer grafted graphene oxide sheets using a Ce(Ⅳ)/HNO3 redox system in an aqueous solution", 《CARBON》 * |
| 王娴: "功能化石墨烯/聚合物基复合材料性能研究进展", 《精细化工原料及中间体》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106893052A (en) * | 2017-03-13 | 2017-06-27 | 东北大学秦皇岛分校 | A kind of preparation method of graphene oxide/polyacrylamide composite aquogel |
| CN110117004A (en) * | 2018-02-05 | 2019-08-13 | 庄鹏宇 | A kind of preparation method of redox graphene group compound film |
| CN110772659A (en) * | 2019-06-28 | 2020-02-11 | 复向医药科技(上海)有限公司 | Preparation method of chitosan graphene nano medical dressing for resisting bacteria and promoting wound healing |
| CN111484644A (en) * | 2020-04-17 | 2020-08-04 | 东华理工大学 | Method for preparing, separating and enriching uranium from polyamidoxime/graphene nanoribbon composite aerogel |
| CN111454409A (en) * | 2020-04-30 | 2020-07-28 | 宁波锋成纳米科技有限公司 | Polymer grafted graphene material and preparation method and application thereof |
| CN111454409B (en) * | 2020-04-30 | 2022-11-18 | 宁波锋成纳米科技有限公司 | Polymer grafted graphene material and preparation method and application thereof |
| CN113943982A (en) * | 2021-11-03 | 2022-01-18 | 绍兴绿地针织有限公司 | Volcanic rock thermal fiber and thermal socks |
| CN113943982B (en) * | 2021-11-03 | 2024-04-05 | 绍兴绿地针织有限公司 | Volcanic rock thermal insulation fiber and thermal insulation sock |
| CN114797503A (en) * | 2022-06-28 | 2022-07-29 | 南通纳爱斯环保科技有限公司 | Graphene-quaternary ammonium salt modified polyacrylonitrile composite fiber filtering membrane and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105732917B (en) | 2018-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105732917A (en) | Preparation method of reduced graphene oxide-grafted polyacrylonitrile | |
| Mei et al. | An ultra-thin carbon-fabric/graphene/poly (vinylidene fluoride) film for enhanced electromagnetic interference shielding | |
| Yang et al. | Multifunctional Ti3C2TX MXene/Aramid nanofiber/Polyimide aerogels with efficient thermal insulation and tunable electromagnetic wave absorption performance under thermal environment | |
| CN101781459A (en) | Graphene/polyaniline conductive composite material and preparation method thereof | |
| CN104672502B (en) | Cyanoethyl cellulose based high-dielectric flexible nano-composite film and preparation method thereof | |
| CN102040714A (en) | Preparation method of polymer-grafted graphene | |
| CN103087386A (en) | Preparation method of low-percolation graphene/macromolecule electromagnetism shielding material | |
| CN105860062A (en) | Preparation method of carbon nanotube/polyaniline nanoparticle with negative dielectric constant | |
| CN108822452B (en) | Polytetrafluoroethylene conductive film and preparation method thereof | |
| CN108557812B (en) | Preparation method of graphene oxide grafted polyvinylidene fluoride | |
| CN108864622A (en) | A kind of preparation method of polymer-based dielectric composite material | |
| CN109056104A (en) | A kind of preparation method of conducting polypropylene fiber | |
| CN105906846A (en) | Cyanoethyl cellulose-based high-dielectric nano composite film and preparation method thereof | |
| CN102532894A (en) | Preparation method of graphite oxide/polypyrrole composite material | |
| CN103160053A (en) | Preparation method of polyacrylonitrile electromagnetic shielding nanocomposite | |
| CN110791096B (en) | 5G PPS film and preparation method thereof | |
| CN111892805B (en) | High-temperature-resistant and high-dielectric polymer-based composite dielectric material, and preparation method and application thereof | |
| CN103467986A (en) | Nano titanium carbide/polyimide composite material modified by small organic molecules | |
| KR20180066347A (en) | Method for Manufacturing Non Metallic Silicon Complex Using Nano Hole of CNT and the Silicon Complex | |
| CN102199341B (en) | Preparation method of microwave absorbing material | |
| CN116092723B (en) | High-dispersion high-conductivity graphene composite conductive slurry, preparation method and application | |
| CN104558777B (en) | Preparation method of natural graphite/polymer electromagnetic shielding composite | |
| CN106336486B (en) | A kind of conductive polymer polymer and preparation method thereof | |
| CN110041565A (en) | A kind of biology based flameproofing and its preparation method and application | |
| CN111002674B (en) | Composite electromagnetic shielding material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20181228 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |