CN109679161A - A kind of carboxy nitrile rubber/stannic oxide/graphene nano composite material and preparation method obstructing hazardous chemical solvent - Google Patents
A kind of carboxy nitrile rubber/stannic oxide/graphene nano composite material and preparation method obstructing hazardous chemical solvent Download PDFInfo
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- CN109679161A CN109679161A CN201811425326.3A CN201811425326A CN109679161A CN 109679161 A CN109679161 A CN 109679161A CN 201811425326 A CN201811425326 A CN 201811425326A CN 109679161 A CN109679161 A CN 109679161A
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2309/02—Copolymers with acrylonitrile
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
Abstract
The present invention relates to a kind of carboxy nitrile rubber/stannic oxide/graphene nano composite material and preparation methods for obstructing hazardous chemical solvent, stannic oxide/graphene nano piece is orientated in carboxy nitrile rubber matrix along in-plane, it effectively realizes in thickness direction to chemical solvent permeation barrier, wherein, the mass fraction of polyethyleneimine is 0.001-0.10wt% in composite material, the mass fraction of graphene oxide is 0.01-1wt%, and the mass fraction of carboxy nitrile rubber is 98.90-99.99wt%.Carboxy nitrile rubber of the invention/stannic oxide/graphene nano composite membrane can be greater than 2h, and good mechanical properties with a thickness of 1mm to a variety of chemical solvent guard times.Preparation method of the present invention is simply ingenious, easy to operate, large-scale industrial production preparation easy to accomplish, and has good machinability, and fire protection boots, fire protection gloves etc. can be prepared by the method for melting extrusion.
Description
Technical field
The invention belongs to field of polymer composite material, are related to a kind of carboxyl butyronitrile rubber for obstructing hazardous chemical solvent
Glue/stannic oxide/graphene nano composite material and preparation method, prepared carboxy nitrile rubber/graphene oxide composite material have
The characteristic of excellent barrier chemical solvent infiltration.
Background technique
Graphene oxide is with sp2The two-dimentional monoatomic layer of hydbridized carbon atoms composition.As a kind of novel nano-material,
Numerous areas has a wide application, for example, new energy, catalysis, senser element, electromagnetic shielding and with traditional rubber-plastics material
It is compound to enhance gas barrier property.But it since graphene surface has and a small amount of functional group, is allowed to be difficult in the polymer
Dispersion well, easily reunites.It is compared to for graphene, graphene oxide contains more oxygen-containing functional group because of its surface
Such as carboxyl, hydroxyl, epoxy group and sulfonic acid group etc. can with polymer occur chemical action, can overcome agglomeration traits but also
Increase its interaction force (electrostatic force, hydrogen bond) between polymer.Therefore people fill out frequently with graphene oxide at present
Polymeric matrix is filled, various graphene functional composite materials are prepared with this.
Carboxy nitrile rubber is the rubber that resistance to apolar medium is best in general purpose rubber, and wearability is high, heat-resist, bonding
Power is strong.Carboxy nitrile rubber is the outstanding of the comprehensive performances such as oil resistivity, physical mechanical property and chemical resistance, is most generation
One of rubber of table.When the harmful substances such as dangerization organic solvent, inorganic acid alkali salt touch the Working gloves of fireman, rubber
The surface of glue material can play first layer protective barrier first.
But organic solvent can be swollen and break after dangerization organic solvent or dangerization acid-alkali salt touch protective materials
The surface layer of bad rubber material, inorganic acid alkali salt can then make the surface of rubber material that chemical passivation generation cracking occur, and can edge
Segmentation crack continue endosmosis.By taking Tianjin harmful influence warehouse huge explosion in 2015 as an example, due to speedily carrying out rescue work in early days, fireman enters
The protection effect of common fire-entry suit is bad after to dangerous operation field, causes the unnecessary casualties of early stage.
The prior art has similar material, as to disclose a kind of dispersibility good for Chinese Patent Application No. 201510095850.9
Good carboxy nitrile rubber/graphene nanocomposite material, which includes: graphite oxide 0.1-8 weight
Part, carboxyl fix one's eyes upon 10 parts by weight of latex, hydrazine hydrate 0.1-8 parts by weight, flocculating agent, used preparation method organic solvent uses
Seldom, graphene is dispersed in carboxy nitrile rubber matrix amount with nanoscale graphite sheet form, and it is uniform to obtain particle size
Co-agglomeration particle, and without increasing any ancillary equipment, simple process environmental protection is low in cost.Separately there is Chinese patent application
201611203880.8 a kind of functionalized rubber/modified graphene oxide composite material and preparation method is disclosed, by rubber
Matrix body and be scattered in the rubber-based intracorporal modified graphene oxide composition, wherein the amount of modified graphene oxide be 0.1~
30wt%.The functional groups such as its hydroxyl, carboxyl for being had using surface of graphene oxide, amino modified nano-ZnO is grafted to
Surface of graphene oxide, nanometer enhancing even activating agent can be played the role of by making it in the composite.Continue using CTBN
Graft modification makes modified graphene oxide and rubber carry out blending and modifying Shi Nengyu polymeric matrix and entanglement and co-vulcanization occurs,
Improve interfacial interaction.But required barrier property is all not achieved, and graphene oxide is the emulsion blending during
Poor dispersion, the problem that easy to reunite, binding force is poor are still to urgently to be resolved.
Summary of the invention
In order to solve the above-mentioned problems in the prior art, the purpose of the present invention is to provide a kind of barrier hazardous chemicals
The carboxy nitrile rubber of product solvent/stannic oxide/graphene nano composite material and preparation method, solves graphene oxide in cream
Poor dispersion in liquid Blending Processes, problem easy to reunite, binding force is poor obtain a kind of with to chemical solvent high-barrier infiltration
The carboxy nitrile rubber of permeability/stannic oxide/graphene nano composite material.
The scheme that the present invention takes is as follows: a kind of carboxy nitrile rubber/graphene oxide obstructing hazardous chemical solvent
Nanocomposite, stannic oxide/graphene nano piece is orientated in carboxy nitrile rubber matrix along in-plane, in thickness direction
It effectively realizes to chemical solvent permeation barrier, wherein the mass fraction of polyethyleneimine is 0.001- in composite material
0.10wt%, the mass fraction of graphene oxide are 0.01-1wt%, and the mass fraction of carboxy nitrile rubber is 98.90-
99.99wt%。
In the preferred embodiments of the present invention, the acrylonitrile content of the carboxy nitrile rubber is high acrylonitrile
Content, high acrylonitrile content or middle high acrylonitrile content；Wherein, the high acrylonitrile content refers to that mass percent is greater than
43%, the high acrylonitrile content refers to that mass percent is 36-42%, and the middle high acrylonitrile content refers to that mass percent is
31-35%。
In the preferred embodiments of the present invention, between 0.5-50 μm, the number of plies exists the lamella size of graphene oxide
Between 1-10 layers.
In the preferred embodiments of the present invention, graphene oxide is prepared by improved Hummers method.
The present invention also protects above-mentioned carboxy nitrile rubber/stannic oxide/graphene nano composite material preparation method, including
Following steps:
(1) graphene oxide concentrate made from Hummers method is diluted with water dispersion, ultrasonic vibration obtains graphene oxide
Graphene oxide dispersion is uniformly mixed with polyethyleneimine aqueous dispersions, is ultrasonically treated by dispersion liquid；
(2) graphene oxide/polyethyleneimine dispersion liquid is mixed evenly with diluted carboxylic acrylonitrile butadiene rubber latex；
(3) the system temperature control of step (2) is stirred at 30-60 DEG C, then mixed emulsion is moved in ultrasonic vibration machine,
It is ultrasonic under conditions of 30-60 DEG C；
(4) in ultrasonic procedure, calcium chloride saturated solution is added, carries out " dynamic flocculate " and stir in ultrasound, finally by
To block rubber is washed with deionized water, dries, as masterbatch；
(5) masterbatch obtained in step (4) carries out mill with block carboxy nitrile rubber according to the proportion, calendering, vulcanization obtain
Carboxy nitrile rubber/stannic oxide/graphene nano composite material.
In the preferred embodiments of the present invention, the speed of agitator of step (4) is 600-2000rpm, and ultrasonic power is
60-100W。
Carboxy nitrile rubber prepared by the present invention/stannic oxide/graphene nano composite material structure is graphene oxide sheet
It is orientated in carboxy nitrile rubber matrix along in-plane, is based on this structure, composite material can satisfy to various gases, powder
The effective protection of the pollutants such as dirt, common harmful influence.Preparation method is compound with rubber in aqueous systems by graphene oxide,
Nano-dispersion can be achieved, degree of scatter is high, dispersing method green high-efficient.
On the one hand, graphene oxide of the invention is obtained by improved Hummers method, lamella size 0.5-50 μm it
Between, the number of plies is between 1-10 layers.And it joined polyethyleneimine in graphene oxide, using flocculated " the dynamic wadding of ultrasound
Solidifying method ", obtains graphene oxide evenly dispersed, not easy to reunite/carboxy nitrile rubber nanocomposite, and graphite oxide
The covalent bond effect for forming " bridge like " between alkene and carboxy nitrile rubber by polyethyleneimine, makes graphene oxide and carboxyl fourth
Combination between nitrile rubber strand is more secured, quickening while keeping graphene oxide evenly dispersed in carboxylic acrylonitrile butadiene rubber latex
Flocculation time improves preparation efficiency.
On the other hand ,-COOH is had again with highly polar-CN due to carboxy nitrile rubber, on the one hand makes rubber point
Interaction of hydrogen bond is formed between subchain and graphene oxide makes graphene oxide reach uniform in carboxy nitrile rubber matrix
Dispersion；- the COOH of institute's band and polyethyleneimine form amido bond polyethyleneimine simultaneously in another aspect graphene oxide layer
Amido bond is formed between carboxy nitrile rubber strand, is just had between such graphene oxide and carboxy nitrile rubber strand
Covalent key connection, the presence that keeps graphene oxide stable in carboxy nitrile rubber matrix.The two above aspects make
Carboxy nitrile rubber/stannic oxide/graphene nano composite material plays the role of good in first step protective barrier.Dangerization is organic
Solvent and inorganic acid alkali salt enter graphene oxide/rubber material inside after breaching surface layer protection, in this process
In, two-dimensional stannic oxide/graphene nano piece and rubber material play synergistic effect.
Compared with prior art, carboxy nitrile rubber of the invention/graphene oxide barrier protective materials has following excellent
Point: graphene nanometer sheet is uniformly directed dispersion in rubber matrix, has excellent mechanical property, to chemical reagent barrier property
By force, flexibility is good.The carboxy nitrile rubber/stannic oxide/graphene nano composite membrane can be to a variety of chemistry with a thickness of 1mm
Solvent guard time is greater than 2h, and good mechanical properties.Preparation method of the present invention is simply ingenious, easy to operate, easy to accomplish
Large-scale industrial production preparation, and there is good machinability, fire-fighting can be prepared by the method for melting extrusion
Protective Boots, fire protection gloves etc..
Detailed description of the invention
It is further described with reference to the accompanying drawing:
Fig. 1-2 is the microcosmic scanning electron microscope (SEM) photograph of carboxy nitrile rubber/graphene oxide that embodiment 1 is prepared；
Fig. 3-4 is the microcosmic scanning electron microscope (SEM) photograph of carboxy nitrile rubber/graphene oxide that embodiment 2 is prepared；
Fig. 5-6 is the microcosmic scanning electron microscope (SEM) photograph of carboxy nitrile rubber/graphene oxide that embodiment 3 is prepared；
Fig. 7-8 is the microcosmic scanning electron microscope (SEM) photograph of carboxy nitrile rubber/graphene oxide that embodiment 4 is prepared.
Specific embodiment
Below according to specific embodiment, the invention will be further described, but is not limited to following embodiment.
Embodiment 1
The synthesis of graphene oxide:
(1) the high-quality natural flake graphite of 300 purpose of 10g, 10g NaNO are weighed3It is put in spare in the three-necked flask of 1000ml；
(2) (5 DEG C or less) under ice bath, in 1000ml three-necked flask, the dense H of 300ml is added2SO4, then in Chinese mugwort card blender
Lower stirring 30min, makes whole system fall temperature；
(3) by 30g KMnO4Respectively 5 times, be added every 12min primary, added after 1h, guarantee 5 DEG C of T < in the process, add
Complete last time KMnO4After react 10min, remove ice bath, normal-temperature reaction 30min；
(4) three-necked flask is warming up to 35 DEG C, reacts 6h；
(5) 400ml deionized water is added in three-necked flask, guarantees 100 DEG C of T <, 15min is kept the temperature in 95-100 DEG C；
(6) product after reaction is poured into large beaker, 400ml deionized water is added, and the H of 100ml is added2O2, to remove
Extra KMnO4, stratification；
(7) the dilute hydrochloric acid cleaning of 1000ml twice, is finally centrifugated, stops centrifugation after centrifuged supernatant to neutrality, collect
Sediment.
The preparation of carboxy nitrile rubber/stannic oxide/graphene nano composite material:
(1) a certain amount of water dilution dispersion of 0.1 portion of graphene oxide concentrate is weighed, ultrasonic vibration 2h obtains diluted oxidation
Graphene dispersing solution；
(2) graphene oxide dispersion and 0.001-0.1 parts of polyethyleneimines are mixed, ultrasonic disperse 2h；
(3) above-mentioned (1), (2) dispersion liquid are mixed with carboxylic acrylonitrile butadiene rubber latex, is ultrasonically treated 2h, whipping temp, ultrasound after stirring 6h
Temperature is 35 DEG C；
(4) when ultrasonic disperse closes to an end, side stirring becomes ultrasound and CaCl is added2Saturated solution carry out " dynamic flocculate ", it is " dynamic
Carboxy nitrile rubber/graphene oxide rubber blocks 1h is washed with deionized water after state flocculation ", is repeated 5 times.
(5) the preparation barrier protecting film using block rubber obtained in step (4) as masterbatch, through mill, calendering, vulcanization
The barrier protecting film with a thickness of 1mm is obtained afterwards.
The pattern of preparation-obtained carboxy nitrile rubber/graphene oxide is as shown in Figs. 1-2.Embodiment 1 is prepared to be obtained
To barrier property protecting film have compared to the prior art to the protective of the purer carboxy nitrile rubber film of the protective of chemical solvent
Apparent raising, the results are shown in Table 1.
Embodiment 2
Graphene oxide is synthesized by the step in example 1.
The preparation of carboxy nitrile rubber/stannic oxide/graphene nano composite material:
(1) it weighs 0.3 part of a certain amount of water of graphene oxide concentrate addition to be diluted, ultrasonic vibration 2h obtains oxidation stone
Black alkene dispersion liquid；
(2) graphene oxide dispersion and 0.001-0.1 parts of polyethyleneimines are mixed, ultrasonic disperse 2h；
(3) above-mentioned (1), (2) dispersion liquid are mixed with carboxylic acrylonitrile butadiene rubber latex, is ultrasonically treated 2h, whipping temp, ultrasound after stirring 6h
Temperature is 35 DEG C；
(4) when ultrasonic disperse closes to an end, side stirring becomes ultrasound and CaCl is added2Saturated solution carry out " dynamic flocculate ", it is " dynamic
Carboxy nitrile rubber/graphene oxide rubber blocks 1h is washed with deionized water after state flocculation ", is repeated 5 times.
(5) the preparation barrier protecting film using block rubber obtained in step (4) as masterbatch, through mill, calendering, vulcanization
The barrier protecting film with a thickness of 1mm is obtained afterwards.
The pattern of preparation-obtained carboxy nitrile rubber/graphene oxide is as shown in Figure 3-4.Embodiment 2 is prepared to be obtained
To barrier property protecting film have to the protective of the purer carboxy nitrile rubber film of the protective of chemical solvent and extremely significantly mention
High and be compared to example 1, the guard time of barrier chemical solvent is also extended, and the results are shown in Table 1.
Embodiment 3
Graphene oxide is synthesized by the step in example 1.
The preparation of carboxy nitrile rubber/stannic oxide/graphene nano composite material:
(1) it weighs 0.6 part of a certain amount of water of graphene oxide concentrate addition to be diluted, ultrasonic vibration 2h obtains oxidation stone
Black alkene dispersion liquid；
(2) graphene oxide dispersion and 0.001-0.1 parts of polyethyleneimines are mixed, ultrasonic disperse 2h；
(3) above-mentioned (1), (2) dispersion liquid are mixed with carboxylic acrylonitrile butadiene rubber latex, is ultrasonically treated 2h, whipping temp, ultrasound after stirring 6h
Temperature is 35 DEG C；
(4) when ultrasonic disperse closes to an end, side stirring becomes ultrasound and CaCl is added2Saturated solution carry out " dynamic flocculate ", it is " dynamic
Carboxy nitrile rubber/graphene oxide rubber blocks 1h is washed with deionized water after state flocculation ", is repeated 5 times.
(5) the preparation barrier protecting film using block rubber obtained in step (4) as masterbatch, through mill, calendering, vulcanization
The barrier protecting film with a thickness of 1mm is obtained afterwards.
The pattern of preparation-obtained carboxy nitrile rubber/graphene oxide is as seen in figs. 5-6.Embodiment 3 is prepared to be obtained
To barrier property protecting film have to the protective of the purer carboxy nitrile rubber film of the protective of chemical solvent and extremely significantly mention
High and be compared to embodiment 1,2, the guard time of barrier chemical solvent is also extended, and the results are shown in Table 1.
Embodiment 4
Graphene oxide is synthesized by the step in example 1.
The preparation of carboxy nitrile rubber/stannic oxide/graphene nano composite material:
(1) it weighs 0.9 part of a certain amount of water of graphene oxide concentrate addition to be diluted, ultrasonic vibration 2h obtains oxidation stone
Black alkene dispersion liquid；
(2) graphene oxide dispersion and 0.001-0.1 parts of polyethyleneimines are mixed, ultrasonic disperse 2h；
(3) above-mentioned (1), (2) dispersion liquid are mixed with carboxylic acrylonitrile butadiene rubber latex, is ultrasonically treated 2h, whipping temp, ultrasound after stirring 6h
Temperature is 35 DEG C；
(4) when ultrasonic disperse closes to an end, side stirring becomes ultrasound and CaCl is added2Saturated solution carry out " dynamic flocculate ", it is " dynamic
Carboxy nitrile rubber/graphene oxide rubber blocks 1h is washed with deionized water after state flocculation ", is repeated 5 times.
(5) the preparation barrier protecting film using block rubber obtained in step (4) as masterbatch, through mill, calendering, vulcanization
The barrier protecting film with a thickness of 1mm is obtained afterwards.
The pattern of preparation-obtained carboxy nitrile rubber/graphene oxide is as Figure 7-8.Embodiment 4 is prepared to be obtained
To barrier property protecting film have to the protective of the purer carboxy nitrile rubber film of the protective of chemical solvent and extremely significantly mention
High and be compared to embodiment 1,2,3, the guard time of barrier chemical solvent is also extended, and the results are shown in Table 1:
The resulting experimental result of specific embodiment 1-4 please refers to the following table 1.
Carboxy nitrile rubber/stannic oxide/graphene nano composite material protection effect prepared by 1. embodiment 1-4 of table
In conclusion the obtained carboxy nitrile rubber of preparation method/stannic oxide/graphene nano composite material according to the invention
Good chemical solvent barrier property is all had compared to the prior art.And the carboxyl butyronitrile obtained in the conditions of example 4
Rubber/stannic oxide/graphene nano composite material is especially prominent to the barrier property of chemical solvent, is not only significantly higher than the prior art
Common level, the even more significantly larger than level of embodiment 1-3.
Following embodiment will be helpful to those skilled in the art and further understand the present invention, but not limit in any form
The present invention.It should be pointed out that those skilled in the art, without departing from the inventive concept of the premise, also
Several modifications and improvements can be made.These are all within the scope of protection of the present invention.
Claims (6)
1. a kind of carboxy nitrile rubber/stannic oxide/graphene nano composite material for obstructing hazardous chemical solvent, which is characterized in that
Stannic oxide/graphene nano piece is orientated in carboxy nitrile rubber matrix along in-plane, is effectively realized to chemistry in thickness direction
Solvent penetration barrier, wherein the mass fraction of polyethyleneimine is 0.001-0.10wt% in composite material, graphene oxide
Mass fraction is 0.01-1wt%, and the mass fraction of carboxy nitrile rubber is 98.90-99.99wt%.
2. composite material according to claim 1, which is characterized in that the acrylonitrile content of the carboxy nitrile rubber is
High acrylonitrile content, high acrylonitrile content or middle high acrylonitrile content；Wherein, the high acrylonitrile content refers to quality
Percentage is greater than 43%, and the high acrylonitrile content refers to that mass percent is 36-42%, and the middle high acrylonitrile content refers to matter
Amount percentage is 31-35%.
3. composite material according to claim 1, which is characterized in that the lamella size of graphene oxide 0.5-50 μm it
Between, the number of plies is between 1-10 layers.
4. composite material according to claim 1, which is characterized in that graphene oxide is prepared by improved Hummers method.
5. carboxy nitrile rubber of any of claims 1-4/stannic oxide/graphene nano composite material preparation method,
Characterized by comprising the following steps:
(1) graphene oxide concentrate made from Hummers method is diluted with water dispersion, ultrasonic vibration obtains graphene oxide
Graphene oxide dispersion is uniformly mixed with polyethyleneimine aqueous dispersions, is ultrasonically treated by dispersion liquid；
(2) graphene oxide/polyethyleneimine dispersion liquid is mixed evenly with diluted carboxylic acrylonitrile butadiene rubber latex；
(3) the system temperature control of step (2) is stirred at 30-60 DEG C, then mixed emulsion is moved in ultrasonic vibration machine,
It is ultrasonic under conditions of 30-60 DEG C；
(4) in ultrasonic procedure, calcium chloride saturated solution is added, carries out " dynamic flocculate " and stir in ultrasound, finally by
To block rubber is washed with deionized water, dries, as masterbatch；
(5) masterbatch obtained in step (4) carries out mill with block carboxy nitrile rubber according to the proportion, calendering, vulcanization obtain
Carboxy nitrile rubber/stannic oxide/graphene nano composite material.
6. preparation method according to claim 5, which is characterized in that the speed of agitator of step (4) is 600-2000rpm,
Ultrasonic power is 60-100W.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111269452A (en) * | 2019-06-20 | 2020-06-12 | 中原工学院 | Preparation method of carboxyl nitrile rubber composite film for electromagnetic shielding |
| CN111484636A (en) * | 2020-04-24 | 2020-08-04 | 河北铁科翼辰新材科技有限公司 | Graphene oxide carboxyl nitrile rubber microsphere composite material and preparation method thereof |
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