CN110028680A - The preparation method of carbon nanotube composite hydrogel - Google Patents
The preparation method of carbon nanotube composite hydrogel Download PDFInfo
- Publication number
- CN110028680A CN110028680A CN201910292205.4A CN201910292205A CN110028680A CN 110028680 A CN110028680 A CN 110028680A CN 201910292205 A CN201910292205 A CN 201910292205A CN 110028680 A CN110028680 A CN 110028680A
- Authority
- CN
- China
- Prior art keywords
- carbon nanotube
- reactor
- agar
- acrylic acid
- polyvinyl alcohol
- 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.)
- Withdrawn
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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- 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
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- 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
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/12—Agar-agar; Derivatives thereof
-
- 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
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
-
- 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
- C08K3/041—Carbon nanotubes
-
- 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
- C08K3/28—Nitrogen-containing compounds
-
- 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
Abstract
The present invention discloses a kind of preparation method of carbon nanotube composite hydrogel, using the raw material of following mass ratio: 0~2% agar, 0~5% polyvinyl alcohol, 30%~50% acrylic acid, 0~2% Fe(NO3)39H2O, 0~1% crosslinking agent, 0~1% initiator, 50%~60% water and 0~1% modified carbon nano-tube, pass through improved technology route, there is provided a kind of completely new preparation method: the first layer for being first cooled into physical crosslinking using the preparation method treated different things alike is crisp, frangible agar network, it is strong that free radical polymerization forms the second layer, acrylic acid-iron ion network of tough and tensile ion collaboration coordination, the third layer polyvinyl alcohol network of physical crosslinking is formed by freeze-thaw circulation, crosslinking of the carbon nanotube as crosslinking points enhancing gel is introduced in triplicated network simultaneously Degree forms covalent bond and hydrogen bond, final that the nanotube composite hydrogel with good thermal stability, high mechanical strength, high moisture content and low swelling ratio carbon is made.
Description
Technical field
The invention belongs to field of polymer material preparing technology, are related to a kind of preparation side of carbon nanotube composite hydrogel
Method.
Background technique
Hydrogel belongs to hydrophilic polymer, and a large amount of water is swollen and retained after capable of absorbing water and can maintain its three dimensional network
Network structure.In general, hydrogel is by chemistry or to be physical crosslinking, and passes through covalent bond between the hydrogel of chemical crosslinking
Crosslinking is insoluble in water, and passes through Van der Waals force, ionic interaction, hydrogen bond or hydrophobic between the hydrogel being physical crosslinking
Interaction, these physical gels have sol-gel invertibity.However the material that hydrogel is soft and wet as one kind, it
Mechanical strength is weak, stability is poor, it is easy absorb a large amount of water and be swollen and loose porous structure causes moisture to be easy to run off, easily
It is destroyed, great limitation thus is produced to the application of hydrogel, so preparation high intensity, thermal stability, high-moisture
Content and low swelling ratio hydrogel have become a hot topic of research.Wherein typical high intensity hydrogel refers mainly to organic/inorganic and receives
Rice composite hydrogel, topological hydrogel, double-network hydrogel and ionic hydrogels etc..
The hydrogel molecules amount of three-dimensional net structure is considered as the unlimited, (packet when minor change occurs for external environment
Include pH value, temperature, electric field, ionic strength, salt form, solvent, external stress or light), volume can be reversibly changed in response type gel
It responds, due to the unique network structure of three network aqueous gels and surface nature, is widely studied and applied.
With the progress of nanosecond science and technology and complex technique, organic/inorganic nano composite hydrogel becomes the hot spot of research.
Carbon nanotube as a kind of inorganic material, structure but to high molecular material and its similar and with outstanding mechanical property and soft
Toughness.Carbon nanotube (Carbon nanotubes, CNTs) has the draw ratio of superelevation, unique single-layer or multi-layer tubular structure
With excellent mechanical property and physical property, such as high intensity, high thermal conductivity, high conduction performance and low thermal coefficient of expansion, it is considered as
Prepare the ideal reinforcement of high-performance composite materials.In recent years, domestic and foreign scholars are multiple to carbon nanotubes reinforced polymer base
The research of condensation material has made great progress.PCL (polycaprolactone dihydric alcohol) is grafted to by Jing to be modified through nitration mixture
The surface CNTs is obtained the carbon nanotube (MWCNT-PCL) of functionalization, and is prepared using functionalized carbon nano-tube and polyurethane (PU)
A kind of Nanometer composite hydrogel.By scanning electron microscope (SEM) and transmission electron microscope (TEM) discovery feature carbon nano tube in poly- ammonia
It is well dispersed in ester system.Infrared spectroscopy (FTIR) and Raman spectrum (Raman) the result shows that, polymer molecular chain and carbon nanometer
There is stronger interactions between pipe.Mechanical experimental results show the tensile strength and modulus point of nanocomposite
51.2% and 33.5% are not increased.In addition, the carbon nanotube of chemical modification is combined in cellulose gel by Zhang, discovery
The swellbility of the gel reduces with the increase of content of carbon nanotubes, and the compression strength of gel is 83KPa when high swelling degree, most
In terms of big strain is 99.98%, while the nano-gel material can also be used for drug release and bioengineering.In addition to this carbon is received
Mitron composite hydrogel also has important application in terms of Dye Adsorption, battery material.Duman has found carbon nanotube plural gel material
Material can methylene blue cation in quick adsorption dyestuff.Zheng utilizes the good mechanics electric conductivity of CNTs, by CNTs and nanometer
Particle and conductive polymer gel have been prepared into dynamical lithium electrode.The composite material has preferable mechanical property, conduction
Property and good ion transport capacity, be suitable for supercapacitor and battery etc..In addition, in order to improve nanofiller
Performance, according to the principle of material structure, performance complement, can by two or more nanofillers it is compound after to obtain performance more excellent
Composite filled object.Ma receives two-dimentional Go and one-dimensional CNTs by the graphene/carbon that gamma-ray irradiation is prepared for 3D reticular structure
Mitron (GO/CNTs) hydridization filler is combined to polyvinyl alcohol (PVA) hydrogel network using radical polymerization in situ
In.Test result shows that GO/CNTs hydridization filler is dispersed in gel structure, and GO/CNTs and PVA system it
Between there are the interaction forces such as stronger covalent bond, hydrogen bond.Meanwhile when the mass fraction of nano hybridization filler GO/CNTs is 1%
When, the mechanical property and thermal stability of Nanometer composite hydrogel are greatly improved than not adding the PVA pure condensate glue of GO/CNTs,
If tensile strength improves 56%, reach 8.19 × 104KPa；Young's modulus improves 33.6%, reaches 3.9 × 106KPa.So
Metal iron ion and acrylic acid ligand complex are prepared the composite hydrogel of second layer physical crosslinking by Wang afterwards, and the above research provides
The strategy that the nanofiller of different-shape is combined as a whole, the research for enhancing composite material correlated performance later provide one
The new idea and method of kind.By the way that carbon nanotube is introduced into agar/three network aqueous gel of acrylic acid/polyvinyl alcohol, Ke Yiyou
Raising hydrogel thermal stability, mechanical performance, moisture content and the low swelling ratio of effect expand it and lead in industry, biology, medical treatment etc.
The application in domain.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of preparation method of carbon nanotube composite hydrogel, for water
The mechanical strength of gel is weak, stability is poor, easy absorb a large amount of water and is swollen and loose porous structure causes moisture easily to flow
The shortcomings that mistake, by changing the technology path of three network aqueous gels, carbon nanotube is added and using a kind of new preparation method, from
And thermal stability, mechanical performance and the moisture content of hydrogel are improved, there is low swelling ratio.
The present invention is implemented as follows:
A kind of preparation method of carbon nanotube composite hydrogel, the carbon nanotube composite hydrogel include following mass ratio
Raw material: 0~2% agar, 0~5% polyvinyl alcohol, 30%~50% acrylic acid, 0~2% Fe(NO3)39H2O,
0~1% crosslinking agent, 0~1% initiator, 50%~60% water and 0~1% modified carbon nano-tube；
Its specific preparation method the following steps are included:
S1, agar, polyvinyl alcohol, acrylic acid and the first raw material for accounting for raw material water inventory 90% are weighed by above-mentioned mass ratio
Water is added in first reactor, excludes the air in first reactor under nitrogen protection, and first reactor is being sealed
It is placed in 5~10min of heating in 85~95 DEG C of oil bath pan under state, continuously stirs after forming uniform solution, by the first reaction
Device is cooled to room temperature, and is placed in 1~5min in -1~-10 DEG C of low temperature environments, forms the first layer agar network of physical crosslinking；
S2, the second raw water of modified carbon nano-tube, Fe(NO3)39H2O, crosslinking agent, initiator and residue 10% is added
Enter in second reactor, stirs evenly；
S3, the solution in second reactor is added in first reactor under nitrogen protection, is uniformly mixed；
S4, the mixed solution in first reactor is added in third reactor, is sealed, by third reactor at 60 DEG C
Water-bath in react 2~6h, free radical polymerization formed have collaboration coordination second layer acrylic acid-iron ion network, will
The gel of preparation takes out；
S5, the gel of taking-up is freezed into 2~6h at -10~-20 DEG C, then thaw 2~6h at room temperature, so recycles
The third layer polyvinyl alcohol network of 2~5 formation hydrogel physical crosslinkings, finally obtains carbon nanotube composite hydrogel.
Preferably, modified carbon nano-tube is the carbon nanotube after acidification, specific acidization are as follows: impregnate carbon nanotube
In the HNO that volume ratio is 1:33And H2SO4Mixed acid solution in ultrasound 5h then diluted, filtered and cold repeatedly with deionized water
It is lyophilized dry.
Preferably, the water during carbon nanotube acidification in ultrasonic machine is replaced 2~3 times, has carbon nanotube better
Dispersion effect.
Preferably, the carbon nanotube after acidification is dispersed using preceding ground processing.
Preferably, the crosslinking agent is N, N ' methylene-bisacrylamide.
Preferably, the initiator is the mixed initiator system that ammonium persulfate and potassium peroxydisulfate form.
Compared with prior art, the invention has the following advantages:
The preparation method that the present invention provides a kind of carbon nanotube composite hydrogel provides one kind by improved technology route
Completely new preparation method: crisp, the frangible agar of the first layer that physical crosslinking is first cooled into using the preparation method treated different things alike
Network, free radical polymerization form acrylic acid-iron ion network of strong, the tough and tensile ion collaboration coordination of the second layer, pass through
Freeze-thaw circulation forms the third layer polyvinyl alcohol network of physical crosslinking, while carbon nanotube conduct is introduced in triplicated network
The degree of cross linking that crosslinking points enhance gel forms covalent bond and hydrogen bond, finally obtained carbon nanotube composite hydrogel, and which improve water
The mechanical strength of gel itself is weak, stability is poor, easy absorb a large amount of water and is swollen and loose porous structure leads to moisture
The shortcomings that being easy to run off, the degree of cross linking for introducing modified carbon nanotube as network cross-linked point enhancing gel form covalent bond and hydrogen
Key, so that final hydrogel obtained has good thermal stability, high mechanical strength, high moisture content and low swelling ratio.
Detailed description of the invention
Fig. 1 is the fourier transform infrared spectroscopy figure before and after carbon nano-tube modification；
Fig. 2 is the X-ray diffraction spectra figure before and after carbon nano-tube modification；
Fig. 3 is the dispersed comparative diagram before and after carbon nano-tube modification；
Fig. 4 is agar/acrylic acid/polyvinyl alcohol, agar/acrylic acid-iron ion/polyvinyl alcohol, agar/acrylic acid-iron
Ion/three network aqueous gel of polyvinyl alcohol/carbon nanotube fourier transform infrared spectroscopy figure；
Fig. 5 is agar/acrylic acid/polyvinyl alcohol, agar/acrylic acid-iron ion/polyvinyl alcohol, agar/acrylic acid-iron
Ion/three network aqueous gel of polyvinyl alcohol/carbon nanotube X-ray diffraction spectra figure；
Fig. 6 is agar/acrylic acid/polyvinyl alcohol, agar/acrylic acid-iron ion/polyvinyl alcohol, agar/acrylic acid-iron
Ion/three network aqueous gel of polyvinyl alcohol/carbon nanotube hot weight curve；
Fig. 7 a is agar/acrylic acid/polyvinyl alcohol, agar/acrylic acid-iron ion/polyvinyl alcohol, agar/acrylic acid-iron
Ion/three network aqueous gel of polyvinyl alcohol/carbon nanotube stress strain curve figure；
Fig. 7 b is agar/acrylic acid/polyvinyl alcohol, agar/acrylic acid-iron ion/polyvinyl alcohol, agar/acrylic acid-iron
Ion/three network aqueous gel of polyvinyl alcohol/carbon nanotube compression curve figure；
Fig. 8 a is agar/acrylic acid/polyvinyl alcohol, agar/acrylic acid-iron ion/polyvinyl alcohol, agar/acrylic acid-iron
Ion/three network aqueous gel of polyvinyl alcohol/carbon nanotube swelling ratio；
Fig. 8 b is agar/acrylic acid/polyvinyl alcohol, agar/acrylic acid-iron ion/polyvinyl alcohol, agar/acrylic acid-iron
Ion/three network aqueous gel of polyvinyl alcohol/carbon nanotube moisture content figure；
Fig. 8 c is agar/acrylic acid/polyvinyl alcohol, agar/acrylic acid-iron ion/polyvinyl alcohol, agar/acrylic acid-iron
Ion/three network aqueous gel of polyvinyl alcohol/carbon nanotube gel fraction figure；
Fig. 9 a is the scanning electron microscope (SEM) photograph of carbon nanotube composite hydrogel of the invention；
Fig. 9 b is the scanning electron microscope (SEM) photograph of carbon nanotube composite hydrogel of the invention.
Specific embodiment
Below with reference to the attached drawing exemplary embodiment that the present invention will be described in detail, feature and aspect of performance.
Raw material used by present invention preparation carbon nanotube composite hydrogel includes the component of following mass ratio: 0~2%
Agar, 0~5% polyvinyl alcohol, 30%~50% acrylic acid, 0~2% Fe(NO3)39H2O, 0~1% crosslinking agent,
0~1% initiator, 50%~60% water and 0~1% modified carbon nano-tube.
Modified Nano pipe is the carbon nanotube after acidification, specific acidization are as follows: carbon nanotube is immersed in volume ratio
For the HNO of 1:33And H2SO4Mixed acid solution in ultrasound 5h then diluted repeatedly with deionized water, filter, be freeze-dried.Carbon
Water in nanotube acidization in ultrasonic machine is replaced 2~3 times, and carbon nanotube is made to have better dispersion effect.After acidification
Carbon nanotube is dispersed using preceding ground processing.Fig. 1 is the fourier transform infrared spectroscopy figure before and after carbon nano-tube modification,
It can be seen from the figure that the carbon nano tube surface functional group derivatization after acidified, changes the surface knot of carbon nanotube
Structure simultaneously successfully introduces hydroxy functional group on its surface；Fig. 2 is the X-ray diffraction spectra figure before and after carbon nano-tube modification, acid
The phenomenon that carbon nanotube winding degree after change reduces, is not in heap knot；Fig. 3 is the dispersibility control before and after carbon nano-tube modification
Figure, modified carbon nano-tube have good dispersibility in water.
Preferably, crosslinking agent N, N ' methylene-bisacrylamide.Initiator is that ammonium persulfate and potassium peroxydisulfate form
Mixed initiator system.The cross-linking agent aqueous solution and initiator solution that the preceding compound concentration first of preparation is 5~20mg/ml.
The preparation method of carbon nanotube composite hydrogel of the invention specifically includes the following steps:
S1, agar, polyvinyl alcohol, acrylic acid and the first raw material for accounting for raw material water inventory 90% are weighed by above-mentioned mass ratio
Water is added in first reactor, excludes the air in first reactor under nitrogen protection, and first reactor is being sealed
5~10min of heating is placed in 85~95 DEG C of oil bath pan under state, in oil bath pan heating time it is unsuitable it is too long no more than
Otherwise 10min is easy initiated polymerization, continuously stir after forming uniform solution, first reactor is cooled to room temperature, and
It is placed in 1~5min in -1~-10 DEG C of low temperature environments, forms the first layer agar network of physical crosslinking；
S2, the second raw water of modified carbon nano-tube, Fe(NO3)39H2O, crosslinking agent, initiator and residue 10% is added
Enter in second reactor, stirs evenly；
S3, the solution in second reactor is quickly added in first reactor under nitrogen protection, is uniformly mixed,
Rapidly joining and carrying out mixing is that iron ion and acrylic acid exothermic heat of reaction cause polymerization in order to prevent；
S4, the mixed solution in first reactor is added in third reactor, is sealed, sealed molten in order to prevent to mix
Third reactor is reacted 2~6h by liquid ingress of air initiation reaction in 60 DEG C of water-bath, and free radical polymerization, which is formed, has collaboration
Second layer acrylic acid-iron ion network of coordination takes out the gel of preparation；
S5, the gel of taking-up is freezed into 2~6h at -10~-20 DEG C, then thaw 2~6h at room temperature, so recycles
The third layer polyvinyl alcohol network of 2~5 formation hydrogel physical crosslinkings, finally obtains carbon nanotube composite hydrogel.
Carbon nanotube composite hydrogel produced by the present invention is substantially agar/acrylic acid-iron ion/polyvinyl alcohol/carbon and receives
Three network aqueous gel of mitron.
Embodiment 1
S1,0.15g agar, 0.15g polyvinyl alcohol, 4g acrylic acid and 4.9797ml water are weighed, is added to first reactor
In, the air in first reactor is excluded under nitrogen protection, and first reactor is placed in 95 DEG C of oil in sealed states
5min is heated in bath, continuously stirs after forming uniform solution, first reactor is cooled to room temperature, and is placed in -3 DEG C of environment
Middle 5min forms the first layer agar network of physical crosslinking；
S2, cross-linking agent aqueous solution and initiator solution that concentration is 10mg/ml is respectively configured, 0.001g acidification carbon is received
Mitron, 0.12ml cross-linking agent aqueous solution, 0.2ml initiator solution, 0.15g Fe(NO3)39H2O and 0.5533ml water are added the
In two reactors, stir evenly；
S3, the solution in second reactor is added in first reactor under nitrogen protection, is uniformly mixed；
S4, the mixed solution in first reactor is added in third reactor, is sealed, by third reactor at 60 DEG C
Water-bath in react 3h, free radical polymerization forms the second layer acrylic acid-iron ion network with collaboration coordination, will prepare
Gel take out；
S5, the gel of taking-up is freezed into 2h at -10 DEG C, then thaw 2h at room temperature, so recycles 3 formation water-settings
The third layer polyvinyl alcohol network of glue physical crosslinking, finally obtains carbon nanotube composite hydrogel.
Embodiment 2
S1,0.15g agar, 0.25g polyvinyl alcohol, 4g acrylic acid and 4.8897ml water are weighed, is added to first reactor
In, the air in first reactor is excluded under nitrogen protection, and first reactor is placed in 95 DEG C of oil in sealed states
10min is heated in bath, continuously stirs after forming uniform solution, first reactor is cooled to room temperature, and is placed in -3 DEG C of rings
5min in border forms the first layer agar network of physical crosslinking；
S2, cross-linking agent aqueous solution and initiator solution that concentration is 10mg/ml is respectively configured, 0.001g acidification carbon is received
Mitron, 0.12ml cross-linking agent aqueous solution, 0.2ml initiator solution, 0.15g Fe(NO3)39H2O, 0.5433ml water are added the
In two reactors, stir evenly；
S3, the solution in second reactor is added in first reactor under nitrogen protection, is uniformly mixed；
S4, the mixed solution in first reactor is added in third reactor, is sealed, by third reactor at 60 DEG C
Water-bath in react 3h, free radical polymerization forms the second layer acrylic acid-iron ion network with collaboration coordination, will prepare
Gel take out；
S5, the gel of taking-up is freezed into 6h at -15 DEG C, then thaw 2h at room temperature, so recycles 4 formation water-settings
The third layer polyvinyl alcohol network of glue physical crosslinking, finally obtains carbon nanotube composite hydrogel.
Embodiment 3
S1,0.2g agar, 0.25g polyvinyl alcohol, 4g acrylic acid and 4.8447ml water are weighed, is added to first reactor
In, the air in first reactor is excluded under nitrogen protection, and first reactor is placed in 85 DEG C of oil in sealed states
8min is heated in bath, continuously stirs after forming uniform solution, first reactor is cooled to room temperature, and is placed in -5 DEG C of environment
Middle 3min forms the first layer agar network of physical crosslinking；
S2, cross-linking agent aqueous solution and initiator solution that concentration is 10mg/ml is respectively configured, 0.001g acidification carbon is received
Mitron, 0.6ml cross-linking agent aqueous solution, 1ml initiator solution, 0.15g Fe(NO3)39H2O, 0.5383ml water are added second instead
It answers in device, stirs evenly；
S3, the solution in second reactor is added in first reactor under nitrogen protection, is uniformly mixed；
S4, the mixed solution in first reactor is added in third reactor, is sealed, by third reactor at 60 DEG C
Water-bath in react 4h, free radical polymerization forms the second layer acrylic acid-iron ion network with collaboration coordination, will prepare
Gel take out；
S5, the gel of taking-up is freezed into 6h at -20 DEG C, then thaw 2h at room temperature, so recycles 5 formation water-settings
The third layer polyvinyl alcohol network of glue physical crosslinking, finally obtains carbon nanotube composite hydrogel.
Embodiment 4
S1,0.2g agar, 0.25g polyvinyl alcohol, 3.5g acrylic acid and 5.2866ml water are weighed, is added to first reactor
In, the air in first reactor is excluded under nitrogen protection, and first reactor is placed in 85 DEG C of oil in sealed states
8min is heated in bath, continuously stirs after forming uniform solution, first reactor is cooled to room temperature, and is placed in -5 DEG C of environment
Middle 3min forms the first layer agar network of physical crosslinking；
S2, cross-linking agent aqueous solution and initiator solution that concentration is 10mg/ml is respectively configured, 0.01g acidification carbon is received
Mitron, 0.6ml cross-linking agent aqueous solution, 1ml initiator solution, 0.15g Fe(NO3)39H2O and 0.5874ml water are added second
In reactor, stir evenly；
S3, the solution in second reactor is added in first reactor under nitrogen protection, is uniformly mixed；
S4, the mixed solution in first reactor is added in third reactor, is sealed, by third reactor at 60 DEG C
Water-bath in react 5h, free radical polymerization forms the second layer acrylic acid-iron ion network with collaboration coordination, will prepare
Gel take out；
S5, the gel of taking-up is freezed into 6h at -20 DEG C, then thaw 6h at room temperature, so recycles 2 formation water-settings
The third layer polyvinyl alcohol network of glue physical crosslinking, finally obtains carbon nanotube composite hydrogel.
Embodiment 5
S1,0.2g agar, 0.25g polyvinyl alcohol, 3.5g acrylic acid and 5.1894ml water are weighed, is added to first reactor
In, the air in first reactor is excluded under nitrogen protection, and first reactor is placed in 90 DEG C of oil in sealed states
8min is heated in bath, continuously stirs after forming uniform solution, first reactor is cooled to room temperature, and is placed in -10 DEG C of rings
5min in border forms the first layer agar network of physical crosslinking；
S2, cross-linking agent aqueous solution and initiator solution that concentration is 15mg/ml is respectively configured, 0.01g acidification carbon is received
Mitron, 0.6ml cross-linking agent aqueous solution, 1ml initiator solution, 0.25g Fe(NO3)39H2O and 0.5766ml water are added second
In reactor, stir evenly；
S3, the solution in second reactor is added in first reactor under nitrogen protection, is uniformly mixed；
S4, the mixed solution in first reactor is added in third reactor, is sealed, by third reactor at 60 DEG C
Water-bath in react 6h, free radical polymerization forms the second layer acrylic acid-iron ion network with collaboration coordination, will prepare
Gel take out；
S5, the gel of taking-up is freezed into 3h at -20 DEG C, then thaw 6h at room temperature, so recycles 3 formation water-settings
The third layer polyvinyl alcohol network of glue physical crosslinking, finally obtains carbon nanotube composite hydrogel.
Embodiment 6
S1,0.15g agar, 0.25g polyvinyl alcohol, 4g acrylic acid and 4.8843ml water are weighed, is added to first reactor
In, the air in first reactor is excluded under nitrogen protection, and first reactor is placed in 90 DEG C of oil in sealed states
8min is heated in bath, continuously stirs after forming uniform solution, first reactor is cooled to room temperature, and is placed in -10 DEG C of rings
5min in border forms the first layer agar network of physical crosslinking；
S2, cross-linking agent aqueous solution and initiator solution that concentration is 15mg/ml is respectively configured, 0.005g acidification carbon is received
Mitron, 0.6ml cross-linking agent aqueous solution, 0.6ml initiator solution, 0.15g Fe(NO3)39H2O and 0.5427ml water are added the
In two reactors, stir evenly；
S3, the solution in second reactor is added in first reactor under nitrogen protection, is uniformly mixed；
S4, the mixed solution in first reactor is added in third reactor, is sealed, by third reactor at 60 DEG C
Water-bath in react 6h, free radical polymerization forms the second layer acrylic acid-iron ion network with collaboration coordination, will prepare
Gel take out；
S5, the gel of taking-up is freezed into 5h at -20 DEG C, then thaw 2h at room temperature, so recycles 2 formation water-settings
The third layer polyvinyl alcohol network of glue physical crosslinking, finally obtains carbon nanotube composite hydrogel.
Embodiment 7
S1,0.2g agar, 0.25g polyvinyl alcohol, 4g acrylic acid and 4.7412ml water are weighed, is added to first reactor
In, the air in first reactor is excluded under nitrogen protection, and first reactor is placed in 90 DEG C of oil in sealed states
10min is heated in bath, continuously stirs after forming uniform solution, first reactor is cooled to room temperature, and is placed in -8 DEG C of rings
4min in border forms the first layer agar network of physical crosslinking；
S2, cross-linking agent aqueous solution and initiator solution that concentration is 20mg/ml is respectively configured, 0.05g acidification carbon is received
Mitron, 0.7ml cross-linking agent aqueous solution, 0.9ml initiator solution, 0.2g Fe(NO3)39H2O and 0.5268ml water are added second
In reactor, stir evenly；
S3, the solution in second reactor is added in first reactor under nitrogen protection, is uniformly mixed；
S4, the mixed solution in first reactor is added in third reactor, is sealed, by third reactor at 60 DEG C
Water-bath in react 6h, free radical polymerization forms the second layer acrylic acid-iron ion network with collaboration coordination, will prepare
Gel take out；
S5, the gel of taking-up is freezed into 6h at -20 DEG C, then thaw 2h at room temperature, so recycles 3 formation water-settings
The third layer polyvinyl alcohol network of glue physical crosslinking, finally obtains carbon nanotube composite hydrogel.
Structural characterization is carried out to hydrogel using infrared spectrometer, Fig. 4 is agar/acrylic acid/polyvinyl alcohol, agar/the third
Olefin(e) acid-iron ion/polyvinyl alcohol, agar/acrylic acid-iron ion/three network aqueous gel of polyvinyl alcohol/carbon nanotube Fourier
Transform infrared spectroscopy figure, it is identical from figure can intuitively to see that the infrared absorption peak of this 3 three network aqueous gels appears in
Position shows that carbon nano tube surface is fully wrapped around by gel, the crosslinking points as gel network.In figure it is available
3400cm-1Left and right is the strong stretching vibration peak of-OH and C-OH, in 1710cm-1There is weak C=O and shakes peak in left and right,
1450cm-1Left and right occurs that C-O-H flexural vibrations peak, appears in 1260cm-1And 1130cm-1Absorption vibration peak be N-H and
C-N key derives from crosslinking agent.
Using x-ray diffractometer to hydrogel carry out structural characterization, Fig. 5 be agar/acrylic acid/polyvinyl alcohol, agar/
Acrylic acid-iron ion/polyvinyl alcohol, agar/acrylic acid-iron ion/three network aqueous gel of polyvinyl alcohol/carbon nanotube X are penetrated
Line diffraction light spectrogram, Cong Tuzhong is it is observed that add agar/acrylic acid-iron ion/polyvinyl alcohol/carbon nanometer of carbon nanotube
Significantly becoming smaller occurs in the intensity of three network aqueous gel absorption peak of pipe, and absorption peak becomes short narrow and illustrates adding for carbon nanotube
The degree of cross linking for entering to improve strand is conducive to generate crystallization.
Structural characterization is carried out to hydrogel using thermogravimetric analyzer, Fig. 6 is agar/acrylic acid/polyvinyl alcohol, agar/the third
Olefin(e) acid-iron ion/polyvinyl alcohol, agar/acrylic acid-iron ion/three network aqueous gel of polyvinyl alcohol/carbon nanotube thermogravimetric are bent
Line chart, agar/acrylic acid-iron ion/three network aqueous gel of polyvinyl alcohol/carbon nanotube is 50~150 it is known from figures that
Apparent Mass lost is not occurred between DEG C and just occurs apparent quality decline curve until 387 DEG C, illustrates gel cross-linkage
Covalent bond between the raising and strand and carbon nanotube of degree makes the even closer stabilization of network promote the thermostabilization of hydrogel
Property is improved.
Compression and Expansion performance test is carried out to hydrogel by universal testing machine, Fig. 7 a is agar/acrylic acid/polyethylene
Alcohol, agar/acrylic acid-iron ion/polyvinyl alcohol, agar/acrylic acid-three network water-setting of iron ion/polyvinyl alcohol/carbon nanotube
The stress strain curve figure of glue, Fig. 7 b are agar/acrylic acid/polyvinyl alcohol, agar/acrylic acid-iron ion/polyvinyl alcohol, agar/the third
Olefin(e) acid-iron ion/three network aqueous gel of polyvinyl alcohol/carbon nanotube compression curve figure, agar/acrylic acid-iron ion/poly- second
Test stretching and compression performance, the stretching under the sensor of 100N and 3000N respectively of three network aqueous gel of enol/carbon nanotube
Stress and breaking strain can achieve 1.5Mpa, 14.24mm/mm, and the compression stress of gel can be under 80% deformation
Reach 1.69Mpa.
At room temperature test different time under hydrogel swelling ratio, Fig. 8 a be agar/acrylic acid/polyvinyl alcohol, agar/
Acrylic acid-iron ion/polyvinyl alcohol, agar/acrylic acid-iron ion/three network aqueous gel of polyvinyl alcohol/carbon nanotube swelling
Rate, Fig. 8 b be agar/acrylic acid/polyvinyl alcohol, agar/acrylic acid-iron ion/polyvinyl alcohol, agar/acrylic acid-iron ion/
The moisture content figure of three network aqueous gel of polyvinyl alcohol/carbon nanotube tests moisture content and the time of hydrogel at 40 DEG C
Relationship, agar/acrylic acid-iron ion/three network aqueous gel of polyvinyl alcohol/carbon nanotube swelling ratio is lower, and moisture contains
Amount is higher, and Fig. 8 c is agar/acrylic acid/polyvinyl alcohol, agar/acrylic acid-iron ion/polyvinyl alcohol, agar/acrylic acid-iron
Ion/three network aqueous gel of polyvinyl alcohol/carbon nanotube gel fraction figure, by agar/acrylic acid of identical size/poly- second
Enol, agar/acrylic acid-iron ion/polyvinyl alcohol, agar/acrylic acid-three network water of iron ion/polyvinyl alcohol/carbon nanotube
Gel is placed in freeze-drying, agar/acrylic acid-iron ion/three network aqueous gel of polyvinyl alcohol/carbon nanotube in freeze drier
Gel fraction is minimum, and unreacted monomer and polymer are more in network structure；Fig. 9 a is carbon nanotube Compound Water of the invention
The scanning electron microscope (SEM) photograph of gel, Fig. 9 b are the scanning electron microscope (SEM) photograph of carbon nanotube composite hydrogel of the invention, since hydrogel is added
After carbon nanotube in its network structure and not formed loose porous structure, but carbon nanotube plays the role of crosslinking points and makes
The degree of cross linking of strand is improved, and generates strong covalent bond with gel molecular chain and moisture is prevented to enter gel network and water
Divide and is lost when the temperature rises.
To sum up, hydrogel produced by the present invention has good thermal stability, high mechanical strength, high moisture content and low
Swelling ratio.
Finally, it should be noted that above-described each embodiment is merely to illustrate technical solution of the present invention, rather than it is limited
System；Although the present invention is described in detail referring to the foregoing embodiments, those skilled in the art should understand that: its
It can still modify to technical solution documented by previous embodiment, or part of or all technical features are carried out
Equivalent replacement；And these modifications or substitutions, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution
Range.
Claims (6)
1. a kind of preparation method of carbon nanotube composite hydrogel, it is characterised in that:
The carbon nanotube composite hydrogel includes the raw material of following mass ratio: 0~2% agar, 0~5% polyvinyl alcohol,
30%~50% acrylic acid, 0~2% Fe(NO3)39H2O, 0~1% crosslinking agent, 0~1% initiator, 50%~
60% water and 0~1% modified carbon nano-tube；
Its specific preparation method the following steps are included:
S1, agar, polyvinyl alcohol, acrylic acid and the first raw water for accounting for raw material water inventory 90% are weighed by above-mentioned mass ratio, add
Enter into first reactor, excludes the air in first reactor under nitrogen protection, and by first reactor in sealing state
Under be placed in 85~95 DEG C of oil bath pan 5~10min of heating, continuously stir after forming uniform solution, first reactor is cold
But to room temperature, it is placed in 1~5min in -1~-10 DEG C of low temperature environments, forms the first layer agar network of physical crosslinking；
S2, the second raw water of modified carbon nano-tube, Fe(NO3)39H2O, crosslinking agent, initiator and residue 10% is added the
In two reactors, stir evenly；
S3, the solution in second reactor is added in first reactor under nitrogen protection, is uniformly mixed；
S4, the mixed solution in first reactor is added in third reactor, is sealed, the water by third reactor at 60 DEG C
2~6h is reacted in bath, free radical polymerization forms the second layer acrylic acid-iron ion network with collaboration coordination, will prepare
Gel take out；
S5, the gel of taking-up is freezed into 2~6h at -10~-20 DEG C, then thaw 2~6h at room temperature, so recycles 2~5
The secondary third layer polyvinyl alcohol network for forming hydrogel physical crosslinking, finally obtains carbon nanotube composite hydrogel.
2. the preparation method of carbon nanotube composite hydrogel according to claim 1, it is characterised in that: modified carbon nano-tube
For the carbon nanotube after acidification, specific acidization are as follows:
Carbon nanotube is immersed in the HNO that volume ratio is 1:33And H2SO4Mixed acid solution in ultrasound 5h then use deionized water
It dilutes, filter and is freeze-dried repeatedly.
3. the preparation method of carbon nanotube composite hydrogel according to claim 2, it is characterised in that: carbon nanotube acidification
The water in ultrasonic machine is replaced 2~3 times in the process, and carbon nanotube is made to have better dispersion effect.
4. the preparation method of carbon nanotube composite hydrogel according to claim 1 or 3, it is characterised in that: after acidification
Carbon nanotube is dispersed using preceding ground processing.
5. the preparation method of carbon nanotube composite hydrogel according to claim 1, it is characterised in that: the crosslinking agent is
N, N ' methylene-bisacrylamide.
6. the preparation method of carbon nanotube composite hydrogel according to claim 1, it is characterised in that: the initiator is
The mixed initiator system of ammonium persulfate and potassium peroxydisulfate composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910292205.4A CN110028680A (en) | 2019-04-12 | 2019-04-12 | The preparation method of carbon nanotube composite hydrogel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910292205.4A CN110028680A (en) | 2019-04-12 | 2019-04-12 | The preparation method of carbon nanotube composite hydrogel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110028680A true CN110028680A (en) | 2019-07-19 |
Family
ID=67238249
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910292205.4A Withdrawn CN110028680A (en) | 2019-04-12 | 2019-04-12 | The preparation method of carbon nanotube composite hydrogel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110028680A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110862558A (en) * | 2019-11-26 | 2020-03-06 | 浙江清华柔性电子技术研究院 | Conductive gel and preparation method thereof |
| CN112934129A (en) * | 2021-01-28 | 2021-06-11 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | Efficient photo-thermal water evaporation carbon nanotube hydrogel and preparation method and application thereof |
| CN113307909A (en) * | 2021-06-22 | 2021-08-27 | 武汉轻工大学 | Hydrogel filled with nitrogen-doped carbon nanotubes and preparation method thereof |
| CN113896834A (en) * | 2021-11-03 | 2022-01-07 | 桂林电子科技大学 | Preparation method and application of composite hydrogel photothermal conversion material |
| CN113908781A (en) * | 2021-11-03 | 2022-01-11 | 深圳市橘井舒泉技术有限公司 | Gel for storing ozone and preparation method thereof |
| WO2023108868A1 (en) * | 2021-12-13 | 2023-06-22 | 广东海洋大学 | Preparation method for carbon nano tube/polyacrylic acid hydrogel, and product and application of carbon nano tube/polyacrylic acid hydrogel |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188575A (en) * | 2016-07-19 | 2016-12-07 | 湖北工业大学 | The preparation method of agar/polyacrylic acid dual network natural hydrogel material |
| CN107903406A (en) * | 2017-09-14 | 2018-04-13 | 刘志勇 | A kind of preparation method of three network aqueous gel of high intensity selfreparing |
-
2019
- 2019-04-12 CN CN201910292205.4A patent/CN110028680A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188575A (en) * | 2016-07-19 | 2016-12-07 | 湖北工业大学 | The preparation method of agar/polyacrylic acid dual network natural hydrogel material |
| CN107903406A (en) * | 2017-09-14 | 2018-04-13 | 刘志勇 | A kind of preparation method of three network aqueous gel of high intensity selfreparing |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110862558A (en) * | 2019-11-26 | 2020-03-06 | 浙江清华柔性电子技术研究院 | Conductive gel and preparation method thereof |
| CN110862558B (en) * | 2019-11-26 | 2023-11-21 | 浙江清华柔性电子技术研究院 | Conductive gel and preparation method thereof |
| CN112934129A (en) * | 2021-01-28 | 2021-06-11 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | Efficient photo-thermal water evaporation carbon nanotube hydrogel and preparation method and application thereof |
| CN113307909A (en) * | 2021-06-22 | 2021-08-27 | 武汉轻工大学 | Hydrogel filled with nitrogen-doped carbon nanotubes and preparation method thereof |
| CN113896834A (en) * | 2021-11-03 | 2022-01-07 | 桂林电子科技大学 | Preparation method and application of composite hydrogel photothermal conversion material |
| CN113908781A (en) * | 2021-11-03 | 2022-01-11 | 深圳市橘井舒泉技术有限公司 | Gel for storing ozone and preparation method thereof |
| WO2023108868A1 (en) * | 2021-12-13 | 2023-06-22 | 广东海洋大学 | Preparation method for carbon nano tube/polyacrylic acid hydrogel, and product and application of carbon nano tube/polyacrylic acid hydrogel |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110028680A (en) | The preparation method of carbon nanotube composite hydrogel | |
| Wu et al. | Large-scale fabrication of flexible EPDM/MXene/PW phase change composites with excellent light-to-thermal conversion efficiency via water-assisted melt blending | |
| Zhang et al. | Fabrication of novel MXene (Ti 3 C 2)/polyacrylamide nanocomposite hydrogels with enhanced mechanical and drug release properties | |
| Li et al. | Preparation and characterization of pH-and temperature-responsive hydrogels with surface-functionalized graphene oxide as the crosslinker | |
| CN104448396B (en) | It is a kind of based on the dual network cellulose gel based material being chemically and physically crosslinked | |
| Cheng et al. | Adsorption of polyethylene glycol (PEG) onto cellulose nano-crystals to improve its dispersity | |
| Zhu et al. | Photothermally sensitive poly (N‐isopropylacrylamide)/graphene oxide nanocomposite hydrogels as remote light‐controlled liquid microvalves | |
| Huang et al. | Preparation and swelling properties of graphene oxide/poly (acrylic acid-co-acrylamide) super-absorbent hydrogel nanocomposites | |
| CN105110313B (en) | A kind of polyimide-based compound carbon aerogels and preparation method thereof | |
| Liu et al. | Polyethyleneimine-modified graphene oxide/PNIPAm thermoresponsive hydrogels with rapid swelling/deswelling and improved mechanical properties | |
| CN105949760B (en) | A kind of spinning grade high heat conduction graphene/nylon composite materials in-situ polymerization method for preparing | |
| Ling et al. | Epoxy resin reinforced with nanothin polydopamine-coated carbon nanotubes: a study of the interfacial polymer layer thickness | |
| CN104558323B (en) | A kind of highly-water-soluble nano-hexagonal boron nitride and the preparation method of polymer composite aquogel thereof | |
| Hu et al. | Tough and stretchable Fe3O4/MoS2/PAni composite hydrogels with conductive and magnetic properties | |
| Saif et al. | Irradiation applications for polymer nano-composites: A state-of-the-art review | |
| Fu et al. | Superabsorbent nanocomposite based on methyl acrylic acid-modified bentonite and sodium polyacrylate: Fabrication, structure and water uptake | |
| Viana et al. | Microwave-assisted synthesis of polyacrylamide-aminated graphene oxide hybrid hydrogel with improved adsorption properties | |
| CN108404980A (en) | A kind of synthesis and application of the high performance high strength plural gel of load gold nano particle | |
| CN103146231B (en) | Method for preparing core-shell type carbon nano-tube filling by coating carbon nano-tube through polyionic liquid | |
| CN109293982B (en) | Preparation method of composite aerogel with high mechanical strength | |
| Wu et al. | Preparation of carbon nanotubes/waterborne polyurethane composites with the emulsion particles assisted dispersion of carbon nanotubes | |
| Sun et al. | Preparation of hemicellulose‐g‐poly (methacrylic acid)/carbon nanotube composite hydrogel and adsorption properties | |
| CN102660097B (en) | Preparation method of reinforced polyvinyl alcohol compound | |
| Olad et al. | Physicochemical evaluation of nanocomposite hydrogels with covalently incorporated poly (vinyl alcohol) functionalized graphene oxide | |
| Jansomboon et al. | Raman spectroscopic study of reinforcement mechanisms of electron beam radiation crosslinking of natural rubber composites filled with graphene and silica/graphene mixture prepared by latex mixing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20190719 |
|
| WW01 | Invention patent application withdrawn after publication |