CN106629688B - Temperature sensitive poly ion liquid water phase removing two-dimensional material and its application - Google Patents

Temperature sensitive poly ion liquid water phase removing two-dimensional material and its application Download PDF

Info

Publication number
CN106629688B
CN106629688B CN201611244035.5A CN201611244035A CN106629688B CN 106629688 B CN106629688 B CN 106629688B CN 201611244035 A CN201611244035 A CN 201611244035A CN 106629688 B CN106629688 B CN 106629688B
Authority
CN
China
Prior art keywords
boron nitride
molybdenum disulfide
added
layer
ion liquid
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.)
Active
Application number
CN201611244035.5A
Other languages
Chinese (zh)
Other versions
CN106629688A (en
Inventor
王雄伟
武培怡
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fudan University
Original Assignee
Fudan University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Fudan University filed Critical Fudan University
Priority to CN201611244035.5A priority Critical patent/CN106629688B/en
Publication of CN106629688A publication Critical patent/CN106629688A/en
Application granted granted Critical
Publication of CN106629688B publication Critical patent/CN106629688B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/06—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
    • C01B21/0648—After-treatment, e.g. grinding, purification
    • 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
    • C08F228/00—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 a bond to sulfur or by a heterocyclic ring containing sulfur
    • C08F228/02—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 a bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • 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
    • C08J2329/00—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
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2339/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
    • C08J2339/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08J2339/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
    • 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
    • C08J2341/00—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 a bond to sulfur or by a heterocyclic ring containing sulfur; Derivatives of such polymers
    • 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
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/02—Polyalkylene oxides

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention belongs to two-dimensional slice field of material technology, specially a kind of temperature sensitive poly ion liquid water phase removing two-dimensional slice material and its application.The present invention is specially that temperature sensitive poly ion liquid water phase removes three kinds of two-dimensional slice material graphite, molybdenum disulfide and boron nitride, then utilizes poly ion liquid-molybdenum disulfide composite hydrogel of removing two-dimensional nano piece preparation responsiveness and the layer upon layer boron nitride film of high thermal conductivity.The present invention passes through general radical first and polymerize to obtain temperature sensitive poly ion liquid, then with poly ion liquid aqueous solution come ultrasonic removing graphite, molybdenum disulfide and boron nitride.Then it is obtained using the molybdenum disulfide nano sheet in-situ polymerization ionic liquid of removing with the poly ion liquid-molybdenum disulfide composite hydrogel responded to temperature and near-infrared；The boron nitride pellicle with high heat conductance even is obtained through continuous film of taking out using the boron nitride nanosheet of removing.The method of the present invention, easy to operate, lower production costs are easy to mass, large-scale production, have broad application prospects.

Description

Temperature sensitive poly ion liquid water phase removing two-dimensional material and its application
Technical field
The invention belongs to two-dimensional slice field of material technology, and in particular to a kind of temperature sensitive poly ion liquid water phase removing two dimension Sheet layer material and its application.
Background technique
Recently, all kinds of two-dimensional slice materials, such as graphene, molybdenum disulfide (MoS2), tungsten disulfide (WS2) and six sides nitridation Boron (h-BN), since their high specific surface areas and unique properties have attracted extensive concern and research.These materials All have between unique lamella stacked structure namely lamella and is mutually deposited in one along vertical plane direction by Van der Waals force It rises.Relative to original material, the two-dimensional material of single layer or several layers, since it is with great radius-thickness ratio and a large amount of exposure Atom is to make its various types of properties that significant change, such as heating conduction, optical property, bandwidth and electrochemistry also occur Energy is equal.Chemical vapour deposition technique from bottom to top is considered as the important method for obtaining high quality monolayer two-dimensional nano piece, still Due to its harsh working condition, high temperature and high vacuum are such as required, and is extremely restricted.Therefore pass through top-to-bottom method It is considered as the method for being most hopeful to realize large-scale production to remove to obtain the two-dimensional nano piece of single layer or several layers.
Because two-dimensional slice material direction in face has strong chemistry key connection, and direction is by weak in vertical plane Van der Waals force connection, therefore be possible by overcoming the Van der Waals force in direction in its vertical plane to carry out removing to material, and A large amount of experiment also demonstrates this point.There is mechanical stripping for the main method of the removing report of two-dimensional slice material at present, changes Learn removing, thermal expansion removing etc..The features such as mechanical stripping is due to comparatively environmentally friendly, easy to operate and suitable large-scale production Receive more concerns.Liquid phase micromechanics stripping after liquid phase ultrasound removes all kinds of two-dimensional slice materials is reported from coleman etc. Two-dimensional material is removed from research is widely used for.The definition of liquid phase removing is that original two-dimensional material is directly passed through micromechanics Power removes into the two-dimensional nano piece of single layer or several layers in the liquid phase.Here micromechanical forces can also be in addition to ultrasonic force cuts Shear force, frictional force etc..In addition, liquid phase removing usually requires that the solvent used can preferably soak and disperse the two-dimentional material of removing Material, namely require the solvent of selection that can match with the surface of two-dimensional material.However common two-dimensional material such as graphene, nitridation Boron and molybdenum disulfide etc. have lower surface can, therefore carry out liquid phase removing to it and often need high boiling to have with selection is some Solvent, such as -2 pyrrolidones of N- methyl, n,N-Dimethylformamide, isopropanol.It is envisioned that these higher boilings are organic molten A large amount of uses of agent can bring many problems, first is that solvent is difficult to remove, second is that not environmentally friendly enough low-carbon, third is that operating environment is more Badly.Based on these problems of Traditional liquid phase removing, solvent is used water as to be considered as solving to micromechanics removing is carried out The best approach of these problems.In order to promote hydrophobic two-dimensional material in the dispersion of water phase, it usually needs some promotions point are added Powder, such as surfactant, certain water-soluble polymers, ionic liquid etc..However promote the effect of the water phase removing of dispersing agent auxiliary Rate is generally lower, and is generally difficult to universally go to remove a variety of two-dimensional materials.Therefore how universally to be gone using some way It removes a variety of two-dimensional materials and is not only water phase micromechanics removing field, and the research heat in entire two-dimensional material removing field Point.
The present invention is just being directed to universally realize water phase ultrasound removing graphite, molybdenum disulfide and nitrogen using some way Change these three two-dimensional materials of boron.The characteristic of partial ion liquid and the spy of polymer are had both using the temperature sensitive poly ion liquid of synthesis Property, during water phase removes two-dimensional material, the positive tetrabutyl phosphonium bromide phosphorus of cationic portion may be implemented to insert two-dimensional material Layer, thus weaken the interaction force between lamella, and the polystyrolsulfon acid part of anion part can receive removing Rice piece plays stabilization.Therefore the aqueous solution of the poly ion liquid can remove three kinds of two-dimension nano materials, Er Qieqi simultaneously Polyvinylpyrrolidone and polyvinyl alcohol will be significantly higher than to the peeling effect of molybdenum disulfide.Additionally due to polyion used Liquid has Thermo-sensitive, therefore temperature can also be realized to the reversible control of the two-dimensional nano piece dispersity of removing.Further We utilize the MoS removed2It is that nanometer sheet is prepared for having good compression recoverability and there is temperature and near-infrared to ring simultaneously The MoS of answering property2- PILs hydrogel has been obtained in the way of continuously taking out film imitative with layer upon layer by removing BN nanometer sheet The high fever guided membrane of mussel structure.
Summary of the invention
The purpose of the present invention is to provide a kind of temperature sensitive poly ion liquid water phase remove a variety of two-dimensional materials and its method and Using, i.e., using removing two-dimensional nano piece preparation temperature, near-infrared responsiveness molybdenum disulfide-poly ion liquid hydrogel and The bionical boron nitride layer layer heap integrated membrane of high thermal conductivity.
The preparation method of temperature sensitive poly ion liquid water phase removing two-dimensional material provided by the invention, specific steps are as follows:
(1) it weighs 5-15 g tetrabutyl phosphonium bromide phosphorus and 3-8 g vinyl sodium benzosulfonate is added in 100 ~ 300 ml water, 2-24 is stirred at room temperature, and methylene chloride is then added and is extracted, takes subnatant to be spin-dried for, obtains ionic liquid monomer, be denoted as ILs；
(2) it takes 1-5 g ILs to be dissolved in 10 ~ 100 ml solvents, 20 ~ 80 mg azo-bis-isobutyl cyanides is added, lead to nitrogen 5- 60 min are placed on reaction 1-12 h in 70 DEG C of oil baths, are re-dissolved in chloroform after being then spin-dried for reaction solution, are finally vigorously stirred Under Precipitation is carried out in n-hexane, obtain poly ion liquid after drying, be denoted as PILs；
(3) 25 ~ 1000 mg PILs are weighed to be dissolved in 20 ~ 200 ml water, the commercially available molybdenum disulfide of 0.5 ~ 2 g is then added (MoS2) powder or boron nitride (BN) powder or graphite powder, then 6 ~ 32 h of ultrasound in a water bath；After ultrasound, by stripper It is centrifuged 10 ~ 40 min under the centrifugal speed of 2000 ~ 8000 rpm, takes upper liquid to get water phase stripping nano piece two dimension material is arrived Material (including: the boron nitride nanosheet dispersion liquid of water phase removing molybdenum disulfide nano sheet dispersion liquid or water phase removing).
Solvent described in step (2) of the present invention is one of deionized water, ethyl alcohol and N,N-dimethylformamide.
Water phase prepared by the present invention removes two-dimensional nano piece, can be used for the molybdenum disulfide-of preparation temperature and near-infrared response Poly ion liquid (MoS2- PILs) composite hydrogel and high thermal conductivity layer upon layer boron nitride film.
The MoS of temperature and near-infrared response2The preparation step of-PILs composite hydrogel are as follows:
Weigh 0.5 ~ 3 g ILs, 40 ~ 150 mg N, N- methylene-bisacrylamides, 10 ~ 60 mg ammonium persulfates and 2 ~ 6 The water phase removing molybdenum disulfide nano sheet dispersion liquid of 0.1 ~ 0.5 mg/ml of ml is added in 8-10 ml water, leads to nitrogen 10 ~ 30 Min is then injected into 20 ~ 100 μ L N, N, N, N- tetramethylethylenediamines, stands 12 ~ 36 h at room temperature, obtains MoS2-PILs Composite hydrogel.
The preparation step of the layer upon layer boron nitride film of high thermal conductivity are as follows:
The boron nitride nanosheet dispersion liquid of 20 ~ 50 ml water phases removing is measured, the polymerization of 6 wt% of 0.1 ~ 0.5 ml is added The aqueous solution of object, after 10 ~ 30 min of ultrasound, be added to take out carried out in film device it is continuous take out film, it is thin to obtain layer upon layer boron nitride Film.
In the present invention, the polymer is one of polyvinyl alcohol, polyvinylpyrrolidone and polyethylene glycol oxide.
Method provided by the invention may be implemented the ultrasound in water phase and remove a variety of two-dimensional slice materials, mainly pass through conjunction At temperature sensitive poly ion liquid aqueous solution come efficiently ultrasound removing graphite, molybdenum disulfide and boron nitride material, then recycle The molybdenum disulfide of removing carrys out molybdenum disulfide-poly ion liquid hydrogel of preparation temperature and near-infrared response, utilizes the nitrogen of removing Change boron nanometer sheet and obtains the boron nitride high thermal conductivity film of layer upon layer through continuous film of taking out.
The present invention using removing molybdenum disulfide preparation composite hydrogel, due to poly ion liquid itself have it is temperature sensitive Property, and molybdenum disulfide has good light thermal property, therefore composite hydrogel is sensitive to temperature and near-infrared, with temperature increase by Bottle green becomes white.The boron nitride pellicle of the layer upon layer of preparation, due to accumulating close, tool between boron nitride nanosheet There is thermal conductivity in higher face.
Operation of the present invention is convenient, and preparation condition is simple, and production cost is low, is easy to mass, large-scale production, has good Industrialized production basis and wide application prospect.
Detailed description of the invention
Dispersity photo of the tri- kinds of two-dimensional slice materials of Fig. 1 before and after PILs is added in water.
Turbidity variation of the 10 wt% PILs aqueous solution of Fig. 2 in temperature-rise period and the dispersion in 25 DEG C and 60 DEG C State photo.
The dilute dispersion liquid of molybdenum disulfide, graphene and the boron nitride that Fig. 3 peel separation obtains stands the dispersion of 3 days front and backs State photo.
Fig. 4 .(a, d) removing molybdenum disulfide nano sheet, the graphene nanometer sheet of (b, e) removing, the nitrogen of (c, f) removing Change the transmitted electron fibrogram of boron nanometer sheet and the lattice diffraction pattern of response.
Fig. 5 .(a) removing molybdenum disulfide nano sheet, (b) remove graphene nanometer sheet, (c) remove boron nitride receive The atomic force microscope height map and corresponding altitude curve of rice piece.
Fig. 6 .(a) removing front and back molybdenum disulfide, (b) removing front and back graphene, (c) removing front and back boron nitride X X ray diffration pattern x.
Fig. 7 .(a) removing front and back molybdenum disulfide, (b) removing front and back graphene Raman spectrogram.
The molybdenum disulfide nano sheet aqueous dispersions that Fig. 8 (a) difference PILs concentration of aqueous solution is removed it is ultraviolet-can Light-exposed spectrogram, (b) PILs and polyvinylpyrrolidone and polyvinyl alcohol water solution are removed under 2 mg/ml of same concentrations Molybdenum disulfide is received
The UV-visible spectrum of rice piece dispersion liquid.
The pure PILs hydrogel of Fig. 9 (a) and MoS2The photo and MoS of-PILS composite hydrogel2- PILs composite hydrogel The hydrogel color change with near-infrared laser irradiation is increased with temperature.(b) MoS2- PILs composite hydrogel is in compression process Change in shape and reply photo.
The pure PILs hydrogel of Figure 10 (a) and MoS2The compression stress strain curve of-PILs composite hydrogel.(b) MoS2- The Repeated Compression cyclic stress-strain curve of PILs composite hydrogel.
Figure 11 (a) continuously takes out the photo under the normal condition for the boron nitride nanosheet film that film obtains, rolled state； (b) tensile stress strain curve of the boron nitride film of different polyvinyl alcohol contents；(c) polyvinyl alcohol content is the nitrogen of 7.5 wt% Change the brittle failure Surface scan electron microscope picture of boron film；(d) the thermal conductivity figure of the boron nitride nanosheet film of different polyvinyl alcohol contents.
Specific embodiment
Present invention be described in more detail by the following examples, and temperature sensitive poly ion liquid water phase removes a variety of two-dimensional slices Composite molybdenum disulfide-poly ion liquid the hydrogel and layer of the preparation method of material and the nanometer sheet preparation responsiveness using removing The high thermal conductivity boron nitride film of layer heap product, the examples of implementation are merely possible to provide explanation rather than the restriction present invention.
Embodiment 1
(1) 9.7 g tetrabutyl phosphonium bromide phosphorus are weighed and 6 g vinyl sodium benzosulfonates are added in 200 ml water, room temperature is stirred 24 h are mixed, methylene chloride is then added and is extracted, subnatant is taken to be spin-dried for obtaining ionic liquid monomer (ILs)；
(2) it takes 3 g ILs to be dissolved in certain solvent of 35 ml, 48.8 mg azo-bis-isobutyl cyanides is added, lead to nitrogen 30 Min, which is placed in 70 DEG C of oil baths, reacts 12 h, is re-dissolved in chloroform after being then spin-dried for reaction solution, then with vigorous stirring Precipitation is carried out in n-hexane, and poly ion liquid (PILs) is obtained after drying；
(3) 200 mg PIL are weighed to be dissolved in 100 ml water, the commercially available molybdenum disulfide powder (MoS of 2 g is then added2) or 2 G boron nitride powder (BN) or 1 g graphite powder, then 18 h of ultrasound in a water bath.After ultrasound, by stripper in 3000 rpm Centrifugal speed under be centrifuged 20 min, take upper liquid be remove two-dimensional nano piece；
(4) 2 g ILs, 120 mg N, N- methylene bisacrylamides temperature and near-infrared response composite hydrogel preparation: are weighed The MoS that amide, 40 mg ammonium persulfates and 1.25 front mg/ml 4 ml are removed2Aqueous dispersions are added in 8 ml water, lead to nitrogen 30 min of gas is then injected into 60 μ L N, N, N, N- tetramethylethylenediamines, stands 36 h at room temperature, obtain responsiveness MoS2- PILs composite hydrogel；
(5) the layer upon layer boron nitride film preparation of high thermal conductivity: measuring the BN nanometer sheet aqueous dispersions that 30 fronts ml are removed, Then it is added the aqueous solution of certain polymer of 6 wt% of 0.3 ml, after 30 min of ultrasound, is added to take out in film device and is connected It is continuous to take out film, obtain layer upon layer BN film.
The temperature sensitive PILs synthesized as seen from Figure 1 has Thermo-sensitive really, and concentration is the phase transition temperature of 10 wt% aqueous solutions It is 56 DEG C or so, solution colour gradually becomes white opacity by clear in phase transition process.By Fig. 2 it can be seen that, Shao Liangwen The addition of quick PILs can significantly improve the dispersion of three kinds of hydrophobic two-dimensional slice materials in water.By Fig. 3 it can be seen that, PILs The weak solution of three kinds of two-dimensional nano pieces of aqueous solution removing has excellent dispersion stabilization, and it is obvious that appearance is had no after standing 3 days Precipitating, this is because the PILs strand of two-dimensional nano piece adsorption can promote their dispersions in water.Fig. 4 is shown Lower ultrasound is assisted to may be implemented to remove three kinds of two-dimensional materials really through PILs, since removing lamella is relatively thin, part nanometer Piece is crimped.Furthermore it can see the two-dimensional nano piece that PILs water phase ultrasound is removed from diffraction pattern to all have preferably Crystallinity, in terms of lamella edge probably between 4-8 layers.The atomic force microscopy of the two-dimensional material lamella further obtained by removing Height map (Fig. 5) it can be seen that the thickness of molybdenum disulfide probably in 2 nm or so, the thickness of graphene sheet layer probably in 2-3 nm, The thickness of boron nitride nanosheet is substantially close with the result of transmission electron microscopy figure probably between 2-4 nm.Before being removed by Fig. 6 X-ray diffractogram afterwards can see, opposite with initial molybdenum disulfide powder after molybdenum disulfide removing, is greater than 20 degree and spreading out It penetrates peak and is obviously reduced and even disappear；Graphene removing front and back shows that 26 degree or so of peak is moved to by 26.86 degree of removing front and back 26.71 degree, illustrate that the interlamellar spacing between lamella increases, the stacking characteristic peak of the boron nitride before and after removing is similarly observed that similar Phenomenon.It is shown by the Raman figure of Fig. 7 removing front and back, relative to its characteristic peak of initial molybdenum disulfide powder after molybdenum disulfide removing E1 2gAnd A1gOccur to illustrate the broken and removing of molybdenum disulfide nano sheet to lower wave number movement significantly；And for removing after Its I of grapheneD/IGValue is significantly increased relative to graphite, and significant blue shift occurs for characteristic peak G band position, these also all imply graphite The removing of alkene stripping process lamella is crushed and strong interaction between PILs strand.Conclusions synthesis can illustrate The water phase removing to molybdenum disulfide, boron nitride and graphite may be implemented in PILs really.
Embodiment 2
(1) 9.7 g tetrabutyl phosphonium bromide phosphorus are weighed and 6 g vinyl sodium benzosulfonates are added in 200 ml water, room temperature is stirred 24 h are mixed, methylene chloride is then added and is extracted, subnatant is taken to be spin-dried for obtaining ionic liquid monomer (ILs)；
(2) it takes 3 g ILs to be dissolved in certain solvent of 35 ml, 48.8 mg azo-bis-isobutyl cyanides is added, lead to nitrogen 30 Min, which is placed in 70 DEG C of oil baths, reacts 12 h, is re-dissolved in chloroform after being then spin-dried for reaction solution, then with vigorous stirring Precipitation is carried out in n-hexane, and poly ion liquid (PILs) is obtained after drying；
(3) 100 mg PIL are weighed to be dissolved in 100 ml water, the commercially available molybdenum disulfide powder (MoS of 2 g is then added2) or 2 G boron nitride powder (BN) or 1 g graphite powder, then 18 h of ultrasound in a water bath.After ultrasound, by stripper in 3000 rpm Centrifugal speed under be centrifuged 20 min, take upper liquid be remove two-dimensional nano piece；
(4) 2 g ILs, 120 mg N, N- methylene bisacrylamides temperature and near-infrared response composite hydrogel preparation: are weighed The MoS that amide, 40 mg ammonium persulfates and 1.25 front mg/ml 4 ml are removed2Aqueous dispersions are added in 8 ml water, lead to nitrogen 30 min of gas is then injected into 60 μ L N, N, N, N- tetramethylethylenediamines, stands 36 h at room temperature, obtain responsiveness MoS2- PILs composite hydrogel；
(5) the layer upon layer boron nitride film preparation of high thermal conductivity: measuring the BN nanometer sheet aqueous dispersions that 30 fronts ml are removed, Then it is added the aqueous solution of certain polymer of 6 wt% of 0.1 ml, after 30 min of ultrasound, is added to take out in film device and is connected It is continuous to take out film, obtain layer upon layer BN film.
Embodiment 3
(1) 9.7 g tetrabutyl phosphonium bromide phosphorus are weighed and 6 g vinyl sodium benzosulfonates are added in 200 ml water, room temperature is stirred 24 h are mixed, methylene chloride is then added and is extracted, subnatant is taken to be spin-dried for obtaining ionic liquid monomer (ILs)；
(2) it takes 3 g ILs to be dissolved in certain solvent of 35 ml, 48.8 mg azo-bis-isobutyl cyanides is added, lead to nitrogen 30 Min, which is placed in 70 DEG C of oil baths, reacts 12 h, is re-dissolved in chloroform after being then spin-dried for reaction solution, then with vigorous stirring Precipitation is carried out in n-hexane, and poly ion liquid (PILs) is obtained after drying；
(3) 300 mg PIL are weighed to be dissolved in 100 ml water, the commercially available molybdenum disulfide powder (MoS of 2 g is then added2) or 2 G boron nitride powder (BN) or 1 g graphite powder, then 18 h of ultrasound in a water bath.After ultrasound, by stripper in 3000 rpm Centrifugal speed under be centrifuged 20 min, take upper liquid be remove two-dimensional nano piece；
(4) 2 g ILs, 120 mg N, N- methylene bisacrylamides temperature and near-infrared response composite hydrogel preparation: are weighed The MoS that amide, 40 mg ammonium persulfates and 1.25 front mg/ml 4 ml are removed2Aqueous dispersions are added in 8 ml water, lead to nitrogen 30 min of gas is then injected into 60 μ L N, N, N, N- tetramethylethylenediamines, stands 36 h at room temperature, obtain responsiveness MoS2- PILs composite hydrogel；
(5) the layer upon layer boron nitride film preparation of high thermal conductivity: measuring the BN nanometer sheet aqueous dispersions that 30 fronts ml are removed, Then it is added the aqueous solution of certain polymer of 6 wt% of 0.2 ml, after 30 min of ultrasound, is added to take out in film device and is connected It is continuous to take out film, obtain layer upon layer BN film.
Embodiment 4
(1) 9.7 g tetrabutyl phosphonium bromide phosphorus are weighed and 6 g vinyl sodium benzosulfonates are added in 200 ml water, room temperature is stirred 24 h are mixed, methylene chloride is then added and is extracted, subnatant is taken to be spin-dried for obtaining ionic liquid monomer (ILs)；
(2) it takes 3 g ILs to be dissolved in certain solvent of 35 ml, 48.8 mg azo-bis-isobutyl cyanides is added, lead to nitrogen 30 Min, which is placed in 70 DEG C of oil baths, reacts 12 h, is re-dissolved in chloroform after being then spin-dried for reaction solution, then with vigorous stirring Precipitation is carried out in n-hexane, and poly ion liquid (PILs) is obtained after drying；
(3) 400 mg PIL are weighed to be dissolved in 100 ml water, the commercially available molybdenum disulfide powder (MoS of 2 g is then added2) or 2 G boron nitride powder (BN) or 1 g graphite powder, then 18 h of ultrasound in a water bath.After ultrasound, by stripper in 3000 rpm Centrifugal speed under be centrifuged 20 min, take upper liquid be remove two-dimensional nano piece；
(4) 2 g ILs, 120 mg N, N- methylene bisacrylamides temperature and near-infrared response composite hydrogel preparation: are weighed The MoS that amide, 40 mg ammonium persulfates and 1.25 front mg/ml 4 ml are removed2Aqueous dispersions are added in 8 ml water, lead to nitrogen 30 min of gas is then injected into 60 μ L N, N, N, N- tetramethylethylenediamines, stands 36 h at room temperature, obtain responsiveness MoS2- PILs composite hydrogel；
(5) prepared by high thermal conductivity layer upon layer boron nitride film: measuring the BN nanometer sheet aqueous dispersions that 30 fronts ml are removed, so Be added the aqueous solution of certain polymer of 6 wt% of 0.4 ml afterwards, after 30 min of ultrasound, be added to take out carried out in film device it is continuous Film is taken out, layer upon layer BN film is obtained.
Embodiment 5
(1) 9.7 g tetrabutyl phosphonium bromide phosphorus are weighed and 6 g vinyl sodium benzosulfonates are added in 200 ml water, room temperature is stirred 24 h are mixed, methylene chloride is then added and is extracted, subnatant is taken to be spin-dried for obtaining ionic liquid monomer (ILs)；
(2) it takes 3 g ILs to be dissolved in certain solvent of 35 ml, 48.8 mg azo-bis-isobutyl cyanides is added, lead to nitrogen 30 Min, which is placed in 70 DEG C of oil baths, reacts 12 h, is re-dissolved in chloroform after being then spin-dried for reaction solution, then with vigorous stirring Precipitation is carried out in n-hexane, and poly ion liquid (PILs) is obtained after drying；
(3) 500 mg PIL are weighed to be dissolved in 100 ml water, the commercially available molybdenum disulfide powder (MoS of 2 g is then added2) or 2 G boron nitride powder (BN) or 1 g graphite powder, then 18 h of ultrasound in a water bath.After ultrasound, by stripper in 3000 rpm Centrifugal speed under be centrifuged 20 min, take upper liquid be remove two-dimensional nano piece；
(4) 2 g ILs, 120 mg N, N- methylene bisacrylamides temperature and near-infrared response composite hydrogel preparation: are weighed Amide, 40 mg ammonium persulfates are added in 12 ml water, are led to 30 min of nitrogen, are then injected into 60 μ L N, N, N, N- tetramethyl second Diamines stands 36 h at room temperature, obtains responsiveness MoS2- PILs composite hydrogel；
(5) prepared by high thermal conductivity layer upon layer boron nitride film: measuring the BN nanometer sheet aqueous dispersions that 30 fronts ml are removed, so Be added the aqueous solution of certain polymer of 6 wt% of 0.5 ml afterwards, after 30 min of ultrasound, be added to take out carried out in film device it is continuous Film is taken out, layer upon layer BN film is obtained.
The aqueous solution that Fig. 8 has studied different PILs concentration compares the peeling effect of molybdenum disulfide, and uses ultraviolet-visible light It composes qualitatively to observe the absorption value of two characteristic peaks, it can be seen that removing of the PILs aqueous solution of 2 mg/ml to molybdenum disulfide Have the effect of best.It compared at 2 mg/ml of same concentration simultaneously, different water-soluble polymer aqueous solutions is to curing The peeling effect of molybdenum, it can be seen that PILs has the removing of molybdenum disulfide relative to polyvinylpyrrolidone and polyvinyl alcohol Better effect.
Fig. 9 shows that clear is presented in pure PIls hydrogel, and the Compound Water of the molybdenum disulfide nano sheet of removing is added Bottle green is presented in gel.Study MoS2- PILs composite hydrogel finds as the temperature rises the response of temperature and near-infrared With the irradiation of near-infrared laser, composite hydrogel is undergone phase transition, and becomes canescence from original bottle green.Furthermore composite hydrogel With good compression reaction performance.
Figure 10 tests pure PIls hydrogel and MoS2The compression performance of-PILs composite hydrogel finds composite hydrogel Compressive strength to be significantly higher than the hydrogel of pure PIls liquid, and composite hydrogel has excellent Repeated Compression cyclicity Energy.
Figure 11 shows that the boron nitride film that continuous pumping film obtains has excellent flexibility and bending performance repeatedly, and studies not Stress strain curve with the boron nitride film obtained under polyvinyl alcohol addition finds the increase with polyvinyl alcohol content, boron nitride Tensile strength increases accordingly.It can see boron nitride film from the brittle failure face of boron nitride film and boron nitride nanosheet layer upon layer be presented Mussel structure is imitated, is completely embedded between adjacent sheets, this is conducive to hot being effectively conducted in face.Different polyvinyl alcohol are studied to contain The thermal conductivity for measuring lower boron nitride film finds that the thermal conductivity of the film when polyvinyl alcohol content is 7.5 wt% reaches maximum, too low and excessively high Polyvinyl alcohol content be all unfavorable for the raising of thermal conductivity.

Claims (4)

1. molybdenum disulfide-poly ion liquid that a kind of water phase stripping nano piece two-dimensional material is responded in preparation temperature and near-infrared MoS2Application in-PILs composite hydrogel and the layer upon layer boron nitride pellicle of high thermal conductivity；The water phase stripping nano piece two dimension Specific step is as follows for the preparation method of material:
(1) it weighs 5-15 g tetrabutyl phosphonium bromide phosphorus and 3-8 g vinyl sodium benzosulfonate is added in 100 ~ 300 ml water, room temperature Then lower stirring 2-24 is added methylene chloride and is extracted, takes subnatant to be spin-dried for, obtain ionic liquid monomer, be denoted as ILs；
(2) it takes 1-5 g ILs to be dissolved in 10 ~ 100 ml solvents, 20 ~ 80 mg azo-bis-isobutyl cyanides is added, lead to nitrogen 5-60 Min is placed on reaction 1-12 h in 70 DEG C of oil baths, is re-dissolved in chloroform after being then spin-dried for reaction solution, is finally vigorously stirred down Precipitation is carried out in n-hexane, is obtained poly ion liquid after drying, is denoted as PILs；
(3) 25 ~ 1000 mg PILs are weighed to be dissolved in 20 ~ 200 ml water, the commercially available molybdenum disulfide (MoS of 0.5 ~ 2 g is then added2) Powder or boron nitride (BN) powder, then 6 ~ 32 h of ultrasound in a water bath；After ultrasound, by stripper 2000 ~ 8000 It is centrifuged 10 ~ 40 min under the centrifugal speed of rpm, takes upper liquid to get water phase stripping nano piece two-dimensional material is arrived；
Solvent described in step (2) is one of deionized water, ethyl alcohol and N,N-dimethylformamide.
2. application according to claim 1, which is characterized in that preparation temperature and near-infrared response molybdenum disulfide-gather from Sub- liquid MoS2The preparation step of-PILs composite hydrogel are as follows:
Weigh 0.5 ~ 3 g ILs, 40 ~ 150 mg N, N- methylene-bisacrylamides, 10 ~ 60 mg ammonium persulfates and 2 ~ 6 ml The water phase removing molybdenum disulfide nano sheet dispersion liquid of 0.1 ~ 0.5 mg/ml is added in 8-10 ml water, leads to nitrogen 10 ~ 30 Min is then injected into 20 ~ 100 μ L N, N, N, N- tetramethylethylenediamines, stands 12 ~ 36 h at room temperature, obtains MoS2-PILs Hydrogel.
3. application according to claim 2, which is characterized in that the preparation step of preparation layer upon layer boron nitride pellicle are as follows: It measures 20 ~ 50 ml water phases and removes boron nitride nanosheet dispersion liquid, the aqueous solution of the polymer of 6 wt% of 0.1 ~ 0.5 ml is added, After 10 ~ 30 min of ultrasound, it is added to and takes out the continuous pumping film of progress in film device, obtain layer upon layer boron nitride pellicle.
4. application according to claim 3, which is characterized in that the polymer is polyvinyl alcohol, polyvinylpyrrolidone One of ketone and polyethylene glycol oxide.
CN201611244035.5A 2016-12-29 2016-12-29 Temperature sensitive poly ion liquid water phase removing two-dimensional material and its application Active CN106629688B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611244035.5A CN106629688B (en) 2016-12-29 2016-12-29 Temperature sensitive poly ion liquid water phase removing two-dimensional material and its application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611244035.5A CN106629688B (en) 2016-12-29 2016-12-29 Temperature sensitive poly ion liquid water phase removing two-dimensional material and its application

Publications (2)

Publication Number Publication Date
CN106629688A CN106629688A (en) 2017-05-10
CN106629688B true CN106629688B (en) 2019-12-03

Family

ID=58836507

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611244035.5A Active CN106629688B (en) 2016-12-29 2016-12-29 Temperature sensitive poly ion liquid water phase removing two-dimensional material and its application

Country Status (1)

Country Link
CN (1) CN106629688B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111393641A (en) * 2020-03-24 2020-07-10 四川大学 Surfactant capable of simultaneously stripping and vinylating two-dimensional lamellar material, preparation and application

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108640154A (en) * 2018-06-15 2018-10-12 西南交通大学 A kind of molybdenum disulfide nano material and preparation method thereof
CN110982011B (en) * 2019-11-29 2021-08-03 河北大学 Light-directing bending material and preparation method thereof
CN112918030B (en) * 2019-12-05 2023-08-08 中国科学院深圳先进技术研究院 Boron nitride film with plane orientation, preparation method thereof, boron nitride composite film containing boron nitride film, thermal interface material and application
CN112591797A (en) * 2020-12-23 2021-04-02 陕西科技大学 High-concentration high-dispersibility ultrathin molybdenum disulfide dispersion liquid and preparation method thereof
CN116574277A (en) * 2023-06-12 2023-08-11 陕西科技大学 Boron nitride/aramid fiber/polyvinyl alcohol heat conduction hydrogel and preparation method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100429153C (en) * 2006-12-20 2008-10-29 浙江大学 Preparation method for ion liquid assisted hydrothermal synthesis of MoS2 microsphere
CN105161691B (en) * 2015-10-10 2017-04-26 岭南师范学院 Preparation method of less-layer MoS2/phosphorus-doped graphene electrochemical sodium-storage combined electrode
CN105502311B (en) * 2015-12-29 2017-11-17 复旦大学 The preparation method of the strippings of two chalcogen compounds, functional modification and Intelligent Composite gel

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111393641A (en) * 2020-03-24 2020-07-10 四川大学 Surfactant capable of simultaneously stripping and vinylating two-dimensional lamellar material, preparation and application

Also Published As

Publication number Publication date
CN106629688A (en) 2017-05-10

Similar Documents

Publication Publication Date Title
CN106629688B (en) Temperature sensitive poly ion liquid water phase removing two-dimensional material and its application
Prakash et al. Phosphor polymer nanocomposite: ZnO: Tb3+ embedded polystyrene nanocomposite thin films for solid-state lighting applications
JP6147860B2 (en) Method for making silver nanostructures and copolymers useful in the same
TWI284134B (en) PVC-PCC nanocomposites resin composition with superior impact strength and method for preparing the same
TWI671146B (en) Processes for making silver nanostructures,silver nanostructures obtained therefrom,dispersion comprising the silver nanostructures and electrically conductive coating made using the dispersion
CN103265714B (en) Polyvinyl alcohol/graphene oxide composite film preparation method
Mayer et al. Hybrid hydrogels obtained by the copolymerization of acrylamide with aggregates of methacryloyl derivatives of polyoxotungstates. A comparison with polyacrylamide hydrogels with trapped aggregates
Sakai-Otsuka et al. Self-assembly of carbohydrate-block-poly (3-hexylthiophene) diblock copolymers into sub-10 nm scale lamellar structures
CN114074927B (en) Two-dimensional material, preparation method thereof and composite membrane
CN105218996B (en) A kind of preparation method of modified graphene polyvinyl alcohol compound film
Kowsari et al. Ultrasound and ionic-liquid-assisted synthesis and characterization of polyaniline/Y2O3 nanocomposite with controlled conductivity
CN105502311B (en) The preparation method of the strippings of two chalcogen compounds, functional modification and Intelligent Composite gel
Wei et al. Enhanced antistatic and self-heatable wearable coating with self-tiered structure caused by amphiphilic MXene in waterborne polymer
CN105218845B (en) A kind of preparation method of modified graphene polymethyl methacrylate laminated film
CN106432561A (en) Method for preparing black phosphorus heteropolymer in situ
CN107082873B (en) A method of preparing the PEDOT/PSS aqueous dispersions of nano-scale
Ma et al. POSS-pendanted in epoxy chain inorganic-organic hybrid for highly thermo-mechanical, permeable and hydrothermal-resistant coatings
Lin et al. Scalable Preparation of Cylindrical Block Copolymer Micelles with a Liquid-Crystalline Perfluorinated Core by Photoinitiated Reversible Addition-Fragmentation Chain Transfer Dispersion Polymerization
Huang et al. Polymer precursor strategy toward the precise synthesis of uniform hairy carbon dots with tunable sizes and size effects over their fluorescence
Liu et al. Facile design of renewable lignin copolymers by photoinitiated RAFT polymerization as Pickering emulsion stabilizers
Wang et al. Large scale synthesis of single-chain/colloid Janus nanoparticles with tunable composition
Zeng et al. Preparation of Carboxyl‐Functionalized Polystyrene/Silica Composite Nanoparticles
CN111747412A (en) Two-dimensional BP/Ti3C2Preparation method and application of heterojunction
Reichstein et al. Poly (3-hexylthiophene)-block-poly (tetrabutylammonium-4-styrenesulfonate) Block Copolymer Micelles for the Synthesis of Polymer Semiconductor Nanocomposites
CN109265664B (en) Method for improving stability of perovskite material in water by adopting co-insertion polymer

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
GR01 Patent grant
GR01 Patent grant