CN102936357B - Antistatic agent made from silver nanowire and functional carbon nano tube (CNT) and preparation method - Google Patents
Antistatic agent made from silver nanowire and functional carbon nano tube (CNT) and preparation method Download PDFInfo
- Publication number
- CN102936357B CN102936357B CN201210429090.7A CN201210429090A CN102936357B CN 102936357 B CN102936357 B CN 102936357B CN 201210429090 A CN201210429090 A CN 201210429090A CN 102936357 B CN102936357 B CN 102936357B
- Authority
- CN
- China
- Prior art keywords
- carbon nanotube
- cnt
- platinum
- silver nanowire
- solution
- 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
Links
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides an antistatic agent made from a silver nanowire and a functional CNT and a preparation method, and belongs to the technical field of antistatic agents. The silver nanowire grows in situ on the surface-thiolated CNT through a platinum seed crystal. The method includes that thiolation modification on the surface of the CNT is performed, the platinum seed crystal is anchored on the surface of the CNT according to coordination of sulfydryl, and the silver nanowire grows in situ through the platinum seed crystal on the surface of the CNT to prepare the CNT and silver nanowire composite antistatic agent. The antistatic agent is small in amount, and the defect of phase splitting of different components caused by blending modification of the CNT and the silver nanowire is overcome.
Description
Technical field
The present invention relates to a kind of nano silver wire functionalized carbon nanotubes static inhibitor and utilize the method for carbon nano tube surface grappling platinum crystal seed growth in situ nano silver wire, belong to static inhibitor technical field.
Background technology
In recent years, along with macromolecular material in every field widespread use, thereby macromolecular material functional proposed to more and more many requirements, wherein general engineering materials is as polyimide (PI), polycarbonate (PC), polyetherimide (PEI), polyether-ether-ketone (PEEK), due to mechanical property and the resistance toheat of itself excellence, at the aspects such as component of medical equipment, chemical industry equipment, electronic installation and automatization, use in a large number.Yet it is as electric poor conductor, when material friction or electron device produces in environment for use electric charge cannot be leaked in time, while running up to a certain degree, will produces static, and then cause human injury or cause electronic product to damage.Therefore reducing material resistance reveals electric charge in time, prevents the active demand that above material is proposed that becomes of static.
Static inhibitor as addition type mainly comprises carbon system and metallic stuffing system, from adding the conduction property of material itself, adopt metal matrix static inhibitor best beyond doubt for the specific conductivity that improves matrix material, but the threshold concentration of metal interpolation material is larger, generally in 50% left and right, therefore the amount needing is larger, larger to cost increase, the a large amount of interpolation of metal matrix functional stuffing and the consistency of the two are poor in addition often has a negative impact to forming the mechanical property of matrix material, moreover the density difference of the two is apart from large, affected again the stability of matrix material, therefore metal one-dimensional nano line is more easily formed to conductive network under low concentration in matrix external phase, thereby greatly reduce the consumption of metallic stuffing, weaken the disadvantageous effect to body material of bringing due to filler.Carbon is that carbon nanotube in static inhibitor attracts tremendous attention in the field of study at present, it is that a kind of radial dimension is nano level, and the carbon material of the cannulated constitutional features that axial dimension is micron dimension, has high-modulus, high strength, is considered to desirable reinforcing function filler.The similar graphite of carbon nano-tube conductive energy, and when making it add in matrix, its outstanding length-to-diameter ratio is more conducive to form the network structure of chain type than graphitized carbon black in matrix external phase, but its main drawback is its bad dispersibility in polymeric matrix, need surperficial organic modification to improve surface polarity, dispersion and the interface binding power of raising in polymeric matrix, gives full play to the two-layer effect of its reinforcement and functionalization.Carbon is that static inhibitor another one shortcoming is composite products color owing to reaching functional requirement, thereby addition affect greatly material true qualities, therefore needs assurance to give the addition of the functional prerequisite decline of body material low-carbon nano pipe.
In view of the outstanding advantage of above bi-material, by obtaining the composite antistatic agent in conjunction with both advantages at carbon nano tube surface growth in situ nano silver wire, for it, preparing transparent electrode material and antistatic material provides and has avoided a kind of solution of shortcoming separately.
Summary of the invention
Technical problem to be solved by this invention is: by the surface organic of carbon nanotube being improved to its dispersiveness in matrices of composite material, strengthened and matrix between interface binding power, utilize the coordination grappling platinum crystal seed of functional group's sulfydryl of surface organic to pt atom simultaneously, then growth in situ nano silver wire, prepares anti-static composite material.
The technical solution adopted for the present invention to solve the technical problems is: a kind of nano silver wire functionalized carbon nanotubes static inhibitor, and provide the method for modifying of carbon nano tube surface sulfhydrylation, and utilize the coordination of sulfydryl at carbon nano tube surface grappling platinum crystal seed, utilization, at the platinum crystal seed growth in situ nano silver wire of carbon nano tube surface, is prepared carbon nanotube and nano silver wire composite antistatic agent.
A nano silver wire functionalized carbon nanotubes static inhibitor, is characterized in that, static inhibitor is by platinum crystal seed direct in-situ, to grow by the complex body of nano silver wire on surperficial mercapto carbon nanometer pipe.
The preparation method of the functionalized nano silver wire static inhibitor of a kind of carbon nanotube, it is characterized in that, comprise the following steps: after (1) acidification, carbon nanotube obtains hydrosulphonyl functionalized carbon nanotube with the reactive organic molecule containing the polyfunctionality of sulfydryl, after acidification carbon nanotube with the organic molecule mass ratio of polyfunctionality that contains sulfydryl between 10～1:1; (2) by hydrosulphonyl functionalized carbon nanotube dispersed in polyvalent alcohol, the polyhydric alcohol solutions that adds platinum source, by the mass ratio of hydrosulphonyl functionalized carbon nanotube and platinum element, be 10000:0.1～1, solution is warmed up to 150 ℃ of reaction 10min and obtains the carbon nanotube that grappling has platinum crystal seed subsequently; Wherein said platiniferous source be platinous chloride, Platinic chloride; (3) after the reaction of the carbon nanotube of grappling platinum crystal seed finishes, to the polyhydric alcohol solutions that adds Silver Nitrate and structure directing agent in solution, wherein the mass ratio of hydrosulphonyl functionalized carbon nanotube and silver element is between 1:0.1～1, in solution between silver ions and mol ratio 1:5～10 of structure directing agent, solution is warming up to after 150～180 ℃, 1～3h is carried out in reaction, centrifugation, the dry carbon nanotube that obtains surface in situ growth nano silver wire of washing.
The organic molecule of the wherein said polyfunctionality containing sulfydryl is mercaptoethylamine, Thiovanic acid, 3-thiohydracrylic acid or to Thiosalicylic acid.Described polyvalent alcohol is selected from ethylene glycol, propylene glycol, butyleneglycol; Described structure directing agent is selected from polyvinylpyrrolidone (PVP), sodium lauryl sulphate (SDS), hexadecyl brometo de amonio (CTAB), oleic acid, oleyl amine.
Polyvalent alcohol in the present invention plays reductive agent and dispersion agent, according to general consumption, can fully reduce and disperse.In the present invention, sulfydryl consumption is many, and complexible platinum is many, and the nano silver wire number that can grow increases accordingly, be generally after acidification carbon nanotube and containing the organic molecule mass ratio of the polyfunctionality of sulfydryl between 10～1:1.
The consumption of the static inhibitor that the present invention that uses obtains when reaching antistatic requirement is few; Phase-splitting problem between the different components that anti-static composite material of the present invention has brought while having overcome carbon nanotube and silver-colored line blending and modifying, and the probability that the present invention forms conductive network in matrix increases during with respect to one dimension carbon nanotube and silver-colored line composite anti-static to some extent, overcome in the large shortcoming of the inner contact resistance of matrix, improved the synergistic enhancing effect of two kinds of heterogeneous static inhibitor.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the composite anti-static that obtains of embodiment 1;
Its cathetus be nano silver wire, the mean diameter of nano silver wire is about 100nm, crooked carbon nanotube;
Fig. 2 be pure nano-carbon tube under same amount with embodiment 1 in the conductivity map of composite antistatic agent in different matrix resin of preparation.
Embodiment
Embodiment 1
The first step: the N that acidifying carbon nanotube dispersed is arrived, ultrasonic 2h in N dimethyl formamide, the DMAP that adds again Thiovanic acid and catalysis equivalent, after 85 ℃ of reaction 24h, filtering and washing is dried and obtains hydrosulphonyl functionalized carbon nanotube, acidifying carbon nanotube wherein: DMF: Thiovanic acid=1g:150ml:0.1g.
Second step: be distributed in ethylene glycol the carbon nanotube of sulfhydrylation is ultrasonic, the platinous chloride ethylene glycol solution that the platinum ion concentration adding is 1mg/L, be warming up to the carbon nanotube that 150 ℃ of reaction 10min obtain Supported Pt Nanoparticles crystal seed, wherein the carbon nanotube of sulfhydrylation: ethylene glycol: platinous chloride ethylene glycol solution=100mg:100ml:5ml.
The 3rd step: the ethylene glycol solution that adds the Polyvinylpyrolidone (PVP) of 0.1mol/L Silver Nitrate and 0.6mol/L when previous step reaction finishes, be warming up to 160 ℃, reaction 2h, reaction finishes the dry matrix material that obtains the nano silver wire of carbon nanotube growth in situ of rear centrifuge washing, the wherein carbon nanotube of second step sulfhydrylation: the ethylene glycol solution of Silver Nitrate: the ethylene glycol solution=100mg:10ml:10ml of Polyvinylpyrolidone (PVP).
The first step: 1g acidifying carbon nanotube dispersed, to ultrasonic 2h in the DMF of 150ml, then is added to the DMAP of 1g to Thiosalicylic acid and catalysis equivalent, and after 85 ℃ of reaction 24h, filtering and washing is dry obtains hydrosulphonyl functionalized carbon nanotube.
Second step: be distributed in 100ml propylene glycol the carbon nanotube of 100mg sulfhydrylation is ultrasonic, the platinous chloride propylene glycol solution that the platinum ion concentration that adds 10ml is 1mg/L, is warming up to the carbon nanotube that 150 ℃ of reaction 10min obtain Supported Pt Nanoparticles crystal seed.
The 3rd step: each 10ml of propylene glycol solution that adds the Polyvinylpyrolidone (PVP) of 0.1mol/L Silver Nitrate and 0.6mol/L when previous step reaction finishes, be warming up to 160 ℃, reaction 2h, reaction finishes the dry matrix material that obtains the nano silver wire of carbon nanotube growth in situ of rear centrifuge washing.
Embodiment 3
The first step: 1g acidifying carbon nanotube dispersed, to ultrasonic 2h in the DMF of 150ml, then is added to 0.1g mercaptoethylamine, react under normal temperature after 24h that filtering and washing is dry obtains hydrosulphonyl functionalized carbon nanotube.
Second step: be distributed in 100ml ethylene glycol the carbon nanotube of 100mg sulfhydrylation is ultrasonic, the Platinic chloride ethylene glycol solution that the platinum ion concentration that adds 10ml is 1mg/L, is warming up to the carbon nanotube that 150 ℃ of reaction 10min obtain Supported Pt Nanoparticles crystal seed.
The 3rd step: add the propylene glycol solution of the sodium lauryl sulphate of 0.1mol/L Silver Nitrate and 1mol/L to be respectively 10ml when previous step reaction finishes, be warming up to 180 ℃, reaction 1h, reaction finishes the dry matrix material that obtains the nano silver wire of carbon nanotube growth in situ of rear centrifuge washing.
Embodiment 4
The first step: 1g acidifying carbon nanotube dispersed, to ultrasonic 2h in the DMF of 150ml, then is added to 0.1g mercaptoethylamine, react under normal temperature after 24h that filtering and washing is dry obtains hydrosulphonyl functionalized carbon nanotube.
Second step: be distributed in 100ml ethylene glycol the carbon nanotube of 100mg sulfhydrylation is ultrasonic, the Platinic chloride ethylene glycol solution that the platinum ion concentration that adds 10ml is 1mg/L, is warming up to the carbon nanotube that 150 ℃ of reaction 10min obtain Supported Pt Nanoparticles crystal seed.
The 3rd step: when previous step reaction finishes, add the propylene glycol solution 10ml of the oleyl amine of 0.1mol/L Silver Nitrate and 1mol/L, be warming up to 180 ℃, reaction 1h, reaction finishes the dry matrix material that obtains the nano silver wire of carbon nanotube growth in situ of rear centrifuge washing.
The specific conductivity test of the composite antistatic agent of preparing in pure nano-carbon tube and embodiment under same amount, in different matrix resin is as follows:
After 100mg carbon nanotube or the obtained composite antistatic agent of 100mg are added respectively and are uniformly dispersed in 10ml N-Methyl pyrrolidone, add 5g polyetherimide PEI, PC, PI or PEEK, at 120 ℃, mechanical stirring is dissolved completely, pour mould into, in vacuum drying oven, completely dry out solvent obtains after film that thickness is 1mm, and room temperature environment is tested and obtained Electrical Conductivity of Composites data by megger.
Claims (4)
1. the preparation method of the functionalized nano silver wire static inhibitor of carbon nanotube, it is characterized in that, comprise the following steps: after (1) acidification, carbon nanotube obtains hydrosulphonyl functionalized carbon nanotube with the reactive organic molecule containing the polyfunctionality of sulfydryl, after acidification carbon nanotube with the organic molecule mass ratio of polyfunctionality that contains sulfydryl between 10～1:1; (2) by hydrosulphonyl functionalized carbon nanotube dispersed in polyvalent alcohol, the polyhydric alcohol solutions that adds platinum source, by the mass ratio of hydrosulphonyl functionalized carbon nanotube and platinum element, be 10000:0.1～1, solution is warmed up to 150 ℃ of reaction 10min and obtains the carbon nanotube that grappling has platinum crystal seed subsequently; Wherein said platiniferous source be platinous chloride, Platinic chloride; (3) after the reaction of the carbon nanotube of grappling platinum crystal seed finishes, to the polyhydric alcohol solutions that adds Silver Nitrate and structure directing agent in solution, wherein the mass ratio of hydrosulphonyl functionalized carbon nanotube and silver element is between 1:0.1～1, in solution between silver ions and mol ratio 1:5～10 of structure directing agent, solution is warming up to after 150～180 ℃, 1～3h is carried out in reaction, centrifugation, the dry carbon nanotube that obtains surface in situ growth nano silver wire of washing;
The described polyvalent alcohol in above-mentioned steps (2) and (3) is selected from as ethylene glycol, propylene glycol or butyleneglycol.
2. according to the method for claim 1, it is characterized in that the organic molecule selected from mercapto ethamine of the described polyfunctionality containing sulfydryl, Thiovanic acid, 3-thiohydracrylic acid, to Thiosalicylic acid.
3. according to the method for claim 1, it is characterized in that, described structure directing agent is selected from polyvinylpyrrolidone (PVP), sodium lauryl sulphate (SDS), hexadecyl brometo de amonio (CTAB), oleic acid, oleyl amine.
4. the functionalized nano silver wire static inhibitor of carbon nanotube obtaining according to the either method of claim 1-3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210429090.7A CN102936357B (en) | 2012-10-31 | 2012-10-31 | Antistatic agent made from silver nanowire and functional carbon nano tube (CNT) and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210429090.7A CN102936357B (en) | 2012-10-31 | 2012-10-31 | Antistatic agent made from silver nanowire and functional carbon nano tube (CNT) and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102936357A CN102936357A (en) | 2013-02-20 |
| CN102936357B true CN102936357B (en) | 2014-04-02 |
Family
ID=47695285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210429090.7A Active CN102936357B (en) | 2012-10-31 | 2012-10-31 | Antistatic agent made from silver nanowire and functional carbon nano tube (CNT) and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102936357B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105170994A (en) * | 2015-09-17 | 2015-12-23 | 浙江工业大学 | Solvent thermal method for preparing copper nanowire |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103614090B (en) * | 2013-12-06 | 2015-06-17 | 苏州贤聚科技有限公司 | Antistatic pressure-sensitive adhesive protective film and preparation method thereof |
| CN104690293B (en) * | 2015-03-18 | 2017-05-03 | 重庆文理学院 | Preparation method for silver nanowires of different length-diameter ratios |
| CN105111467B (en) * | 2015-08-27 | 2018-02-23 | 北京化工大学 | A kind of preparation method of the PEI ultrafine powder of size tunable |
| US11385743B2 (en) * | 2016-03-11 | 2022-07-12 | Toray Industries, Inc. | Light-transmitting conductive laminate and light-transmitting conductive molded body using same |
| CN106144400B (en) * | 2016-08-23 | 2018-06-19 | 衡水起行橡塑有限公司 | One kind securely transmits band |
| CN106192050B (en) * | 2016-08-23 | 2018-03-23 | 浙江海明实业有限公司 | Anti-electrostatic polymer composite fibre |
| CN107189103B (en) * | 2017-06-29 | 2019-10-01 | 过冬 | A kind of conductive filler, preparation method and the usage |
| CN107655598B (en) * | 2017-09-12 | 2020-01-10 | 电子科技大学 | Flexible stress sensor based on carbon nanotube and silver nanowire composite conductive film |
| CN109111714A (en) * | 2018-07-25 | 2019-01-01 | 四川龙华光电薄膜股份有限公司 | Silver nanowires modified fullerenes micro/nano-fibre, preparation method and applications |
| CN109336089B (en) * | 2018-09-11 | 2021-10-26 | 华南理工大学 | Nano-silver modified CNTs composite material and preparation method and application thereof |
| CN111825076B (en) * | 2020-06-19 | 2022-08-26 | 郑州轻工业大学 | Carbon nanotube/MnO 2 composite material of core-sheath nano cable structure and preparation method thereof |
| CN111842923B (en) * | 2020-07-14 | 2022-11-29 | 西安工程大学 | Preparation method of silver nanowire/biomass porous carbon electromagnetic wave absorption material |
| CN114656657B (en) * | 2022-04-06 | 2024-01-30 | 合肥工业大学 | Preparation method of high-conductivity self-healing nano composite organic hydrogel |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1740405A (en) * | 2005-09-23 | 2006-03-01 | 浙江大学 | Silver nanometer wire synthesizing process |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120111661A (en) * | 2011-04-01 | 2012-10-10 | 삼성전자주식회사 | Strechable conductive nano fiber, strechable fiber electrode using the same and method for producing the same |
-
2012
- 2012-10-31 CN CN201210429090.7A patent/CN102936357B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1740405A (en) * | 2005-09-23 | 2006-03-01 | 浙江大学 | Silver nanometer wire synthesizing process |
Non-Patent Citations (2)
| Title |
|---|
| Yugang Sun，et al..Uniform Silver Nanowires Synthesis by Reducing AgNO3 with Ethylene Glycol in the Presence of Seeds and Poly(Vinyl Pyrrolidone).《Chem. Mater.》.2002,第14卷(第11期),4736-4745. * |
| 钮洋,等.水溶液中碳纳米管的表面增强拉曼光谱研究.《化学学报》.2012,第70卷1533-1537. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105170994A (en) * | 2015-09-17 | 2015-12-23 | 浙江工业大学 | Solvent thermal method for preparing copper nanowire |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102936357A (en) | 2013-02-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102936357B (en) | Antistatic agent made from silver nanowire and functional carbon nano tube (CNT) and preparation method | |
| Barisci et al. | Properties of carbon nanotube fibers spun from DNA‐stabilized dispersions | |
| Yu et al. | Polypyrrole-anchored cattail biomass-derived carbon aerogels for high performance binder-free supercapacitors | |
| Zhang et al. | Low percolation threshold in single-walled carbon nanotube/high density polyethylene composites prepared by melt processing technique | |
| KR101812534B1 (en) | Method for preparing GO-CNT composite fibers, GO-Graphene composite fibers, GO-Graphene-CNT composite fibers | |
| Ke et al. | Covalent functionalization of multiwalled carbon nanotubes with a low molecular weight chitosan | |
| CN102877286B (en) | Conductive composite fiber and preparation method thereof | |
| CN102121192B (en) | Elastic conductive composite fiber and preparation method thereof | |
| Das et al. | Electrospinning of polymer nanofibers loaded with noncovalently functionalized graphene | |
| KR100652065B1 (en) | A method for producing a conductive cellulose film and the same manufactured by the same | |
| Chen et al. | Synthesis of aligned carbon nanotube composite fibers with high performances by electrochemical deposition | |
| US20180151885A1 (en) | Discrete carbon nanotubes and microfiber composites | |
| CN101421338A (en) | Conductive carbon nanotube-polymer composite | |
| Schiffman et al. | Carbon black immobilized in electrospun chitosan membranes | |
| Bazbouz et al. | Fabrication of high specific electrical conductivity and high ampacity carbon Nanotube/Copper composite wires | |
| Shi et al. | Highly specific capacitance materials constructed via in situ synthesis of polyaniline in a cellulose matrix for supercapacitors | |
| Kang et al. | Electrically conducting electrospun silk membranes fabricated by adsorption of carbon nanotubes | |
| Beggs et al. | Increasing the resistivity and IFSS of unsized carbon fibre by covalent surface modification | |
| CN113066984B (en) | Conductive paste and preparation method and application thereof | |
| Di Crescenzo et al. | Surfactant hydrogels for the dispersion of carbon‐nanotube‐based catalysts | |
| Kim et al. | A seed-mediated growth of gold nanoparticles inside carbon nanotube fibers for fabrication of multifunctional nanohybrid fibers with enhanced mechanical and electrical properties | |
| CN103806012A (en) | Preparation method of preparing graphene/chitosan composite thin film by one step electro-deposition | |
| CN103556452A (en) | Elastic conductive composite fiber and preparation method thereof | |
| Lay et al. | Combined effect of carbon nanotubes and polypyrrole on the electrical properties of cellulose-nanopaper | |
| Liu et al. | Recent advances in bio‐sourced polymeric carbohydrate/nanotube composites |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |