CN103482601B - Preparation method for three-dimensional multistage porous carbon based on polyvinylidene chloride-polystyrene segmented copolymer - Google Patents
Preparation method for three-dimensional multistage porous carbon based on polyvinylidene chloride-polystyrene segmented copolymer Download PDFInfo
- Publication number
- CN103482601B CN103482601B CN201310405577.6A CN201310405577A CN103482601B CN 103482601 B CN103482601 B CN 103482601B CN 201310405577 A CN201310405577 A CN 201310405577A CN 103482601 B CN103482601 B CN 103482601B
- Authority
- CN
- China
- Prior art keywords
- emulsion
- mass parts
- polyvinylidene chloride
- preparation
- block copolymer
- 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
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method for three-dimensional multistage porous carbon based on a polyvinylidene chloride-polystyrene segmented copolymer. The method comprises the following steps of (1) adding vinylidene chloride (VDC), an amphipathic macromolecular RAFT (reversible addition-fragmentation chain transfer) reagent, a water-soluble initiator and deionized water in a reaction kettle, stirring and emulsifying, charging nitrogen to remove oxygen, heating to perform RAFT active free radical emulsion polymerization, cooling, and eliminating unreacted VDC to obtain active PVDC (polyvinylidene chloride) emulsion; (2) adding a styrene (St) monomer and a water-soluble initiator in the emulsion aforementioned, swelling and emulsifying, and heating to perform styrene RAFT emulsion polymerization to obtain PVDC-b-PS emulsion, demulsifying and condensing, filtering and washing, and drying to obtain a segmented copolymer; and (3) directly carbonizing the segmented copolymer in a muffle furnace for a certain time at a high temperature, and slowly cooling to a room temperature to prepare the multistage porous carbon containing micropores, mesopores and macropores simultaneously. The preparation process disclosed by the invention is simple; and the obtained multistage carbon structure can be adjusted by virtue of the segmented ratio of the copolymer, and has a good application prospect in the fields of new energies, catalyst supports and the like.
Description
Technical field
The present invention relates to the preparation method of multistage porous carbon material, particularly relate to the preparation method of the three-dimensional multistage porous charcoal based on polyvinylidene chloride-polystyrene block copolymer.
Background technology
Porous carbon material has the characteristics such as flourishing pore texture, excellent absorption and electrochemistry, is widely used in fractionation by adsorption, catalyst cupport, electricity occur or the preparation etc. of storage facilities (as ultracapacitor, lithium cell etc.) electrode.According to the regulation of international theory chemistry with applied chemistry federation (IUPAC), the hole in porous charcoal can be divided three classes by pore size: micropore (< 2nm), mesopore (2 ~ 50nm) and macropore (> 50nm).In porous charcoal, the hole of different pore size has different effects.The micropore that aperture is less than 2nm because of number many, specific surface area is large, so the ion less to gas molecule, small molecules liquid or diameter has strong adsorption.The mesopore of aperture within the scope of 2 ~ 50nm is named again mesoporous, mainly plays a part to carry adsorbed material to make it to arrive channeling and the larger adsorbate of binding molecule size at micropore edge.Therefore, the porous charcoal of mesopore prosperity can be used for supported catalyst and the larger material of fractionation by adsorption molecular dimension, has different functions along with the difference of the compound of institute's load.The macropore that aperture is greater than 50nm then mainly plays transfer passages.Pure Microporous Carbon, mesoporous carbon or macropore carbon, be difficult to reach Carbon Materials optimal performance in one aspect.Therefore, have the porous carbon material of micropore, mesopore and/or large pore distribution, namely the research of multistage porous charcoal causes the attention of many investigators simultaneously.The single pore structure of porous charcoal is expanded to hierarchical porous structure, and by regulating the ratio of sizes pore structure, therefrom can select the porous charcoal of best performance, the practical application for future has important meaning.
Traditional porous carbon material, mainly through Organic carbon presoma high temperature pyrolysis, physics and chemistry activation prepare, often there is the deficiencies such as vesicular structure in surperficial defectiveness, pyroprocessing or graphitizing process easily caves in, affect the performance of porous charcoal.In order to overcome these not enough, the many new porous charcoal preparation methods of software engineering researchers invent, comprising: (1) physics or physical/chemical deep activation method; (2) carbonization of the carbon precursor of easy pyrolyzed components and heating charing component is comprised; (3) metal, metal oxide or organometallic compound catalytic activation method; (4) carbonized aerogel or crystal gel method; (5) template is eliminated to the hard template carbon precursor carbonization comprising pre-synthesis; (6) direct carbonization contains the carbon precursor method of self-assembly or the soft template that is separated.Although the preparation method of porous carbon material emerges in an endless stream, differs from one another, acted on by catalyzer or pore-creating agent that carbon matrix forms hole is main path, if activation method utilizes inorganic or organic catalyst and carbon precursor to react, form hole; Sol-gel method makes solvent deviate from by the special drying process such as overcritical while guarantee carbon precursor structural integrity, thus in carbon precursor, leave corresponding hole, and its essence utilizes water or organic solvent as pore-creating agent; Inorganic template method is by chemical agent dissolves inorganic template, and in carbon matrix, leave corresponding pore texture.The structure of charcoal precursor structure, catalyzer or pore-creating agent and content, preparation technology etc. are the important factors of the stuctures and properties affecting porous charcoal.
Vinylidene chloride (VDC) polymkeric substance can not be activated with regard to the obtained porous carbon material based on micropore, therefore receives the concern of Many researchers in recent years.Lamond etc., 700 DEG C, 800 DEG C charings VDC resin (trade(brand)name Saran resin), obtain the carbon molecular sieve that aperture is 0.62nm and 0.8nm.Meanwhile, some patents also report and prepare the technology with Microporous Carbon and Microporous Carbon molecular sieve by VDC polymkeric substance.Xue Li newly waits (Chinese invention patent CN102505188A) report to use polyvinylidene chloride to prepare the way of activated carbon fiber for matrix, can have microporous activated carbon fiber without the need to activating directly preparation.Song Qinhua etc. (Chinese invention patent CN102389827A) report uses vinylidene chloride-acrylonitrile copolymer microballoon as precursor, prepare one for removing micro-halid sorbent material in gas, due to the unique texture of microspheric matrix material, be conducive to mass transfer and the heat transfer of adsorption process, also be conducive to the dispersion of adsorption activity position-metallic silver particles simultaneously and stablize, the sorbent material of preparation has high efficiency.
In vinylidene chloride polymer base porous charcoal, introduce mesopore, the research preparing micropore-mesopore combined multi-stage porous charcoal also has report.(the Carbon such as Kim, 2004,42:1491-1500) first by PVDC 400 DEG C of thermal treatments, then be directly warmed up to 600 ~ 1000 DEG C to carbonize again, or first with the charing that heats up again after KOH activation, find that the pore size of disactivation carbide is at below 1nm, porosity is little, and the aperture activating carbide increases between 1 ~ 2nm, also occur a small amount of mesopore, specific surface area and porosity increases simultaneously.(Carbon, 2002, the 411:1678-1687 such as Tamai; Mol.Cryst.Liq.Cryst., 2002,388:33-37) research has been entered to the standby VDC polymer-based carbon porous charcoal containing mesopore of catalytic activation legal system, find methyl ethyl diketone yttrium [Y (acac)
3] there is the effect promoting VDC polymkeric substance carbide formation mesopore, respectively using VDC-acrylonitrile copolymer, VDC-vinyl chloride copolymer, VDC-methyl acrylate copolymer as carbon precursor, with Y (acac)
3be dissolved in altogether in tetrahydrofuran (THF) (THF) and form mixed solution; after flash distillation removing THF; oxidation or charing pre-treatment, finally utilize steam high-temperature activation to obtain under nitrogen protection mesopore-micropore carbon material that aperture be narrow ditribution, finds that VDC polymer matrices forms, Y (acac)
3the structural parameter such as content, charing and activation condition centering porosity all have considerable influence, as along with Y (acac)
3content increases, and total specific surface of carbide reduces, as Y (acac)
3content is when 0.3 ~ 1.0wt%, and middle pore specific surface area is comparatively large, as Y (acac)
3during content >1.0wt%, though mesoporous is improved, pore volume, total specific surface area and middle pore specific surface area all decline.(the Adsorption such as Choma, 2009,15 (2): 167 ~ 171) take median size as the silica sol particle of 24nm be template, vinylidene chloride-vinylchlorid (VDC-VC) multipolymer (trade(brand)name Saran) is carbon precursor, silica sol is mixed with VDC-VC copolymer particle in aqueous ethanolic solution and heat-treats, silicon oxide particle is made to be adsorbed onto VDC-VC copolymer particle surface, template is gone again, the obtained compound porous Carbon Materials of micropore-mesopore through high temperature carbonization, etching.Because the recombination rate of nano-silica particle and resin particle is lower, using silicon oxide (as silicon oxide: VDC-VC copolymer resins mass ratio is 10:1) also only to obtain micropore-mesopore composite porous charcoal that mesoporous is about 50% in a large number, cause the waste of silicon oxide.(the Chinese invention patent such as Bao Yongzhong, ZL201110189251.5) the vinylidene chloride semi-continuous emulsion polymerizing under adopting nano silicon oxide dispersed particle to exist, obtain vinylidene chloride polymer/nano silicon oxide composite particles that nano oxidized silicone content is high, reunion degree is little, further carbonization and eliminate silicon oxide inorganic template, obtains porosity and specific surface area is large, mesoporous is adjustable mesopore-micropore activated carbon composite.But the research that there is no at present based on the micropore-mesopore-macropore combined multi-stage porous carbon material of vinylidene chloride polymer is reported.The present invention using can pyrolytic polymer polystyrene block as soft template, prepare PVDC-b-PS multipolymer by RAFT Living Radical Emulsion Polymerization, then prepare the multistage porous charcoal of micropore-mesopore-macropore compound by high temperature cabonization.
Soft template method being separated or self-assembly formation nanostructure by organic molecule, then by obtaining corresponding pore texture to the carbonization of carbon matrix precursor, this just requires strictly to control polymer molecule the Nomenclature Composition and Structure of Complexes.Active free radical polymerization provides effective approach for controlling polymer molecule the Nomenclature Composition and Structure of Complexes.In vinylidene chloride radical polymerization, active macromolecules free radical easy phase vinylidene chloride monomer chain tra nsfer, therefore, molecular weight and the molecular chain-end based structures of vinylidene chloride polymer determine primarily of chain transfer reaction, the common active free radical polymerization method terminating as target with Quality Initiative is not suitable for vinylidene chloride polymerization, adds the difficulty of vinylidene chloride polymer molecular composition and structure control.The monomer that reversible addion-fragmentation chain transfer (RAFT) active free radical polymerization is suitable for and solvent are comparatively extensive, are also the methods being comparatively applicable to vinylidene chloride active free radical polymerization at present.Severac etc. (Polymer International, 2002,51 (10): 1117-1122) report the method being prepared vinylidene chloride-methyl acrylate (VDC-MA) multipolymer by RAFT polymerization process the earliest.Recently, Velasquez etc. (Macromolecules, 2013,46 (3): 664-673) report has synthesized VDC base Amphipathilic block polymer.But these reports are all be polymerized in organic solvent, have that long reaction time, the polymericular weight that obtains are less, difficult solvent recovery and high in cost of production not enough, be difficult to industrial applications.
Compare other traditional polymerization, letex polymerization has lot of advantages: polyreaction occurs in the emulsion particle being scattered in aqueous phase inside, although very high at the inner viscosity of emulsion particle, because water is external phase, overall viscosity is not high and change is also little, whole system is conducted heat and is easy to; Owing to there is free radical blanketing effect so high speed of reaction and the polymkeric substance of high molecular can be realized in letex polymerization simultaneously; Most of letex polymerization is dispersion medium with water, avoids expensive solvent and the trouble of recycling design, decrease the pollution to environment.Conventional emulsion polymerizations needs to use the small-molecular emulsifier such as negatively charged ion, nonionic, and the existence of these emulsifying agents can affect the performance of the finished product.Emulsifier-free emulsion polymerization, need not using lower than the emulsifying agent of micelle-forming concentration or carrying out under using reactive emulsifier, can make up the deficiency of conventional emulsion polymerizations.If RAFT polymerization and emulsifier-free emulsion polymerization are combined, then can obtain that molecular weight is controlled, narrow molecular weight distribution, there is not conventional emulsifier, vinylidene chloride polymer emulsion that colloidal stability is high.The report of vinylidene chloride polymer is not prepared at present about RAFT letex polymerization.Luo Yingwu etc. (Macromolecules, 2011,44 (2): 221-229) use polyacrylic acid-b-polystyrene amphiphilic macromolecular chain-transfer agent regulation and control styrene emulsion polymerization to obtain having the high molecular weight polystyrene of narrow ditribution.Chenal etc. (Polymer Chemistry, 2013,4:752-762) directly use polyacrylic acid amphiphilic macromolecular chain-transfer agent to prepare polybutylacrylate latex, and by making reaction controlled about pH regulator to 5.5, latex is stablized.
In view of above reason, the present invention proposes the preparation method of the micropore-mesopore-macropore combined multi-stage porous charcoal based on polyvinylidene chloride-polystyrene block copolymer, namely the vinylidene chloride polymer latex particle obtained using RAFT letex polymerization is as seed, block copolymerization is carried out again with vinylbenzene, with obtained polyvinylidene chloride-polystyrene block copolymer for the direct high temperature cabonization of carbon matrix precursor, utilize polyvinylidene chloride high temperature to become charcoal process to form micropore simultaneously, microphase-separated polystyrene decomposition forms the method for mesopore and macropore, prepare the multistage porous charcoal structure of micropore-mesopore-macropore compound.
Summary of the invention
The object of the invention is the preparation method expanding polyvinylidene chloride porous carbon material, a kind of preparation method of the three-dimensional multistage porous charcoal based on polyvinylidene chloride-polystyrene block copolymer is provided.
Step based on the preparation method of the three-dimensional multistage porous charcoal of polyvinylidene chloride-polystyrene block copolymer is as follows:
1) 300 mass parts deionized waters, 30-100 mass parts vinylidene chloride, 3-12 mass parts amphiphilic macromolecular reversible addition fragmentation chain transfer agent, 0.06-0.27 mass of water-soluble initiator is added in a kettle., stir 30min and make reactant mixing, emulsification, letting nitrogen in and deoxidizing, the Reversible Addition Fragmentation Chain-Transfer Polymerization of 3-10h is carried out at 50-70 DEG C, cooling, eliminating unreacted vinylidene chloride, obtain polyvinylidene chloride emulsion; 3 ~ 18 mass parts styrene monomers are added again by the above polyvinylidene chloride emulsion of every 100 mass parts, stirring 8-24h makes vinylbenzene fully swelling in polyvinylidene chloride seed emulsion, add 0.015 ~ 0.20 mass of water-soluble initiator, be heated to 50-70 DEG C and carry out vinylbenzene reversible addion-fragmentation chain transfer Living Radical Emulsion Polymerization, reaction 10 ~ 24h, obtain polyvinylidene chloride-polystyrene block copolymer emulsion, add 0.1 mass parts sulfuric acid breakdown of emulsion, filtration washing, drying obtain polyvinylidene chloride-polystyrene block copolymer;
2) polyvinylidene chloride-polystyrene block copolymer is placed in crucible, puts into retort furnace, under protection of inert gas; 900 DEG C-1000 DEG C are warmed up to 2 DEG C/min-10 DEG C/min speed; constant temperature 2-6h, then slow cooling is to normal temperature, obtained multistage porous charcoal.
The chemical structural formula of described amphiphilic macromolecular reversible addion-fragmentation chain transfer chain-transfer agent is:
Wherein hydrophilic monomer is vinylformic acid, and lipophilicity monomer is vinylbenzene, and x and y is respectively the polymerization degree of hydrophilic monomer and lipophilicity monomer, and the ratio of x and y is between 3:1 to 7:1.Wherein Z group is C
12sulfydryl; R group is 2-bis-isobutyl acidic group.
Described water soluble starter is Potassium Persulphate, azo two isobutyl imidazoline hydrochloride or azo-bis-isobutyrate hydrochloride.
Described inertia protective gas is helium, neon, argon gas or nitrogen.
Preparation method of the present invention is simple, utilize industrial amplification production, synthesized multistage porous carbon material structure presents three-dimensional structure, there is micropore, mesopore and macropore diameter structure simultaneously, and pore size distribution is narrow, can be adjusted by carbon source block in block polymer and pyrolysis block ratio easily, have a good application prospect in the field such as new forms of energy, Industrial Catalysis.
Accompanying drawing explanation
Fig. 1 is gel permeation chromatography (GPC) graphic representation that before and after example 7 of the present invention polymerization, molecular weight increases;
Fig. 2 is the electron scanning micrograph that the multistage porous charcoal obtained after example 7 of the present invention carbonization amplifies 100,000 times;
Fig. 3 is the isothermal nitrogen adsorption curve comparison figure of the porous charcoal obtained after the multistage porous charcoal and pure PVDC carbonization obtained after example 7 of the present invention carbonization.
Specific embodiments
Amphiphilic macromolecular chain transfer agents chemical structure skeleton symbol used in the embodiment of the present invention mainly contains 3 kinds:
Amphiphilic macromolecular chain transfer agents (1), by vinylformic acid with styrene copolymerizedly to obtain to dodecyl-2-isopropylformic acid three thioesters, wherein acrylic acid polymerization degree is 15, and the cinnamic polymerization degree is 5.
Amphiphilic macromolecular chain transfer agents (2), by vinylformic acid with styrene copolymerizedly to obtain to dodecyl-2-isopropylformic acid three thioesters, wherein acrylic acid polymerization degree is 27, and the cinnamic polymerization degree is 5.
Amphiphilic macromolecular chain transfer agents (3), by vinylformic acid with styrene copolymerizedly to obtain to dodecyl-2-isopropylformic acid three thioesters, wherein acrylic acid polymerization degree is 35, and the cinnamic polymerization degree is 5.
Embodiment 1
Add 300 mass parts distilled water in a kettle., 30 mass parts vinylidene chlorides, 3 mass parts amphiphilic macromolecular reversible addion-fragmentation chain transfer (RAFT) chain-transfer agents (1), 0.06 mass parts Potassium Persulphate (KPS) water soluble starter add in autoclave, stirring at room temperature 30min makes reactant mixing, emulsification, letting nitrogen in and deoxidizing, be heated to 70 DEG C, polyreaction 10h, obtains vinylidene chloride (VDC) polymer emulsion.Again by every 100 mass parts gained seed emulsion, add 3 mass parts block polymerization monomer styrenes, low temperature 24h makes seed emulsion fully swelling, add 0.016 mass parts KPS water soluble starter again, be heated to 70 DEG C, polyreaction 10h, obtain block polymer emulsion, add 0.1 mass parts sulfuric acid breakdown of emulsion, filtration, be placed in vacuum drying oven dry.
The vinylidene chloride group block copolymer of preparation is placed in crucible; put into High Temperature Furnaces Heating Apparatus; first in High Temperature Furnaces Heating Apparatus, pass into protectiveness inert nitrogen gas 30min; be warmed up to 900 DEG C of constant temperature 2h with 2 DEG C/min, then slow cooling is to normal temperature, i.e. obtained multistage porous charcoal; continue in carbonization process to pass into inertia protection gas nitrogen, the speed continuing to pass into inert protective gas is 20ml/min.
Embodiment 2
Add 300 mass parts distilled water in a kettle., 30 mass parts vinylidene chlorides, 3 mass parts amphiphilic macromolecular RAFT agent (2), 0.06 mass parts azo-bis-isobutyrate hydrochloride (V-50) water soluble starter add in autoclave, low temperature stirs 30min and makes reactant mixing, emulsification, letting nitrogen in and deoxidizing, be heated to 70 DEG C, polyreaction 6h, obtains VDC polymer emulsion.Again by every 100 mass parts gained seed emulsion, add 12 mass parts block polymerization monomer styrenes, low temperature 8h makes seed emulsion fully swelling, add 0.018 mass of water-soluble initiator again, be heated to 70 DEG C, polyreaction 24h, obtain block polymer emulsion, add 0.1 mass parts sulfuric acid breakdown of emulsion, filtration, be placed in vacuum drying oven dry.
The vinylidene chloride group block copolymer of preparation is placed in crucible; put into High Temperature Furnaces Heating Apparatus; first in High Temperature Furnaces Heating Apparatus, pass into protectiveness rare gas element argon gas 60min; be warmed up to 1000 DEG C of constant temperature 6h with 10 DEG C/min, then slow cooling is to normal temperature, i.e. obtained multistage porous charcoal; continue in carbonization process to pass into inertia protection gas argon gas, the speed continuing to pass into inert protective gas is 50ml/min.
Embodiment 3
Add 300 mass parts distilled water in a kettle., 30 mass parts vinylidene chlorides, 3 mass parts amphiphilic macromolecular RAFT agent (1), 0.06 mass parts azo two isobutyl imidazoline hydrochloride (VA-044) water soluble starter add in autoclave, low temperature stirs 30min and makes reactant mixing, emulsification, letting nitrogen in and deoxidizing, be heated to 50 DEG C, polyreaction 6h, obtains VDC polymer emulsion.Again by every 100 mass parts gained seed emulsion, add 3 mass parts block polymerization monomer styrenes, low temperature 24h makes seed emulsion fully swelling, add 0.02 mass of water-soluble initiator VA-044 again, be heated to 50 DEG C, polyreaction 24h, obtain block polymer emulsion, add 0.1 mass parts sulfuric acid breakdown of emulsion, filtration, be placed in vacuum drying oven dry.
The vinylidene chloride group block copolymer of preparation is placed in crucible; put into High Temperature Furnaces Heating Apparatus; first in High Temperature Furnaces Heating Apparatus, pass into protectiveness inert gas helium 60min; be warmed up to 900 DEG C of constant temperature 4h with 2 DEG C/min, then slow cooling is to normal temperature, i.e. obtained multistage porous charcoal; continue in carbonization process to pass into inertia protection gas helium, the speed continuing to pass into inert protective gas is 20ml/min.
Embodiment 4
Add 300 mass parts distilled water in a kettle., 100 mass parts vinylidene chlorides, 12 mass parts amphiphilic macromolecular RAFT agent (2), 0.27 mass of water-soluble initiator KPS add in autoclave, low temperature stirs 30min and makes reactant mixing, emulsification, letting nitrogen in and deoxidizing, be heated to 70 DEG C, polyreaction 6h, obtains VDC polymer emulsion.Again by every 100 mass parts gained seed emulsion, add 6 mass parts block polymerization monomer styrenes, low temperature 24h makes seed emulsion fully swelling, add 0.018 amount part water soluble starter KPS again, be heated to 70 DEG C, polyreaction 24h, obtain block polymer emulsion, add 0.1 mass parts sulfuric acid breakdown of emulsion, filtration, be placed in vacuum drying oven dry.
The vinylidene chloride group block copolymer of preparation is placed in crucible; put into High Temperature Furnaces Heating Apparatus; first in High Temperature Furnaces Heating Apparatus, pass into protectiveness inert nitrogen gas 60min; be warmed up to 1000 DEG C of constant temperature 6h with 5 DEG C/min, then slow cooling is to normal temperature, i.e. obtained multistage porous charcoal; continue in carbonization process to pass into inertia protection gas nitrogen, the speed continuing to pass into inert protective gas is 20ml/min.
Embodiment 5
Add 300 mass parts distilled water in a kettle., 30 mass parts vinylidene chlorides, 3 mass parts amphiphilic macromolecular RAFT agent (3), 0.06 mass of water-soluble initiator VA-044 add in autoclave, low temperature stirs 30min and makes reactant mixing, emulsification, letting nitrogen in and deoxidizing, be heated to 50 DEG C, polyreaction 6h, obtains VDC polymer emulsion.Again by 100 mass parts gained seed emulsion, add 3 mass parts block polymerization monomer styrenes, low temperature 10h makes seed emulsion fully swelling, add 0.016 mass of water-soluble initiator VA-044 again, be heated to 50 DEG C, polyreaction 24h, obtain block polymer emulsion, add 0.1 mass parts sulfuric acid breakdown of emulsion, filtration, be placed in vacuum drying oven dry.
The vinylidene chloride group block copolymer of preparation is placed in crucible; put into High Temperature Furnaces Heating Apparatus; first in High Temperature Furnaces Heating Apparatus, pass into protectiveness rare gas element neon 60min; be warmed up to 900 DEG C of constant temperature 4h with 5 DEG C/min, then slow cooling is to normal temperature, i.e. obtained multistage porous charcoal; continue in carbonization process to pass into inertia protection gas neon, the speed continuing to pass into inert protective gas is 20ml/min.
Embodiment 6
Add 300 mass parts distilled water in a kettle., 30 mass parts vinylidene chlorides, 3 mass parts amphiphilic macromolecular RAFT agent (3), 0.06 mass of water-soluble initiator VA-044 add in autoclave, low temperature stirs 30min and makes reactant mixing, emulsification, letting nitrogen in and deoxidizing, be heated to 50 DEG C, polyreaction 6h, obtains VDC polymer emulsion.By every 100 mass parts gained seed emulsion, add 7 mass parts block polymerization monomer styrenes, low temperature 20h makes seed emulsion fully swelling, add 0.016 mass of water-soluble initiator VA-044 again, be heated to 50 DEG C, polyreaction 24h, obtain block polymer emulsion, add 0.1 mass parts sulfuric acid breakdown of emulsion, filtration, be placed in vacuum drying oven dry.
The vinylidene chloride group block copolymer of preparation is placed in crucible; put into High Temperature Furnaces Heating Apparatus; first in High Temperature Furnaces Heating Apparatus, pass into protectiveness inert nitrogen gas 60min; be warmed up to 900 DEG C of constant temperature 4h with 10 DEG C/min, then slow cooling is to normal temperature, i.e. obtained multistage porous charcoal; continue in carbonization process to pass into inertia protection gas nitrogen, the speed continuing to pass into inert protective gas is 20ml/min.
Embodiment 7
Add 300 mass parts distilled water in a kettle., 30 mass parts vinylidene chlorides, 3 mass parts amphiphilic macromolecular RAFT agent (3), 0.06 mass of water-soluble initiator VA-044 add in autoclave, low temperature stirs 30min and makes reactant mixing, emulsification, letting nitrogen in and deoxidizing, be heated to 50 DEG C, polyreaction 6h, obtains VDC polymer emulsion.By every 100 mass parts gained seed emulsion, add 16 mass parts block polymerization monomer styrenes, low temperature 24h makes seed emulsion fully swelling, add 0.016 mass of water-soluble initiator VA-044 again, be heated to 50 DEG C, polyreaction 24h, obtain block polymer emulsion, add 0.1 mass parts sulfuric acid breakdown of emulsion, filtration, be placed in vacuum drying oven dry.
The vinylidene chloride group block copolymer of preparation is placed in crucible; put into High Temperature Furnaces Heating Apparatus; first in High Temperature Furnaces Heating Apparatus, pass into protectiveness inert nitrogen gas 40min; be warmed up to 900 DEG C of constant temperature 2h with 10 DEG C/min, then slow cooling is to normal temperature, i.e. obtained multistage porous charcoal; continue in carbonization process to pass into inertia protection gas nitrogen, the speed continuing to pass into inert protective gas is 50ml/min.
Embodiment 8
Add 300 mass parts distilled water in a kettle., 30 mass parts vinylidene chlorides, 3 mass parts amphiphilic macromolecular RAFT agent (3), 0.06 mass of water-soluble initiator VA-044 add in autoclave, low temperature stirs 30min and makes reactant mixing, emulsification, letting nitrogen in and deoxidizing, be heated to 50 DEG C, polyreaction 6h, obtains VDC polymer emulsion.By every 100 mass parts gained seed emulsion, add 18 mass parts block polymerization monomer styrenes, low temperature 24h makes seed emulsion fully swelling, add 0.016 mass of water-soluble initiator VA-044 again, be heated to 50 DEG C, polyreaction 24h, obtain block polymer emulsion, add 0.1 mass parts sulfuric acid breakdown of emulsion, filtration, be placed in vacuum drying oven dry.
The vinylidene chloride group block copolymer of preparation is placed in crucible; put into High Temperature Furnaces Heating Apparatus; first in High Temperature Furnaces Heating Apparatus, pass into protectiveness rare gas element argon gas 40min; be warmed up to 900 DEG C of constant temperature 2h with 10 DEG C/min, then slow cooling is to normal temperature, i.e. obtained multistage porous charcoal; continue in carbonization process to pass into inertia protection gas argon gas, the speed continuing to pass into inert protective gas is 20ml/min.
Embodiment 9
Add 300 mass parts distilled water in a kettle., 60 mass parts vinylidene chlorides, 5.4 mass parts amphiphilic macromolecular RAFT agent (3), 0.01 mass parts VA-044 water soluble starter add in autoclave, low temperature stirs 30min and makes reactant mixing, emulsification, letting nitrogen in and deoxidizing, be heated to 50 DEG C, polyreaction 6h, obtains VDC polymer emulsion.By every 100 mass parts gained seed emulsion, add 18 mass parts block polymerization monomer styrenes, low temperature 24h makes seed emulsion fully swelling, add 0.016 mass of water-soluble initiator VA-044 again, be heated to 50 DEG C, polyreaction 24h, obtain block polymer emulsion, add 0.1 mass parts sulfuric acid breakdown of emulsion, filtration, be placed in vacuum drying oven dry.
The vinylidene chloride group block copolymer of preparation is placed in crucible; put into High Temperature Furnaces Heating Apparatus; first in High Temperature Furnaces Heating Apparatus, pass into protectiveness inert nitrogen gas 60min; be warmed up to 900 DEG C of constant temperature 4h with 2 DEG C/min, then slow cooling is to normal temperature, i.e. obtained multistage porous charcoal; continue in carbonization process to pass into inertia protection gas nitrogen, the speed continuing to pass into inert protective gas is 20ml/min.
Embodiment 10
Add 300 mass parts distilled water in a kettle., 50 mass parts vinylidene chlorides, 5 mass parts amphiphilic macromolecular RAFT agent (3), 0.009 mass parts V-50 water soluble starter add in autoclave, low temperature stirs 30min and makes reactant mixing, emulsification, letting nitrogen in and deoxidizing, be heated to 70 DEG C, polyreaction 6h, obtains VDC polymer emulsion.By every 100 mass parts gained seed emulsion, add 12 mass parts block polymerization monomer styrenes, low temperature 18h makes seed emulsion fully swelling, add 0.016 mass of water-soluble initiator V-50 again, be heated to 50 DEG C, polyreaction 24h, obtain block polymer emulsion, add 0.1 mass parts sulfuric acid breakdown of emulsion, filtration, be placed in vacuum drying oven dry.
The vinylidene chloride group block copolymer of preparation is placed in crucible; put into High Temperature Furnaces Heating Apparatus; first in High Temperature Furnaces Heating Apparatus, pass into protectiveness inert nitrogen gas 60min; be warmed up to 900 DEG C of constant temperature 4h with 2 DEG C/min, then slow cooling is to normal temperature, i.e. obtained multistage porous charcoal; continue in carbonization process to pass into inertia protection gas nitrogen, the speed continuing to pass into inert protective gas is 20ml/min.
The molecular weight distribution of part RAFT seed emulsion block polymerization example and emulsion particle characteristic
| Embodiment | Molecular weight (gmol -1) | Molecular weight distribution | Emulsion particle diameter D z(nm) | Particle size dispersion index |
| Example 5 | 24120 | 1.52 | 66 | 0.19 |
| Example 6 | 35470 | 1.70 | 68 | 0.14 |
| Example 7 | 76300 | 1.60 | 80 | 0.05 |
| Example 8 | 88800 | 1.66 | 84 | 0.06 |
Polymericular weight and distribution use gel permeation chromatography (GPC) to record; Emulsion particle diameter and dispersion index use dynamic light scattering (DLS) to record, and index is less, shows that grain size is more single.
The three-dimensional multistage porous carbon pore structure data that carbon matrix precursor carbonization obtains
Pore structure data use isothermal nitrogen adsorption test to obtain, wherein S
bETfor specific surface area; S
t-microfor the specific surface area of micropore; V
totalfor total pore volume; V
t-microfor Micropore volume; D
micromicropore size; D
mesofor mesopore pore size.
Claims (4)
1. based on a preparation method for the three-dimensional multistage porous charcoal of polyvinylidene chloride-polystyrene block copolymer, it is characterized in that, the step of method is as follows:
1) 300 mass parts deionized waters, 30-100 mass parts vinylidene chloride, 3-12 mass parts amphiphilic macromolecular reversible addition fragmentation chain transfer agent, 0.06-0.27 mass of water-soluble initiator is added in a kettle., stir 30min and make reactant mixing, emulsification, letting nitrogen in and deoxidizing, the Reversible Addition Fragmentation Chain-Transfer Polymerization of 3-10h is carried out at 50-70 DEG C, cooling, eliminating unreacted vinylidene chloride, obtain polyvinylidene chloride emulsion; 3 ~ 18 mass parts styrene monomers are added again by the above polyvinylidene chloride emulsion of every 100 mass parts, stirring 8-24h makes vinylbenzene fully swelling in polyvinylidene chloride seed emulsion, add 0.015 ~ 0.20 mass of water-soluble initiator, be heated to 50-70 DEG C and carry out vinylbenzene reversible addion-fragmentation chain transfer Living Radical Emulsion Polymerization, reaction 10 ~ 24h, obtain polyvinylidene chloride-polystyrene block copolymer emulsion, add 0.1 mass parts sulfuric acid breakdown of emulsion, filtration washing, drying obtain polyvinylidene chloride-polystyrene block copolymer;
2) polyvinylidene chloride-polystyrene block copolymer is placed in crucible, puts into retort furnace, under protection of inert gas; 900 DEG C-1000 DEG C are warmed up to 2 DEG C/min-10 DEG C/min speed; constant temperature 2-6h, then slow cooling is to normal temperature, obtained multistage porous charcoal.
2. the preparation method of the three-dimensional multistage porous charcoal based on polyvinylidene chloride-polystyrene block copolymer according to claim 1, is characterized in that the chemical structural formula of described amphiphilic macromolecular reversible addion-fragmentation chain transfer chain-transfer agent is:
Wherein hydrophilic monomer is vinylformic acid, and lipophilicity monomer is vinylbenzene, and x and y is respectively the polymerization degree of hydrophilic monomer and lipophilicity monomer, and the ratio of x and y is between 3:1 to 7:l.Wherein Z group is C
12sulfydryl; R group is 2-bis-isobutyl acidic group.
3. the preparation method of the three-dimensional multistage porous charcoal based on polyvinylidene chloride-polystyrene block copolymer according to claim 1, is characterized in that described water soluble starter is Potassium Persulphate, azo two isobutyl imidazoline hydrochloride or azo-bis-isobutyrate hydrochloride.
4. the preparation method of the three-dimensional multistage porous charcoal based on polyvinylidene chloride-polystyrene block copolymer according to claim 1, is characterized in that described inertia protective gas is helium, neon or argon gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310405577.6A CN103482601B (en) | 2013-09-06 | 2013-09-06 | Preparation method for three-dimensional multistage porous carbon based on polyvinylidene chloride-polystyrene segmented copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310405577.6A CN103482601B (en) | 2013-09-06 | 2013-09-06 | Preparation method for three-dimensional multistage porous carbon based on polyvinylidene chloride-polystyrene segmented copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103482601A CN103482601A (en) | 2014-01-01 |
| CN103482601B true CN103482601B (en) | 2015-04-15 |
Family
ID=49823274
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310405577.6A Active CN103482601B (en) | 2013-09-06 | 2013-09-06 | Preparation method for three-dimensional multistage porous carbon based on polyvinylidene chloride-polystyrene segmented copolymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103482601B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105439115B (en) * | 2014-08-08 | 2017-11-07 | 中国石油化工股份有限公司 | The carbon nano-particle and its production method of a kind of Heteroatom doping |
| CN104275152A (en) * | 2014-10-29 | 2015-01-14 | 苏州纳微科技有限公司 | Carbonized micro-ball and preparation method thereof |
| US11439976B2 (en) * | 2016-11-17 | 2022-09-13 | Solvay Sa | Advanced porous carbon adsorbents for CO2 capture and separation |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633961A (en) * | 2012-04-16 | 2012-08-15 | 浙江大学 | Preparation method of segmented copolymer from vinylidene chloride copolymer and polyethylene glycol |
| CN102807206A (en) * | 2012-09-11 | 2012-12-05 | 浙江大学 | Method for preparing mesopore-micropore composite porous carbon on basis of vinylidene chloride polymers |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3527789B2 (en) * | 1994-12-29 | 2004-05-17 | 旭化成ケミカルズ株式会社 | Electrode for electric double layer capacitor and its manufacturing method |
| KR101115318B1 (en) * | 2011-12-26 | 2012-03-06 | 한국기계연구원 | Method for manufacturing Porous carbon materials |
-
2013
- 2013-09-06 CN CN201310405577.6A patent/CN103482601B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633961A (en) * | 2012-04-16 | 2012-08-15 | 浙江大学 | Preparation method of segmented copolymer from vinylidene chloride copolymer and polyethylene glycol |
| CN102807206A (en) * | 2012-09-11 | 2012-12-05 | 浙江大学 | Method for preparing mesopore-micropore composite porous carbon on basis of vinylidene chloride polymers |
Non-Patent Citations (1)
| Title |
|---|
| 偏氯乙烯聚合物基多孔炭的制备及应用研究进展;吴启强 等;《化工生产与技术》;20110625;第18卷(第3期);第45-50页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103482601A (en) | 2014-01-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103466596B (en) | Hollow nanosphere material as well as preparation method and application thereof | |
| CN109671576A (en) | Carbon nano tube-MXene composite three-dimensional porous carbon material and preparation method thereof | |
| CN104261403A (en) | Preparation method for graphene with three-dimensional porous structure | |
| CN107032321A (en) | The hollow carbon sphere material of a kind of nitrogen-phosphor codoping and shell with classification macropore meso-hole structure and its preparation method and application | |
| CN101362598A (en) | Synthetic process of ordered mesoporous carbon material | |
| CN103482601B (en) | Preparation method for three-dimensional multistage porous carbon based on polyvinylidene chloride-polystyrene segmented copolymer | |
| CN108190853B (en) | Preparation method of honeycomb foam wall hollow carbon ball | |
| CN108609602B (en) | Nitrogen-doped microporous carbon material based on energetic polyion liquid and preparation method thereof | |
| Li et al. | Fabrication of carbon microspheres with controllable porous structure by using waste Camellia oleifera shells | |
| CN104292236A (en) | Preparation method of three-dimensional porous g-C3N4 material | |
| CN105080512A (en) | Preparation method and application of oxidized graphene based cadmium ion imprinted polymer | |
| CN105817202A (en) | Preparation method and application of three-dimensional lignin-based hierarchical pore activated carbon material | |
| CN103950915A (en) | Carbon nanoribbon with large specific surface area and preparation method thereof | |
| CN105217627A (en) | A kind of preparation method of coconut husk greying gac | |
| CN108610505B (en) | Preparation method of polymer-based adjustable hierarchical pore material | |
| CN108682875A (en) | A kind of platinum controllable based on platinum carrying capacity-nano hollow carbon sphere catalyst and preparation method thereof | |
| CN101219784B (en) | Process for producing polyacrylonitrile base carbon nanospheres | |
| CN110482521B (en) | Preparation method of hollow carbon spheres | |
| CN101696005B (en) | Method for preparing acrylonitrile polymer based mesoporous carbon | |
| CN102351168B (en) | Preparation method of vinylidene chloride polymer base mesopore-micropore composite porous charcoal | |
| Wang et al. | Salt template synthesis of hierarchical porous carbon adsorbents for Congo red removal | |
| Zhang et al. | Low-temperature organic solvent-based synthesis of amorphous porous carbon nanoparticles with high specific surface area at ambient atmosphere | |
| Sun et al. | Facile fabrication of carbon spheres with tunable morphologies from novel polymeric carbon precursors | |
| Chen et al. | Macroporous conducting matrix: fabrication and application as electrocatalyst support | |
| CN110835091B (en) | PAN-based porous carbon-magnesium alloy loaded Zr-based MOFs hydrogen storage material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |