CN103482601A - 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
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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, relate in particular 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 occurs or the preparation of storage facilities (as ultracapacitor, lithium cell etc.) electrode etc.Regulation according to the 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 factor order that aperture is less than 2nm is many, and specific surface area is large, so gas molecule, small molecules liquid or the less ion of diameter are had to strong adsorption.The mesopore of aperture in 2～50nm scope named again mesoporous, the channeling that mainly plays a part to carry adsorbed material to make it to arrive the micropore edge, and adsorbs the larger adsorbate of molecular dimension.Therefore, the porous charcoal of mesopore prosperity can be used for supported catalyst and the larger material of fractionation by adsorption molecular dimension, along with the difference of the compound of institute's load and have different functions.The macropore that aperture is greater than 50nm mainly works to transport passage.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, i.e. the research of multistage porous charcoal has caused many investigators' attention simultaneously.The single pore structure of porous charcoal is expanded to hierarchical porous structure, by regulating the ratio of sizes pore structure, can therefrom select the porous charcoal of best performance, for following practical application, important meaning is arranged.
Traditional porous carbon material, mainly high temperature pyrolysis, the physics and chemistry activation by organic carbon precursor prepares, and the deficiency such as often exist in surperficial defectiveness, pyroprocessing or graphitizing process vesicular structure easily to cave in affects the performance of porous charcoal.In order to overcome these deficiencies, software engineering researchers invent many new porous charcoal preparation methods, comprising: (1) physics or physical/chemical deep activation method; (2) carbonization of the carbon precursor that comprises easy pyrolyzed components and heating charing component; (3) metal, metal oxide or organometallic compound catalytic activation method; (4) carbonized aerogel or crystal gel method; (5) to the hard template carbon precursor carbonization that comprises pre-synthesis and eliminate template; (6) direct carbonization is containing 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, act on carbon matrix by catalyzer or pore-creating agent that to form hole be main path, as activation method is to utilize inorganic or organic catalyst to react with carbon precursor, the formation hole; Sol-gel method deviates from solvent by the special drying process such as overcritical when guaranteeing the carbon precursor structural integrity, thereby stays corresponding hole in carbon precursor, and its essence is to utilize water or organic solvent as pore-creating agent; Inorganic template is by the inorganic template of chemical agent dissolves, and stays corresponding pore texture in carbon matrix.The structure of charcoal precursor structure, catalyzer or pore-creating agent and content, preparation technology etc. affect the structure of porous charcoal and the important factor of performance.
Vinylidene chloride (VDC) polymkeric substance can not activatedly just make take micropore as main porous carbon material, therefore receives in recent years the concern of Many researchers.Lamond etc., at 700 ℃, 800 ℃ charing VDC resins (trade(brand)name Saran resin), obtain the carbon molecular sieve that aperture is 0.62nm and 0.8nm.Simultaneously, some patents have also been reported the technology that is had Microporous Carbon and Microporous Carbon molecular sieve by the preparation of 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 be without the activation carbon fiber that directly preparation have the micropore activity.Song Qinhua etc. (Chinese invention patent CN102389827A) report is used the vinylidene chloride-acrylonitrile copolymer microballoon as precursor, prepared a kind of for removing the micro-halid sorbent material of gas, unique texture due to the 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 and stablize, the sorbent material of preparation has high efficiency simultaneously.
Introduce mesopore in vinylidene chloride polymer base porous charcoal, the research for preparing micropore-mesopore combined multi-stage porous charcoal also has report.(the Carbon such as Kim, 2004,42:1491-1500) first by PVDC 400 ℃ of thermal treatments, then directly be warmed up to 600～1000 ℃ of charings again, or, first with the charing that heats up again after the KOH activation, find that the pore size of disactivation carbide is below 1nm, porosity is little, and the aperture of activation carbide increases between 1～2nm, a small amount of mesopore also appears simultaneously, specific surface area and porosity increase.(Carbon, 2002, the 411:1678-1687 such as Tamai; Mol.Cryst.Liq.Cryst., 2002,388:33-37) the standby VDC polymer-based carbon porous charcoal containing mesopore of catalytic activation legal system has been entered to research, find methyl ethyl diketone yttrium [Y (acac)
3] there is the effect that promotes VDC polymkeric substance carbide formation mesopore, using respectively 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 THF is removed in flash distillation; oxidation or charing pre-treatment, finally under nitrogen protection, utilize the steam high-temperature activation to obtain aperture be the mesopore-micropore carbon material of narrow distribution, find that the VDC polymer matrices forms, Y (acac)
3content, charing and activation condition all have considerable influence to structural parameter such as mesoporous, 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 larger, as Y (acac)
3content>during 1.0wt%, though mesoporous is improved, pore volume, total specific surface area and middle pore specific surface area all descend.(the Adsorption such as Choma, 2009,15 (2): 167～171) take the silica sol particle that median size is 24nm is template, vinylidene chloride-vinylchlorid (VDC-VC) multipolymer (trade(brand)name Saran) is carbon precursor, silica sol is mixed and heat-treats with the VDC-VC copolymer particle in aqueous ethanolic solution, make silicon oxide particle be adsorbed onto VDC-VC copolymer particle surface, go template through high temperature carbonization, etching again, make the compound porous Carbon Materials of micropore-mesopore.Because the recombination rate of nano silicon oxide particle and resin particle is lower, also only obtain the micropore that mesoporous is 50% left and right-mesopore composite porous charcoal at a large amount of silicon oxide (as silicon oxide: VDC-VC copolymer resins mass ratio is 10:1) that use, cause the waste of silicon oxide.(the Chinese invention patent such as Bao Yongzhong, ZL201110189251.5) adopt the vinylidene chloride semi-continuous emulsion polymerizing under the existence of nano silicon oxide dispersed particle, obtained the vinylidene chloride polymer that nano oxidized silicone content is high, the reunion degree is little/nano silicon oxide composite particles, further carbonization and the inorganic template of elimination silicon oxide, obtained the mesopore that porosity and specific surface area are large, mesoporous is adjustable-micropore activated carbon composite.But, there is no at present the research report of micropore-mesopore based on vinylidene chloride polymer-macropore combined multi-stage porous carbon material.But the present invention is usingd the pyrolytic polymer polystyrene block as soft template, by the RAFT Living Radical Emulsion Polymerization, prepares the PVDC-b-PS multipolymer, then prepare the compound multistage porous charcoal of micropore-mesopore-macropore by high temperature cabonization.
Soft template method is separated or self-assembly formation nanostructure by organic molecule, then obtains corresponding pore texture by the carbonization to carbon matrix precursor, and this just requires the polymer molecule the Nomenclature Composition and Structure of Complexes is strictly controlled.Active free radical polymerization provides effective approach for controlling the polymer molecule the Nomenclature Composition and Structure of Complexes.In vinylidene chloride radical polymerization, the easy phase vinylidene chloride monomer of active macromolecular radical chain shifts, therefore, the molecular weight of vinylidene chloride polymer and molecular chain-end based structures are mainly determined by chain transfer reaction, the common active free radical polymerization method that terminates as target with Quality Initiative is not suitable for the vinylidene chloride polymerization, has increased the difficulty of vinylidene chloride polymer molecular composition and structure control.It is comparatively extensive that reversible addition-fracture chain shifts (RAFT) active free radical polymerization applicable monomer and solvent, is also to be applicable at present the method for vinylidene chloride active free radical polymerization.(Polymer International, 2002,51 (10): 1117-1122) reported the earliest the method for preparing vinylidene chloride-methyl acrylate (VDC-MA) multipolymer by the RAFT polymerization process such as Severac.Recently, (Macromolecules, 2013,46 (3): 664-673) report has synthesized VDC base Amphipathilic block polymer to Velasquez etc.But these reports are all to carry out polymerization in organic solvent, the polymericular weight that have long reaction time, obtains is less, difficult solvent recovery and high in cost of production deficiency, is difficult to industrial applications.
Compare other traditional polymerization, letex polymerization has lot of advantages: polyreaction occurs in the emulsion particle that is scattered in water inside, although very high at the inner viscosity of emulsion particle, because water is external phase, whole viscosity is not high and variation is also little, makes whole system conduct heat and is easy to; So can realize the polymkeric substance of high speed of reaction and high molecular owing to there being the free radical blanketing effect in letex polymerization simultaneously; Most of letex polymerizations are to take water as dispersion medium, have avoided expensive solvent and the trouble that reclaims solvent, have also reduced the pollution to environment.The conventional emulsion polymerization need to be used the small-molecular emulsifiers 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 using under reactive emulsifier and carry out, can make up the deficiency of conventional emulsion polymerization.If RAFT polymerization and emulsifier-free emulsion polymerization are combined, can obtain that molecular weight is controlled, narrow molecular weight distribution, not have conventional emulsifier, vinylidene chloride polymer emulsion that colloidal stability is high.At present not about RAFT, letex polymerization prepares the report of vinylidene chloride polymer.(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 distribution such as Luo Yingwu.Chenal etc. (Polymer Chemistry, 2013,4:752-762) directly use polyacrylic acid amphiphilic macromolecular chain-transfer agent to prepare butyl polyacrylate latex, and make to react controlled by pH regulator to 5.5 left and right, latex is stable.
In view of above reason, the present invention proposes the preparation method of micropore-mesopore based on polyvinylidene chloride-polystyrene block copolymer-macropore combined multi-stage porous charcoal, the vinylidene chloride polymer latex particle that the RAFT letex polymerization of usining obtains is as seed, carry out block copolymerization with vinylbenzene again, polyvinylidene chloride-the polystyrene block copolymer made of take is the direct high temperature cabonization of carbon matrix precursor, utilize polyvinylidene chloride high temperature to become the charcoal process to form micropore simultaneously, the microphase-separated polystyrene is decomposed to form the method for mesopore and macropore, prepare the compound multistage porous charcoal structure of micropore-mesopore-macropore.
Summary of the invention
The objective of the invention is to expand the preparation method of 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.
The preparation method's of the three-dimensional multistage porous charcoal based on polyvinylidene chloride-polystyrene block copolymer step is as follows:
1) add 300 mass parts deionized waters, 30-100 mass parts vinylidene chloride, the reversible addition of 3-12 mass parts amphiphilic macromolecular-fracture chain transfer agents, 0.06-0.27 mass parts water soluble starter in reactor, stir 30min and make reactant mixing, emulsification, letting nitrogen in and deoxidizing, at 50-70 ℃ of Reversible Addition Fragmentation Chain-Transfer Polymerization that carries out 3-10h, cooling, eliminating unreacted vinylidene chloride, obtain the polyvinylidene chloride emulsion; Add 3～18 mass parts styrene monomers by the above polyvinylidene chloride emulsion of every 100 mass parts again, stir 8-24h and make vinylbenzene abundant swelling in the polyvinylidene chloride seed emulsion, add 0.015～0.20 mass parts water soluble starter, be heated to 50-70 ℃ and carry out the reversible addition of vinylbenzene-fracture chain transfer activity free-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 to obtain polyvinylidene chloride-polystyrene block copolymer;
2) polyvinylidene chloride-polystyrene block copolymer is placed in to crucible, puts into retort furnace, under protection of inert gas, with 2 ℃/min-10 ℃/min speed, be warmed up to 900 ℃-1000 ℃, constant temperature 2-6h, then slow cooling makes multistage porous charcoal to normal temperature.
The chemical structural formula that the reversible addition of described amphiphilic macromolecular-fracture chain shifts chain-transfer agent is:
Wherein hydrophilic monomer is vinylformic acid, and the lipophilicity monomer is vinylbenzene, and x and y are respectively the polymerization degree of hydrophilic monomer and lipophilicity monomer, the ratio of x and y at 3:1 between 7:1.Wherein the Z group is C
12sulfydryl; The R group is 2-bis-isobutyl acidic groups.
Described water soluble starter is Potassium Persulphate, azo two isobutyl imidazoline salt hydrochlorate or azo-bis-isobutyrate hydrochlorides.
Described inertia protective gas is helium, neon, argon gas or nitrogen.
Preparation method of the present invention is simple, utilize industrial amplification production, the multistage porous carbon material structure of synthesized 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, be had a good application prospect in fields such as new forms of energy, Industrial Catalysis.
The accompanying drawing explanation
Fig. 1 is gel permeation chromatography (GPC) graphic representation that before and after example 7 polymerizations of the present invention, molecular weight increases;
Fig. 2 is that the multistage porous charcoal obtained after example 7 carbonizations of the present invention is amplified the electron scanning micrograph of 100,000 times;
Fig. 3 is the isothermal nitrogen adsorption curve comparison figure of the porous charcoal that obtains after the multistage porous charcoal that obtains after example 7 carbonizations of the present invention and pure PVDC 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 obtain to dodecyl-2-isopropylformic acid three thioesters, wherein acrylic acid polymerization degree is 15, the cinnamic polymerization degree is 5.
Amphiphilic macromolecular chain transfer agents (2), by vinylformic acid with styrene copolymerizedly obtain to dodecyl-2-isopropylformic acid three thioesters, wherein acrylic acid polymerization degree is 27, the cinnamic polymerization degree is 5.
Amphiphilic macromolecular chain transfer agents (3), by vinylformic acid with styrene copolymerizedly obtain to dodecyl-2-isopropylformic acid three thioesters, wherein acrylic acid polymerization degree is 35, the cinnamic polymerization degree is 5.
Embodiment 1
In reactor, add 300 mass parts distilled water, 30 mass parts vinylidene chlorides, the reversible addition of 3 mass parts amphiphilic macromolecular-fracture chain transfer (RAFT) chain-transfer agent (1), 0.06 mass parts Potassium Persulphate (KPS) water soluble starter to add in autoclave, stirring at room 30min makes reactant mixing, emulsification, letting nitrogen in and deoxidizing, be heated to 70 ℃, polyreaction 10h, obtain vinylidene chloride (VDC) polymer emulsion.Again by every 100 mass parts gained seed emulsion, add 3 mass parts block polymerization monomer styrenes, stir 24h under low temperature and make the abundant swelling of seed emulsion, add again 0.016 mass parts KPS water soluble starter, be heated to 70 ℃, polyreaction 10h, obtain the 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 to 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 ℃ of constant temperature 2h with 2 ℃/min, more slow cooling makes multistage porous charcoal to normal temperature; continue to pass into inertia protection gas nitrogen in carbonization process, the speed that continues to pass into inert protective gas is 20ml/min.
Embodiment 2
In reactor, add 300 mass parts distilled water, 30 mass parts vinylidene chlorides, 3 mass parts amphiphilic macromolecular RAFT chain-transfer agents (2), 0.06 mass parts azo-bis-isobutyrate hydrochloride (V-50) water soluble starter to add in autoclave, low temperature stirs 30min and makes reactant mixing, emulsification, letting nitrogen in and deoxidizing, be heated to 70 ℃, polyreaction 6h, obtain the VDC polymer emulsion.Again by every 100 mass parts gained seed emulsion, add 12 mass parts block polymerization monomer styrenes, stir 8h under low temperature and make the abundant swelling of seed emulsion, add again 0.018 mass parts water soluble starter, be heated to 70 ℃, polyreaction 24h, obtain the 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 to 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 ℃ of constant temperature 6h with 10 ℃/min, more slow cooling makes multistage porous charcoal to normal temperature; continue to pass into inertia protection gas argon gas in carbonization process, the speed that continues to pass into inert protective gas is 50ml/min.
Embodiment 3
In reactor, add 300 mass parts distilled water, 30 mass parts vinylidene chlorides, 3 mass parts amphiphilic macromolecular RAFT chain-transfer agents (1), 0.06 mass parts azo two isobutyl imidazoline salt hydrochlorate (VA-044) water soluble starters to add in autoclave, low temperature stirs 30min and makes reactant mixing, emulsification, letting nitrogen in and deoxidizing, be heated to 50 ℃, polyreaction 6h, obtain the VDC polymer emulsion.Again by every 100 mass parts gained seed emulsion, add 3 mass parts block polymerization monomer styrenes, stir 24h under low temperature and make the abundant swelling of seed emulsion, add again 0.02 mass parts water soluble starter VA-044, be heated to 50 ℃, polyreaction 24h, obtain the 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 to crucible; put into High Temperature Furnaces Heating Apparatus; first in High Temperature Furnaces Heating Apparatus, pass into protectiveness rare gas element helium 60min; be warmed up to 900 ℃ of constant temperature 4h with 2 ℃/min, more slow cooling makes multistage porous charcoal to normal temperature; continue to pass into inertia protection gas helium in carbonization process, the speed that continues to pass into inert protective gas is 20ml/min.
Embodiment 4
In reactor, add 300 mass parts distilled water, 100 mass parts vinylidene chlorides, 12 mass parts amphiphilic macromolecular RAFT chain-transfer agents (2), 0.27 mass parts water soluble starter KPS to add in autoclave, low temperature stirs 30min and makes reactant mixing, emulsification, letting nitrogen in and deoxidizing, be heated to 70 ℃, polyreaction 6h, obtain the VDC polymer emulsion.Again by every 100 mass parts gained seed emulsion, add 6 mass parts block polymerization monomer styrenes, stir 24h under low temperature and make the abundant swelling of seed emulsion, add again 0.018 amount part water soluble starter KPS, be heated to 70 ℃, polyreaction 24h, obtain the 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 to 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 ℃ of constant temperature 6h with 5 ℃/min, more slow cooling makes multistage porous charcoal to normal temperature; continue to pass into inertia protection gas nitrogen in carbonization process, the speed that continues to pass into inert protective gas is 20ml/min.
Embodiment 5
In reactor, add 300 mass parts distilled water, 30 mass parts vinylidene chlorides, 3 mass parts amphiphilic macromolecular RAFT chain-transfer agents (3), 0.06 mass parts water soluble starter VA-044 to add in autoclave, low temperature stirs 30min and makes reactant mixing, emulsification, letting nitrogen in and deoxidizing, be heated to 50 ℃, polyreaction 6h, obtain the VDC polymer emulsion.Again by 100 mass parts gained seed emulsion, add 3 mass parts block polymerization monomer styrenes, stir 10h under low temperature and make the abundant swelling of seed emulsion, add again 0.016 mass parts water soluble starter VA-044, be heated to 50 ℃, polyreaction 24h, obtain the 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 to 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 ℃ of constant temperature 4h with 5 ℃/min, more slow cooling makes multistage porous charcoal to normal temperature; continue to pass into inertia protection gas neon in carbonization process, the speed that continues to pass into inert protective gas is 20ml/min.
Embodiment 6
In reactor, add 300 mass parts distilled water, 30 mass parts vinylidene chlorides, 3 mass parts amphiphilic macromolecular RAFT chain-transfer agents (3), 0.06 mass parts water soluble starter VA-044 to add in autoclave, low temperature stirs 30min and makes reactant mixing, emulsification, letting nitrogen in and deoxidizing, be heated to 50 ℃, polyreaction 6h, obtain the VDC polymer emulsion.By every 100 mass parts gained seed emulsion, add 7 mass parts block polymerization monomer styrenes, stir 20h under low temperature and make the abundant swelling of seed emulsion, add again 0.016 mass parts water soluble starter VA-044, be heated to 50 ℃, polyreaction 24h, obtain the 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 to 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 ℃ of constant temperature 4h with 10 ℃/min, more slow cooling makes multistage porous charcoal to normal temperature; continue to pass into inertia protection gas nitrogen in carbonization process, the speed that continues to pass into inert protective gas is 20ml/min.
Embodiment 7
In reactor, add 300 mass parts distilled water, 30 mass parts vinylidene chlorides, 3 mass parts amphiphilic macromolecular RAFT chain-transfer agents (3), 0.06 mass parts water soluble starter VA-044 to add in autoclave, low temperature stirs 30min and makes reactant mixing, emulsification, letting nitrogen in and deoxidizing, be heated to 50 ℃, polyreaction 6h, obtain the VDC polymer emulsion.By every 100 mass parts gained seed emulsion, add 16 mass parts block polymerization monomer styrenes, stir 24h under low temperature and make the abundant swelling of seed emulsion, add again 0.016 mass parts water soluble starter VA-044, be heated to 50 ℃, polyreaction 24h, obtain the 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 to 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 ℃ of constant temperature 2h with 10 ℃/min, more slow cooling makes multistage porous charcoal to normal temperature; continue to pass into inertia protection gas nitrogen in carbonization process, the speed that continues to pass into inert protective gas is 50ml/min.
Embodiment 8
In reactor, add 300 mass parts distilled water, 30 mass parts vinylidene chlorides, 3 mass parts amphiphilic macromolecular RAFT chain-transfer agents (3), 0.06 mass parts water soluble starter VA-044 to add in autoclave, low temperature stirs 30min and makes reactant mixing, emulsification, letting nitrogen in and deoxidizing, be heated to 50 ℃, polyreaction 6h, obtain the VDC polymer emulsion.By every 100 mass parts gained seed emulsion, add 18 mass parts block polymerization monomer styrenes, stir 24h under low temperature and make the abundant swelling of seed emulsion, add again 0.016 mass parts water soluble starter VA-044, be heated to 50 ℃, polyreaction 24h, obtain the 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 to 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 ℃ of constant temperature 2h with 10 ℃/min, more slow cooling makes multistage porous charcoal to normal temperature; continue to pass into inertia protection gas argon gas in carbonization process, the speed that continues to pass into inert protective gas is 20ml/min.
Embodiment 9
In reactor, add 300 mass parts distilled water, 60 mass parts vinylidene chlorides, 5.4 mass parts amphiphilic macromolecular RAFT chain-transfer agents (3), 0.01 mass parts VA-044 water soluble starter to add in autoclave, low temperature stirs 30min and makes reactant mixing, emulsification, letting nitrogen in and deoxidizing, be heated to 50 ℃, polyreaction 6h, obtain the VDC polymer emulsion.By every 100 mass parts gained seed emulsion, add 18 mass parts block polymerization monomer styrenes, stir 24h under low temperature and make the abundant swelling of seed emulsion, add again 0.016 mass parts water soluble starter VA-044, be heated to 50 ℃, polyreaction 24h, obtain the 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 to 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 ℃ of constant temperature 4h with 2 ℃/min, more slow cooling makes multistage porous charcoal to normal temperature; continue to pass into inertia protection gas nitrogen in carbonization process, the speed that continues to pass into inert protective gas is 20ml/min.
In reactor, add 300 mass parts distilled water, 50 mass parts vinylidene chlorides, 5 mass parts amphiphilic macromolecular RAFT chain-transfer agents (3), 0.009 mass parts V-50 water soluble starter to add in autoclave, low temperature stirs 30min and makes reactant mixing, emulsification, letting nitrogen in and deoxidizing, be heated to 70 ℃, polyreaction 6h, obtain the VDC polymer emulsion.By every 100 mass parts gained seed emulsion, add 12 mass parts block polymerization monomer styrenes, stir 18h under low temperature and make the abundant swelling of seed emulsion, add again 0.016 mass parts water soluble starter V-50, be heated to 50 ℃, polyreaction 24h, obtain the 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 to 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 ℃ of constant temperature 4h with 2 ℃/min, more slow cooling makes multistage porous charcoal to normal temperature; continue to pass into inertia protection gas nitrogen in carbonization process, the speed that continues to pass into inert protective gas is 20ml/min.
Molecular weight distribution and the emulsion particle characteristic of part RAFT seed emulsion block polymerization example
| Embodiment | Molecular weight (gmol -1) | Molecular weight distribution | Emulsion particle diameter D z(nm) | The 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 are used gel permeation chromatography (GPC) to record; Emulsion particle diameter and dispersion index are used 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 the carbon matrix precursor carbonization obtains
The pore structure data are used the isothermal nitrogen adsorption test to obtain, wherein S
bETfor specific surface area; S
t-microspecific surface area for micropore; V
totalfor total pore volume; V
t-microfor Micropore volume; D
micromicropore size; D
mesofor the mesopore aperture.
Claims (4)
1. the preparation method of the three-dimensional multistage porous charcoal based on polyvinylidene chloride-polystyrene block copolymer, is characterized in that, the step of method is as follows:
1) add 300 mass parts deionized waters, 30-100 mass parts vinylidene chloride, the reversible addition of 3-12 mass parts amphiphilic macromolecular-fracture chain transfer agents, 0.06-0.27 mass parts water soluble starter in reactor, stir 30min and make reactant mixing, emulsification, letting nitrogen in and deoxidizing, at 50-70 ℃ of Reversible Addition Fragmentation Chain-Transfer Polymerization that carries out 3-10h, cooling, eliminating unreacted vinylidene chloride, obtain the polyvinylidene chloride emulsion; Add 3 ~ 18 mass parts styrene monomers by the above polyvinylidene chloride emulsion of every 100 mass parts again, stir 8-24h and make vinylbenzene abundant swelling in the polyvinylidene chloride seed emulsion, add 0.015 ~ 0.20 mass parts water soluble starter, be heated to 50-70 ℃ and carry out the reversible addition of vinylbenzene-fracture chain transfer activity free-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 to obtain polyvinylidene chloride-polystyrene block copolymer;
2) polyvinylidene chloride-polystyrene block copolymer is placed in to crucible, puts into retort furnace, under protection of inert gas; be warmed up to 900 ℃-1000 ℃ with 2 ℃/min-10 ℃/min speed; constant temperature 2-6h, then slow cooling makes multistage porous charcoal to normal temperature.
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 that the reversible addition of described amphiphilic macromolecular-fracture chain shifts chain-transfer agent is:
Wherein hydrophilic monomer is vinylformic acid, and the lipophilicity monomer is vinylbenzene, and x and y are respectively the polymerization degree of hydrophilic monomer and lipophilicity monomer, and the ratio of x and y is at 3:1 between 7:l, and wherein the Z group is C
12sulfydryl; The R group is 2-bis-isobutyl acidic groups.
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 salt hydrochlorate or azo-bis-isobutyrate hydrochlorides.
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, argon gas or nitrogen.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105439115A (en) * | 2014-08-08 | 2016-03-30 | 中国石油化工股份有限公司 | Heteroatom doping carbon nanoparticle and production method thereof |
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