WO2019218540A1 - 一种聚丙烯腈基三维大孔碳块的制备方法 - Google Patents

一种聚丙烯腈基三维大孔碳块的制备方法 Download PDF

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WO2019218540A1
WO2019218540A1 PCT/CN2018/103674 CN2018103674W WO2019218540A1 WO 2019218540 A1 WO2019218540 A1 WO 2019218540A1 CN 2018103674 W CN2018103674 W CN 2018103674W WO 2019218540 A1 WO2019218540 A1 WO 2019218540A1
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polyacrylonitrile
foaming
carbon block
dimensional macroporous
precursor
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赵国群
龚洁
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Shandong University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/336—Preparation characterised by gaseous activating agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/318—Preparation characterised by the starting materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/034—Post-expanding of foam beads or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/08—Supercritical fluid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/18—Homopolymers or copolymers of nitriles
    • C08J2333/20—Homopolymers or copolymers of acrylonitrile

Definitions

  • the invention relates to a method for preparing porous carbon, in particular to a method for preparing a polyacrylonitrile-based three-dimensional macroporous carbon block.
  • Porous carbon materials are widely used in fuel cell electrode materials, electric double layer capacitors and lithium ion batteries due to their rich pore structure, large specific surface area, low density, excellent chemical stability and electrical conductivity, and low production cost. Electrode materials, catalyst carriers, electromagnetic shielding materials, water purification filtration, sound absorbing materials and other fields. The structure of the pores is a key factor affecting the application of porous carbon materials. Among them, the controllable preparation of large holes is the key to obtaining three-dimensional monolithic carbon blocks.
  • polyacrylonitrile has a simple molecular structure, controllable carbonization degree, high carbon yield, excellent mechanical properties, and low raw material cost, accounting for more than 90% of the total carbon fiber market.
  • Carbon precursor has a simple molecular structure, controllable carbonization degree, high carbon yield, excellent mechanical properties, and low raw material cost, accounting for more than 90% of the total carbon fiber market.
  • Carbon precursor has a simple molecular structure, controllable carbonization degree, high carbon yield, excellent mechanical properties, and low raw material cost, accounting for more than 90% of the total carbon fiber market.
  • Carbon precursor However, its softening temperature and decomposition temperature are very close, and the melting point is high and the viscosity is large. The existing processing methods are very limited.
  • the template method is divided into a hard template method and a soft template method according to the difference in the sacrifice phase of the template.
  • the no-template method mainly includes a heat to phase separation method and a batch foaming method.
  • the hard template method can better replicate the structure of the template, but the process route is cumbersome, the processing cost is high and the environment is not environmentally friendly, thus greatly limiting the scale application of the method.
  • the dispersibility in the template is not good, and it is difficult to fill the entire volume of the bulk material, especially at the narrow gap between the templates, resulting in many defects in the obtained porous carbon material. Therefore, the hard templating method is difficult to apply to the preparation of a polyacrylonitrile bulk material.
  • the soft template method is simpler than the hard template method, but the controllability of the pore structure is significantly lower than that of the hard template method.
  • both the hard template method and the soft template method are not effective methods for preparing polyacrylonitrile-based three-dimensional macroporous carbon blocks, regardless of controllability, production cost or environmental protection.
  • Tian's research on the preparation and characterization of the foaming method and template method of carbon foam discloses a physical foaming method using mesophase pitch, polyacrylonitrile, polyvinyl chloride and some resins as precursors.
  • the precursor is placed in a mold to form a molded product, and then the molded product is placed in an autoclave, heated under an inert atmosphere and a high pressure to melt the asphalt, and an inert gas is continuously introduced, and then slowly vented, thereby obtaining A porous asphalt foam is finally pre-oxidized and carbonized to obtain a carbon foam.
  • the precursor is prepared by using asphalt as a main material to prepare a molded product, and it is required to press-form at a melting temperature of the asphalt, and does not involve a hot pressing process of pure polyacrylonitrile. Since the softening temperature and the decomposition temperature of the polyacrylonitrile are very close, when heated to above 220 ° C, softening and simultaneous decomposition are started, and the melting point is 317 ° C. Therefore, in order to ensure that the polyacrylonitrile does not decompose, its hot pressing temperature cannot exceed its decomposition temperature. Therefore, a molded article of polyacrylonitrile cannot be produced by this method.
  • the polyacrylonitrile-based three-dimensional macroporous carbon block was prepared and the influence of dimethyl sulfone content on the shape and size of the pore was studied.
  • the polyacrylonitrile foam has a honeycomb structure or a channel-like pore structure depending on the content of dimethyl sulfone, but the cellular structure of the polyacrylonitrile foam has a serious collapse of the pore structure after carbonization.
  • the pore structure obtained by the heat to phase separation method mainly depends on the morphology of the diluted phase, and the morphology of the diluted phase can usually be adjusted only by selecting different diluents and changing the ratio of the solution, therefore, the heat to phase separation method The controllability of the pore structure is low.
  • polyacrylonitrile since polyacrylonitrile is only soluble in a small amount of organic solvent and has low solubility, it has fewer alternative diluents and a narrower dilution window than other polymers. Therefore, it is also difficult to achieve a controllable preparation of a polyacrylonitrile-based three-dimensional macroporous carbon block by heat to phase separation.
  • the present invention provides a method for preparing a polyacrylonitrile-based three-dimensional macroporous carbon block, which aims to solve the problem of hot press forming of polyacrylonitrile below the decomposition temperature in the prior art and a polyacrylonitrile-based three-dimensional macroporous hole.
  • the carbon block preparation process is complicated, the processing cost is high, the environmental protection is poor, and the pore structure is uncontrollable.
  • One of the objects of the present invention is to provide a method for preparing a polyacrylonitrile-based three-dimensional macroporous carbon block, comprising:
  • the sheet is cut, hot pressed into a block sample, and punched into small pieces as a foaming precursor;
  • the foaming precursor described above is physically foamed, pre-oxidized, and carbonized to obtain a polyacrylonitrile-based three-dimensional macroporous carbon block.
  • Chinese patent CN 103985881A discloses a preparation method and application of a three-dimensional porous carbon foam stent electrode, but the present application finds in the subsequent research that the technology has the following problems: First, the precursor sheet prepared by using the watch glass is subsequently foamed. The mechanical strength is poor during the molding process, and it is easy to bend and deform. Second, the solvent remaining in the flakes is volatilized during the subsequent foaming process, so that the shape of the pores is irregular, the porosity is low, and the pore walls are thick. Third, in the process of intermittent foaming of supercritical carbon dioxide, the foaming temperature is too high and the saturation time is too long. There may be solvent small molecules escaping and mutual aggregation, resulting in self-foaming of the solvent in the polyacrylonitrile foaming process. phenomenon.
  • the present application attempts to use a hot pressing process to form a precursor sheet into a block shape to improve the overall strength and redistribute the solvent (to ensure the uniformity of the bulk precursor), but due to the softening temperature of the polyacrylonitrile (220 High °C ⁇ 230 ° C), partial decomposition of polyacrylonitrile, affecting the subsequent foaming properties.
  • this application systematically studied the hot pressing process of polyacrylonitrile: it was found that hot pressing at 140 °C-160 °C can ensure that polyacrylonitrile does not decompose and has the best foaming in the subsequent foaming process. performance.
  • the present application explores the residual solvent content in the polyacrylonitrile precursor and finds: residual solvent and polyacrylonitrile
  • the mass ratio should be controlled in the range of 35 to 55 wt%.
  • the solvent in the mold has good fluidity, and can be hot pressed into a bulk precursor which is consistent with the shape of the mold cavity and uniformly and not layered.
  • the hot pressing conditions preferred in the present application are: hot pressing at 140 to 160 ° C and 10 to 20 MPa for 10 to 20 minutes.
  • the present invention foams the precursor at a lower saturation temperature of 100 to 150 ° C, dimethyl sulfoxide does not rapidly evaporate, and plasticizes the foaming of the polyacrylonitrile.
  • a uniform cell structure can be obtained, and the saturation pressure regulation interval is large, and the cell structure can be regulated.
  • the organic solvent is at least one of dimethyl sulfoxide, dimethylformamide or dimethylacetamide.
  • the polyacrylonitrile is a polyacrylonitrile powder or a polyacrylonitrile fiber.
  • the material is foamed using a supercritical carbon dioxide as a physical blowing agent to prepare a microporous polyacrylonitrile foaming material in an autoclave.
  • the specific step of foaming the material is: first heating the autoclave to a foaming temperature of 100 to 150 ° C, then placing the precursor in a kettle, introducing supercritical carbon dioxide into the kettle and pressurizing to saturation.
  • the pressure is 10.34 ⁇ 31.09Mpa, and after 1 to 3 hours of saturation, the pressure is quickly released to obtain a polyacrylonitrile foam.
  • the pre-oxidation is carried out under conditions of sufficient air.
  • the carbonization is divided into two stages of low temperature carbonization and high temperature carbonization.
  • the carbonization is carried out under inert gas conditions.
  • Another object of the present invention is to provide a polyacrylonitrile-based three-dimensional macroporous carbon block prepared by any of the above methods.
  • the third object of the present invention is to provide any of the above polyacrylonitrile-based three-dimensional macroporous carbon blocks in preparing fuel cell electrode materials, electric double layer capacitors, lithium ion battery electrode materials, catalyst carriers, electromagnetic shielding materials, water purification filtration or Applications in sound absorbing materials.
  • the present invention mainly utilizes uniform mixing of supercritical carbon dioxide and precursor at a near molecular level to prepare a honeycomb polyacrylonitrile foam having a uniform cell structure.
  • the tunable range of cell density, average pore diameter and porosity of the foam was as high as 1.157 ⁇ 10 8 to 5.928 ⁇ 10 10 cells/cm 3 , 5.34 to 51.43 ⁇ m and 74.8% to 93.8%, respectively.
  • a polyacrylonitrile-based three-dimensional macroporous carbon block is obtained.
  • the cell structure of the polyacrylonitrile foam does not change, the pore walls do not collapse, and after the same heat treatment, different cells are formed.
  • the degree of contraction is also very close.
  • the polyacrylonitrile-based three-dimensional macroporous carbon block prepared by the invention has low density and good electrical conductivity, and the pore structure is uniform and controllable, the preparation method is simple, the process condition is mild, the environment is friendly, and the cost is low, which is beneficial to realize Scale production has a good application prospect.
  • the preparation method has the advantages of simple preparation method, high hole-making efficiency, strong practicability and easy promotion.
  • FIG. 1 is a block diagram of a process flow of a preparation process of the present invention.
  • Example 2 is a scanning electron micrograph of a polyacrylonitrile-based three-dimensional macroporous carbon block prepared in Example 1 of the present invention.
  • Example 3 is a scanning electron micrograph of a polyacrylonitrile-based three-dimensional macroporous carbon block prepared in Example 2 of the present invention.
  • Example 4 is a scanning electron micrograph of a polyacrylonitrile-based three-dimensional macroporous carbon block prepared in Example 3 of the present invention.
  • the invention discloses a preparation method of a polyacrylonitrile-based three-dimensional macroporous carbon block, the process comprising the steps of preparing a foaming precursor, preparing a polyacrylonitrile foam and preparing a polyacrylonitrile-based three-dimensional large-pore carbon block.
  • the sheet is obtained and cut into a sheet having the same size as that of the hot-pressed mold cavity, and 10 to 16 sheets are taken, and a block sample is obtained after being heated at 140 to 160 ° C and 10 to 20 Mpa for 10 to 20 minutes, and finally punched into small pieces.
  • the block acts as a foaming precursor.
  • the low temperature carbonization temperature is 300 to 600 ° C
  • the heating rate is 4 to 20 ° C / min
  • the holding time is 0.5 to 4 h.
  • the high temperature carbonization temperature is 800 to 1000 ° C
  • the heating rate is 4 to 20 ° C / min
  • the holding time is 0.5 to 4 h.
  • the method for preparing a foaming precursor wherein the organic solvent is one of dimethyl sulfoxide, dimethylformamide or dimethylacetamide, or a plurality of solvents obtained by mixing in different ratios. .
  • the method for preparing a foamed precursor wherein the polyacrylonitrile is a polyacrylonitrile powder or a polyacrylonitrile fiber.
  • the method for preparing a foamed precursor wherein the stirring is mechanical stirring or magnetic stirring.
  • the method for preparing a polyacrylonitrile-based three-dimensional macroporous carbon block wherein the inert atmosphere is nitrogen or argon.
  • the preparation of the polyacrylonitrile foam according to the present invention adopts a batch foaming method, the principle is: first, the polymer is placed in a certain atmosphere, and the gas is saturated in the polymer by controlling the temperature and pressure, and then the pressure is rapidly lowered. Or heating up, the gas nucleates and grows in the polymer due to supersaturation, forming a polymer foaming material.
  • the principle is simple, the cost is low, the floor space is small, the cell structure is uniform, the process parameters are easy to control, and the scale production can be realized.
  • the preparation method of the polyacrylonitrile foam used in the invention adopts supercritical carbon dioxide as a physical foaming agent, and is characterized in that it has the advantages of being environmentally friendly, non-toxic and inexpensive, and has a large diffusion coefficient and viscosity in a supercritical state. Small, good permeability, can achieve uniform mixing with the polymer at the near molecular level, high density of gas core during the foaming process, can achieve the purpose of controlling the cell structure.
  • the process for preparing a polyacrylonitrile-based three-dimensional macroporous carbon block includes three steps of preparing a foaming precursor, preparing a polyacrylonitrile foam, and preparing a polyacrylonitrile-based three-dimensional large-pore carbon block:
  • the low temperature carbonization temperature is 500 ° C, the heating rate is 5 ° C / min, and the holding time is 2 h.
  • the high temperature carbonization temperature is 800 ° C, the heating rate is 5 ° C / min, and the holding time is 2 h. After carbonization, a polyacrylonitrile-based three-dimensional macroporous carbon block can be obtained.
  • the average pore diameter of the preoxidized foam of this example was reduced by about 13.6% compared to the average pore diameter of the PAN foam, and the average pore diameter of the carbonized foam was reduced by about 18.9% compared with the average pore diameter of the PAN foam.
  • the density of the macroporous carbon block after carbonization at 800 ° C was 0.156 g/cm 3 , and the electrical conductivity at room temperature was 1.08 ⁇ 0.14 S/cm.
  • the process for preparing a polyacrylonitrile-based three-dimensional macroporous carbon block includes three steps of preparing a foaming precursor, preparing a polyacrylonitrile foam, and preparing a polyacrylonitrile-based three-dimensional large-pore carbon block:
  • the low temperature carbonization temperature is 500 ° C, the heating rate is 5 ° C / min, and the holding time is 2 h.
  • the high temperature carbonization temperature is 800 ° C, the heating rate is 5 ° C / min, and the holding time is 2 h. After carbonization, a polyacrylonitrile-based three-dimensional macroporous carbon block can be obtained.
  • the process for preparing a polyacrylonitrile-based three-dimensional macroporous carbon block includes three steps of preparing a foaming precursor, preparing a polyacrylonitrile foam, and preparing a polyacrylonitrile-based three-dimensional large-pore carbon block:
  • the low temperature carbonization temperature is 500 ° C, the heating rate is 5 ° C / min, and the holding time is 2 h.
  • the high temperature carbonization temperature is 900 ° C, the heating rate is 5 ° C / min, and the holding time is 2 h. After carbonization, a polyacrylonitrile-based three-dimensional macroporous carbon block can be obtained.
  • the polyacrylonitrile-based three-dimensional macroporous carbon block of the invention has simple preparation method, mild process condition, environmental friendliness and low cost, and is mainly prepared by uniformly mixing supercritical carbon dioxide and precursor at a near molecular level.
  • a honeycomb polyacrylonitrile foam having a uniform cell structure.
  • the tunable range of cell density, average pore diameter and porosity of the foam was as high as 1.157 ⁇ 10 8 to 5.928 ⁇ 10 10 cells/cm 3 , 5.34 to 51.43 ⁇ m and 74.8% to 93.8%, respectively.
  • the macroporous carbon block is obtained.
  • the cell structure of the polyacrylonitrile foam does not change, the pore walls do not collapse, and after the same heat treatment, the shrinkage degree of the different cells is also very high. Close. Since the polyacrylonitrile-based three-dimensional macroporous carbon block prepared by the invention has low density and good electrical conductivity, and the pore structure is uniform and controllable, it is particularly suitable for large-scale production of high quality large pore carbon blocks. Therefore, the invention effectively solves the problems faced by the prior art polyacrylonitrile-based three-dimensional large-pores carbon block preparation method, and has high industrial utilization value and good application prospect.

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Abstract

一种聚丙烯腈基三维大孔碳块制备方法，其工艺路线是，先将聚丙烯腈完全溶解于有机溶剂中，然后经烘干、裁剪、热压和冲裁后得到发泡前驱体，再通过超临界二氧化碳间歇式发泡法制备泡孔结构可控的聚丙烯腈泡沫，最后经预氧化和碳化处理后得到聚丙烯腈基三维大孔碳块。

Description

一种聚丙烯腈基三维大孔碳块的制备方法 技术领域
本发明涉及一种多孔碳的制备方法，尤其涉及一种聚丙烯腈基三维大孔碳块的制备方法。
背景技术
多孔碳材料具有丰富的孔道结构、大比表面、低密度、优良的化学稳定性和导电性以及较低的生产成本等优点，被广泛应用于燃料电池电极材料、双电层电容器和锂离子电池电极材料、催化剂载体、电磁屏蔽材料、水源净化过滤、吸音材料等领域。孔的结构是影响多孔碳材料应用的关键因素。其中，大孔的可控制备是获得三维整体结构碳块的关键。然而，目前制备的大孔碳材料大都存在孔尺寸、孔径分布及空间排列极其不均匀，或仅表面存在一定的有序孔结构等问题，很难获得三维整体大孔结构材料，目前制备的大孔碳材料孔结构混乱和加工成本高的问题限制了三维大孔碳块的进一步研究和应用。
在众多的碳材料前驱体中，聚丙烯腈分子结构简单、碳化程度可控、碳收率高、力学性能优良、原料成本较低，占目前碳纤维市场总量的90％以上，是一种优秀的碳前驱体。但其软化温度和分解温度十分接近，且熔点高，粘度大，现有加工方法十分局限。
迄今为止，为获得结构可控的聚丙烯腈基三维大孔碳块，研究者们提出了多种不同的方法。这些方法分为模板法和无模板法两大类。模板法根据模板牺牲相的不同，又分为硬模板法和软模板法。无模板法主要包括热至相分离法和间歇式发泡法。
硬模板法能较好地复制模板的结构，但工艺路线繁琐，加工成本高且不环保，因而极大地限制了该方法的规模化应用。同时，由于聚丙烯腈粘度高，在模板中的分散性不好，难以填满块状材料的整个体积空间，尤其是模板之间的狭窄缝隙处，导致获得的多孔碳材料存在许多缺陷。因此，硬模板法难以适用于聚丙烯腈块状材料的制备。软模板法相对硬模板法工艺简单，但孔结构的可控性明显低于硬模板法。同时，粘度高的聚丙烯腈较难与牺牲相合成嵌段共聚物，且聚丙烯腈与聚合物的相分离机制目前也仍不明确。因此，无论从可控程度、生产成本还是环保角度考虑，硬模板法和软模板法均不是制备聚丙烯腈基三维大孔碳块的有效方法。
田辞关于《碳泡沫的发泡法和模板法制备及其表征》的研究公开了采用中间相沥青、聚丙烯腈、聚氯乙烯以及某些树脂为前驱体的物理发泡法。将前驱体放入模具中做成模压制品，然后将此模压制品放入高压釜中，在惰性气氛与高压下加热使沥青融化，同时不断地通入惰 性气体，然后缓慢地放空，就得到了一个多孔的沥青泡沫，最后经预氧化和碳化处理得到碳泡沫。但其前驱体是以沥青为主体材料制备模压制品的，而且需要在沥青的熔融温度以上压制成型，也未涉及纯聚丙烯腈的热压工艺。由于聚丙烯腈的软化温度和分解温度十分接近，当加热至220℃以上时，即开始软化并同时分解，其熔点为317℃。因此，为保障聚丙烯腈不发生分解，其热压温度不能超过其分解温度。所以，无法通过该方法制备聚丙烯腈的模压制品。
吴青芸、徐志康等曾于2013年在《Polymer》上发表了一篇名为“Crystallizable diluent-templated polyacrylonitrile foams for macroporous carbon monoliths”的论文，先采用聚丙烯腈为溶质，二甲基砜为稀释相制备均相溶液，然后降温冷却使体系发生相分离，再用去离子水把二甲基砜萃取出来，接着用乙醇和己烷置换出去离子水并烘干制备聚丙烯腈泡沫，最后经预氧化和碳化处理制备了聚丙烯腈基三维大孔碳块，并研究了二甲基砜含量对孔形状和尺寸的影响规律。聚丙烯腈泡沫随二甲基砜含量不同，具有蜂窝状或通道状的孔结构，但蜂窝状结构的聚丙烯腈泡沫经碳化后孔结构塌陷严重。热至相分离方法所获得的孔结构主要取决于稀释相的形貌，而稀释相的形貌通常仅能通过选择不同的稀释剂和改变溶液的配比来调整，因此，热至相分离法对孔结构的可控性较低。同时，由于聚丙烯腈仅溶于少数有机溶剂且溶解度小，相对于其它聚合物，其可选择的稀释剂种类更少，且稀释窗口更窄。所以，热至相分离法同样难以实现聚丙烯腈基三维大孔碳块的可控制备。
因此，如何解决聚丙烯腈在分解温度以下的热压成型问题以及聚丙烯腈基三维大孔碳块制备工艺复杂、加工成本高、环保性差和孔结构不可控的问题，以实现聚丙烯腈基三维大孔碳块的规模化生产，成为本领域亟待解决的一个重要技术问题。
发明内容
为了克服上述不足，本发明提供一种聚丙烯腈基三维大孔碳块的制备方法，旨在解决现有技术中聚丙烯腈在分解温度以下的热压成型问题以及聚丙烯腈基三维大孔碳块制备工艺复杂、加工成本高、环保性差以及孔结构不可控的问题。
为了实现上述目的，本发明采用如下技术方案：
本发明的目的之一是提供一种聚丙烯腈基三维大孔碳块的制备方法，包括：
将聚丙烯腈溶解在有机溶剂中，蒸除部分溶剂，得薄片；
将上述薄片裁剪后、热压成块状样品，冲裁成小块作为发泡前驱体；
将上述的发泡前驱体经物理发泡、预氧化、碳化，得聚丙烯腈基三维大孔碳块。
中国专利CN 103985881A公开了一种三维孔状碳泡沫支架电极的制备方法及应用，但本申请在后续研究中发现：该技术存在以下问题：一是采用表面皿制备的前驱体薄片在后续发泡成型过程中机械强度差、易弯曲变形。二是薄片中保留的溶剂在后续发泡成型过程中易挥发，使孔的形状不规则、孔隙率较低，孔壁较厚。三是在超临界二氧化碳间歇式发泡的过程中，发泡温度过高、饱和时间过长，可能存在溶剂小分子逸出和相互聚集，导致溶剂在聚丙烯腈发泡过程中产生了自发泡现象。
为此，本申请尝试采用热压工艺将前驱体薄片制成块状，以提高整体强度，并对溶剂进行重新分配(保证块状前驱体的均一性)，但由于聚丙烯腈软化温度(220℃～230℃)较高，使聚丙烯腈产生部分分解，影响了后续的发泡性能。为此，本申请对聚丙烯腈的热压工艺进行了系统研究：发现在140℃-160℃下热压可保证聚丙烯腈不分解，且在后续发泡成型过程中具有最优的发泡性能。同时，为了实现各聚丙烯腈薄片能够在140℃-160℃下结合成块状前驱体，本申请对聚丙烯腈前驱体中的剩余溶剂含量进行了摸索，发现：剩余溶剂与聚丙烯腈的质量比应控制在35～55wt％.范围，此时，模具中的溶剂具有较好的流动性，可热压成与模具型腔形状一致且均匀不分层的块状前驱体。
因此，本申请优选的所述热压的条件为：于140～160℃、10～20Mpa下热压10～20min。
另一方面，本发明在较低的饱和温度为100～150℃下对前驱体进行发泡，二甲基亚砜不会迅速挥发，且对聚丙烯腈的发泡起到增塑作用，因此，可获得均匀的泡孔结构，且饱和压力调控区间大，泡孔结构可调控。
优选的，所述有机溶剂为二甲基亚砜、二甲基甲酰胺或二甲基乙酰胺中的至少一种。
优选的，所述聚丙烯腈为聚丙烯腈粉末或聚丙烯腈纤维。
优选的，所述物料发泡采用超临界二氧化碳作为物理发泡剂在高压釜中制备微孔聚丙烯腈发泡材料。
更优选的，所述物料发泡的具体步骤为：先将高压釜加热至发泡温度100～150℃，然后将前驱体置于釜中，往釜内通入超临界二氧化碳并加压至饱和压力10.34～31.09Mpa，饱和1～3h后，迅速卸压，获得聚丙烯腈泡沫。
优选的，所述预氧化在空气充足的条件下进行。
优选的，所述碳化分为低温碳化和高温碳化两个阶段。
优选的，所述碳化在惰性气体条件下进行。
本发明的目的之二是提供任一上述的方法制备的聚丙烯腈基三维大孔碳块。
本发明的目的之三是提供任一上述的聚丙烯腈基三维大孔碳块在制备燃料电池电极材料、双电层电容器、锂离子电池电极材料、催化剂载体、电磁屏蔽材料、水源净化过滤或吸音材料中的应用。
本发明的有益效果
(1)本发明主要利用超临界二氧化碳与前驱体在近乎分子水平上的均匀混合，制备了泡孔结构均匀的蜂窝状聚丙烯腈泡沫。泡沫的泡孔密度、平均孔径和孔隙率的可调控范围分别高达1.157×10 8～5.928×10 10cells/cm 3、5.34～51.43μm和74.8％～93.8％。进一步通过预氧化和碳化处理，获得了聚丙烯腈基三维大孔碳块，在热解过程中聚丙烯腈泡沫的泡孔结构不改变，孔壁不坍塌，且经相同热处理后，不同泡孔的收缩程度也十分接近。由于本发明制备的聚丙烯腈基三维大孔碳块具有较低的密度和良好的导电性，且孔结构均匀、可控，制备方法简单、工艺条件温和、环境友好、成本低，有利于实现规模生产，具有良好的应用前景。
(2)本发明制备方法简单、制孔效率高、实用性强，易于推广。
附图说明
构成本申请的一部分的说明书附图用来提供对本申请的进一步理解，本申请的示意性实施例及其说明用于解释本申请，并不构成对本申请的不当限定。
图1为本发明的制备过程工艺流程框图。
图2为本发明实施例1制备的聚丙烯腈基三维大孔碳块的扫描电镜图。
图3为本发明实施例2制备的聚丙烯腈基三维大孔碳块的扫描电镜图。
图4为本发明实施例3制备的聚丙烯腈基三维大孔碳块的扫描电镜图。
具体实施方式
应该指出，以下详细说明都是例示性的，旨在对本申请提供进一步的说明。除非另有指明，本文使用的所有技术和科学术语具有与本申请所属技术领域的普通技术人员通常理解的相同含义。
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本申请的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。
下面结合具体的实施例，对本发明做进一步的说明。
一种聚丙烯腈基三维大孔碳块的制备方法，其工艺过程包括制备发泡前驱体、制备聚丙 烯腈泡沫和制备聚丙烯腈基三维大孔碳块共三个步骤。
具体步骤如下：
(1)制备发泡前驱体：在烧瓶中加入有机溶剂和8～12wt％.聚丙烯腈后，于55～75℃下进行搅拌8～24h至聚丙烯腈完全溶解，然后将溶液倒入培养皿中，在60℃下烘干10～16h，部分溶剂蒸干后，剩余溶剂与聚丙烯腈的质量比应控制在35～55wt％.范围内。
得到薄片并裁剪成与热压模具型腔大小相同的薄片，取10～16片，经140～160℃、10～20Mpa热压10～20分钟后获得块状样品，最后将其冲裁成小块作为发泡前驱体。
(2)制备聚丙烯腈泡沫：采用超临界二氧化碳作为物理发泡剂，通过间歇式发泡装置(由高压釜、ISCO高压柱塞泵和PID基温度控制系统组成)发泡。先将高压釜加热至发泡温度100～150℃，然后将前驱体置于釜中，往釜内通入超临界二氧化碳并加压至饱和压力10.34～31.09Mpa，饱和1～3h后，迅速卸压，获得聚丙烯腈泡沫。
(3)制备聚丙烯腈基三维大孔碳块：聚丙烯腈碳化需要经历预氧化和碳化两个阶段。为保证聚丙烯腈泡沫进行充分氧化，首先将泡沫切成厚度约1～5mm的圆片，然后在空气充足的条件下，在鼓风干燥箱中以2～5℃/min的升温速率，升至200～300℃并保温1～5h，进行预氧化处理。碳化过程分低温碳化和高温碳化两个阶段，分别在惰性气氛保护下于管式炉中进行。低温碳化温度为300～600℃，升温速率为4～20℃/min，保温时间为0.5～4h。高温碳化温度为800～1000℃，升温速率为4～20℃/min，保温时间为0.5～4h。碳化后即可获得聚丙烯腈基三维大孔碳块。
所述的制备发泡前驱体的方法，其中，所述有机溶剂为二甲基亚砜、二甲基甲酰胺或二甲基乙酰胺中的一种，或多种经不同比例混合得到的溶剂。
所述的制备发泡前驱体的方法，其中，所述聚丙烯腈为聚丙烯腈粉末或聚丙烯腈纤维。
所述的制备发泡前驱体的方法，其中，所述搅拌为机械搅拌或磁力搅拌。
所述的制备聚丙烯腈基三维大孔碳块的方法，其中，所述惰性气氛为氮气或氩气。
本发明涉及的制备聚丙烯腈泡沫采用的是间歇式发泡法，其原理是：先将聚合物置于一定的气氛中，通过控制温度和压力，使气体在聚合物中饱和，然后快速降压或升温，气体因过饱和在聚合物内形核、长大，形成聚合物发泡材料。其原理简单、成本低、占地面积小、泡孔结构均匀、工艺参数易于控制、可实现规模生产。
本发明涉及的聚丙烯腈泡沫制备方法采用的是超临界二氧化碳作为物理发泡剂，其特点是：具有环境友好、无毒和价格便宜等优点，其在超临界状态下的扩散系数大、粘度小、渗 透性好，可以与聚合物达到近乎分子水平上的均匀混合，在发泡过程中气核密度高，可以达到控制泡孔结构的目的。
实施例1：
本实施例涉及的聚丙烯腈基三维大孔碳块制备方法的工艺过程包括制备发泡前驱体、制备聚丙烯腈泡沫和制备聚丙烯腈基三维大孔碳块共三个步骤：
(1)制备发泡前驱体：在烧瓶中加入二甲基亚砜和10wt％.聚丙烯腈粉末后，于60℃下进行机械搅拌10h至聚丙烯腈完全溶解，然后将溶液倒入培养皿中，在60℃下烘干12h(此时，剩余溶剂与聚丙烯腈的质量为42wt％左右)，得到薄片并裁剪成与热压模具型腔大小相同的薄片，取12片，经160℃、10Mpa热压10分钟后获得块状样品，最后将其冲裁成小块作为发泡前驱体。
(2)制备聚丙烯腈泡沫：采用超临界二氧化碳作为物理发泡剂，通过间歇式发泡装置(由高压釜、ISCO高压柱塞泵和PID基温度控制系统组成)发泡。先将高压釜加热至发泡温度100℃，然后将前驱体置于釜中，往釜内通入超临界二氧化碳并加压至饱和压力24.13Mpa，饱和1.5h后，迅速卸压，获得聚丙烯腈泡沫。
(3)制备聚丙烯腈基三维大孔碳块：聚丙烯腈碳化需要经历预氧化和碳化两个阶段。为保证聚丙烯腈泡沫进行充分氧化，首先将泡沫切成厚度约2mm的圆片，然后在空气充足的条件下，在鼓风干燥箱中以5℃/min的升温速率，升至250℃并保温5h，进行预氧化处理。碳化过程分低温碳化和高温碳化两个阶段，分别在氩气保护下于管式炉中进行。低温碳化温度为500℃，升温速率为5℃/min，保温时间为2h。高温碳化温度为800℃，升温速率为5℃/min，保温时间为2h。碳化后即可获得聚丙烯腈基三维大孔碳块。
本实施例预氧化泡沫的平均孔径比PAN泡沫的平均孔径缩小约13.6％，碳化泡沫的平均孔径比PAN泡沫的平均孔径缩小约18.9％。经800℃碳化后的大孔碳块的密度为0.156g/cm 3，室温下的电导率为1.08±0.14S/cm。
实施例2：
本实施例涉及的聚丙烯腈基三维大孔碳块制备方法的工艺过程包括制备发泡前驱体、制备聚丙烯腈泡沫和制备聚丙烯腈基三维大孔碳块共三个步骤：
(1)制备发泡前驱体：在烧瓶中加入二甲基亚砜和10wt％.聚丙烯腈粉末后，于60℃下进行机械搅拌10h至聚丙烯腈完全溶解，然后将溶液倒入培养皿中，在60℃下烘干12h(此时，剩余溶剂与聚丙烯腈的质量为42wt％左右)，得到薄片并裁剪成与热压模具型腔大小相同 的薄片，取12片，经160℃、10Mpa热压10分钟后获得块状样品，最后将其冲裁成小块作为发泡前驱体。
(2)制备聚丙烯腈泡沫：采用超临界二氧化碳作为物理发泡剂，通过间歇式发泡装置(由高压釜、ISCO高压柱塞泵和PID基温度控制系统组成)发泡。先将高压釜加热至发泡温度130℃，然后将前驱体置于釜中，往釜内通入超临界二氧化碳并加压至饱和压力24.13Mpa，饱和1.5h后，迅速卸压，获得聚丙烯腈泡沫。
(3)制备聚丙烯腈基三维大孔碳块：聚丙烯腈碳化需要经历预氧化和碳化两个阶段。为保证聚丙烯腈泡沫进行充分氧化，首先将泡沫切成厚度约2mm的圆片，然后在空气充足的条件下，在鼓风干燥箱中以5℃/min的升温速率，升至250℃并保温5h，进行预氧化处理。碳化过程分低温碳化和高温碳化两个阶段，分别在氩气保护下于管式炉中进行。低温碳化温度为500℃，升温速率为5℃/min，保温时间为2h。高温碳化温度为800℃，升温速率为5℃/min，保温时间为2h。碳化后即可获得聚丙烯腈基三维大孔碳块。
实施例3：
本实施例涉及的聚丙烯腈基三维大孔碳块制备方法的工艺过程包括制备发泡前驱体、制备聚丙烯腈泡沫和制备聚丙烯腈基三维大孔碳块共三个步骤：
(1)制备发泡前驱体：在烧瓶中加入二甲基亚砜和10wt％.聚丙烯腈粉末后，于60℃下进行机械搅拌10h至聚丙烯腈完全溶解，然后将溶液倒入培养皿中，在60℃下烘干12h，(此时，剩余溶剂与聚丙烯腈的质量为42wt％左右)，得到薄片并裁剪成与热压模具型腔大小相同的薄片，取12片，经160℃、10Mpa热压10分钟后获得块状样品，最后将其冲裁成小块作为发泡前驱体。
(2)制备聚丙烯腈泡沫：采用超临界二氧化碳作为物理发泡剂，通过间歇式发泡装置(由高压釜、ISCO高压柱塞泵和PID基温度控制系统组成)发泡。先将高压釜加热至发泡温度110℃，然后将前驱体置于釜中，往釜内通入超临界二氧化碳并加压至饱和压力31.09Mpa，饱和1.5h后，迅速卸压，获得聚丙烯腈泡沫。
(3)制备聚丙烯腈基三维大孔碳块：聚丙烯腈碳化需要经历预氧化和碳化两个阶段。为保证聚丙烯腈泡沫进行充分氧化，首先将泡沫切成厚度约2mm的圆片，然后在空气充足的条件下，在鼓风干燥箱中以5℃/min的升温速率，升至250℃并保温5h，进行预氧化处理。碳化过程分低温碳化和高温碳化两个阶段，分别在氩气保护下于管式炉中进行。低温碳化温度为500℃，升温速率为5℃/min，保温时间为2h。高温碳化温度为900℃，升温速率为5℃/min， 保温时间为2h。碳化后即可获得聚丙烯腈基三维大孔碳块。
综上所述，本发明的聚丙烯腈基三维大孔碳块的制备方法简单、工艺条件温和、环境友好、成本低，主要利用超临界二氧化碳与前驱体在近乎分子水平上的均匀混合，制备了泡孔结构均匀的蜂窝状聚丙烯腈泡沫。泡沫的泡孔密度、平均孔径和孔隙率的可调控范围分别高达1.157×10 8～5.928×10 10cells/cm 3、5.34～51.43μm和74.8％～93.8％。进一步通过预氧化和碳化处理，获得了大孔碳块，在热解过程中聚丙烯腈泡沫的泡孔结构不改变，孔壁不坍塌，且经相同热处理后，不同泡孔的收缩程度也十分接近。由于本发明制备的聚丙烯腈基三维大孔碳块具有较低的密度和良好的导电性，且孔结构均匀、可控，因此特别适合高质量大孔碳块的规模化生产。所以，本发明有效解决了现有技术中的聚丙烯腈基三维大孔碳块制备方法面临的问题，具有高度产业利用价值和良好的应用前景。
最后应该说明的是，以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述实施例所记载的技术方案进行修改，或者对其中部分进行等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。上述虽然结合附图对本发明的具体实施方式进行了描述，但并非对本发明保护范围的限制，所属领域技术人员应该明白，在本发明的技术方案的基础上，本领域技术人员不需要付出创造性劳动即可做出的各种修改或变形仍在本发明的保护范围以内。

Claims (10)

  1. 一种聚丙烯腈基三维大孔碳块的制备方法，其特征在于，包括：
    将聚丙烯腈溶解在有机溶剂中，蒸除部分溶剂，得薄片；
    将上述薄片裁剪后、热压成块状样品，冲裁成小块作为发泡前驱体；
    将上述的发泡前驱体经物理发泡、预氧化、碳化，得聚丙烯腈基三维大孔碳块。
  2. 如权利要求1所述的方法，其特征在于，所述热压的条件为：于140～160℃、10～20Mpa下热压10～20min。
  3. 如权利要求1所述的方法，其特征在于，所述有机溶剂为二甲基亚砜、二甲基甲酰胺或二甲基乙酰胺中的至少一种。
  4. 如权利要求1所述的方法，其特征在于，所述聚丙烯腈为聚丙烯腈粉末或聚丙烯腈纤维。
  5. 如权利要求1所述的方法，其特征在于，所述物料发泡采用超临界二氧化碳作为物理发泡剂在高压釜中制备微孔聚丙烯腈发泡材料。
  6. 如权利要求5所述的方法，其特征在于，所述物料发泡的具体步骤为：先将高压釜加热至发泡温度100～150℃，然后将前驱体置于釜中，往釜内通入超临界二氧化碳并加压至饱和压力10.34～31.09Mpa，饱和1～3h后，迅速卸压，获得聚丙烯腈泡沫。
  7. 如权利要求1所述的方法，其特征在于，所述预氧化在空气充足的条件下进行。
  8. 如权利要求1所述的方法，其特征在于，所述碳化在惰性气体条件下进行。
  9. 权利要求1-8任一项所述的方法制备的聚丙烯腈基三维大孔碳块。
  10. 权利要求9所述的聚丙烯腈基三维大孔碳块在制备燃料电池电极材料、双电层电容器、锂离子电池电极材料、催化剂载体、电磁屏蔽材料、水源净化过滤或吸音材料中的应用。
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