CN112408360B - Preparation method of hydrophobic porous carbon material - Google Patents
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Abstract
The invention relates to a preparation method of a hydrophobic porous carbon material, belonging to the field of carbon materials and being characterized in that firstly, raw materials of organic silicon, styrene, acrylic ester, an emulsifier and deionized water are pre-emulsified, then potassium persulfate is dripped to carry out emulsion polymerization to obtain silicon propyl benzene latex SSAL, then the SSAL and an oxalic acid solution are blended to obtain a resin matrix PSO, and the PSO is carbonized at high temperature to obtain the hydrophobic porous carbon material; the method takes oxalic acid as an activating agent and is matched with a specific adding step, so that the waste of energy and the generation of waste liquid are avoided while the pore-forming effect is ensured.
Description
Technical Field
The invention relates to the field of carbon materials, in particular to a preparation method of a hydrophobic porous carbon material.
Background
The porous carbon refers to a material with pores of different sizes among carbon carbons, and can be divided into three types according to the diameter of the pores, namely microporous carbon materials (< 2 nm), mesoporous carbon materials (2-50 nm) and macroporous carbon materials (> 50 nm). The porous carbon has the advantages of high specific surface area, excellent conductivity, adjustable physical and chemical properties, low price, easy obtainment and the like, and shows huge application prospects in the fields of energy storage and conversion, catalysis, adsorption and the like. The selection and preparation method of the porous carbon material precursor directly determine the performance and the application range of the porous carbon material precursor.
In the prior art, patent CN109437189A discloses a method for preparing and applying a resin-based spherical activated carbon, which is to use macroporous strong-acid cation exchange resin D001 as an activated carbon precursor, perform a series of pretreatments, then carbonize the activated carbon in a nitrogen atmosphere, and then activate a carbon sample with potassium hydroxide to finally obtain the resin-based spherical activated carbon with a regular shape and a high specific surface area. Patent CN104528720B discloses a method for preparing a hierarchical porous carbon material and a product thereof, which is to blend a carbon source and an activator, and obtain the hierarchical porous carbon material through two-step carbonization and post-treatment, wherein the activator is selected from one or more of ammonium oxalate, potassium hydrogen oxalate, potassium tetraoxalate, sodium oxalate, sodium hydrogen oxalate, sodium tetraoxalate, sodium bicarbonate or potassium bicarbonate, and finally obtain the hierarchical porous carbon material with abundant macropores.
The preparation mode and performance of the porous activated carbon are described in the prior art, but the hydrophobic performance of the activated carbon is not specified, so that the application of the porous activated carbon in some fields with higher requirements on the hydrophobic performance is limited. In addition, the existing polymer has rich structure, and the porous carbon material is prepared by carbonizing resins with different structures, and the pore-forming of the carbon material by selecting potassium hydroxide or potassium salt as an activating agent is a research hotspot of the existing porous carbon material. The commonly adopted process is to take the ready-made or modified resin as a matrix, carbonize the matrix to prepare the carbon material, and then activate the carbon material by an activating agent to finally obtain the porous carbon material. The activating agent used is mostly potassium hydroxide or potassium salt, because the potassium hydroxide or potassium salt can react with carbon to generate potassium carbonate, so that the excellent pore-forming effect is achieved. However, the use of such an activating agent for pore formation of the carbon material brings a series of problems to the subsequent material treatment, and due to the existence of potassium carbonate formed after pore formation, hydrochloric acid and a large amount of water are needed to remove potassium carbonate in the later period, which wastes energy and generates a large amount of waste liquid.
With the sustainable development of the country, a green, environment-friendly and economic society is created, and the selection of an environment-friendly activating agent for pore forming of a carbon source is one of the research hotspots of the current porous carbon material. At present, no data show that oxalic acid is used as an activating agent to activate resin to prepare the porous carbon material, because oxalic acid is easy to decompose at high temperature, and if the process in the prior art is adopted, the oxalic acid is completely decomposed when the resin is not completely carbonized, so that the excellent pore-forming effect cannot be achieved.
Disclosure of Invention
The invention aims to solve the technical problem of providing the preparation method of the hydrophobic porous carbon material which is environment-friendly, has good pore-forming effect and simultaneously endows the material with good hydrophobic property aiming at the defects of the prior art, so that the pore-forming effect is ensured, and the waste of energy and the generation of waste liquid are avoided.
The technical scheme for solving the technical problems is as follows: the preparation method of the hydrophobic porous carbon material is characterized by comprising the following steps of:
1) preparing raw materials of organic silicon, styrene, acrylate, an emulsifier and deionized water, pre-emulsifying in a four-neck flask, heating to 70-95 ℃ in a nitrogen atmosphere, slowly dropwise adding 0.1-1 part by weight of potassium persulfate to carry out emulsion polymerization, and keeping the temperature for a certain time, preferably 2-8 hours, so as to obtain silicon propyl benzene latex SSAL;
wherein the raw materials account for the following parts by weight: 1-5 parts of organic silicon, 20 parts of styrene, 5-10 parts of acrylate, 0.2-2 parts of emulsifier and 30-80 parts of deionized water;
2) dissolving oxalic acid OA in absolute ethyl alcohol to prepare an OA solution;
3) according to SSAL: OA = 1: 0.2-5, mixing the SSAL and the OA solution, stirring for a certain time until the mixture is uniform, preferably 8-36h, forming a new emulsion system, and carrying out forced air drying at 50-90 ℃ for 24-48 h to obtain a resin matrix PSO;
4) in an inert atmosphere, heating PSO in a tube furnace to 700-1000 ℃, then preserving heat for 1-4 h to obtain a porous carbon product, and grinding to obtain the hydrophobic porous carbon material.
Further, in the step 1), the silicone is a single silicone or a composite silicone containing a C = C double bond.
Further, in the step 1), the organosilicon is at least one of dimethoxymethylvinylsilane, dimethyldivinylsilane, vinyltrimethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane and 2,4, 6-trimethyl-2, 4, 6-trivinylcyclotrisilazane.
Further, in the step 1), the acrylate is at least one of ethyl acrylate, butyl acrylate and isooctyl acrylate.
Further, in the step 1), the emulsifier is at least one of lauryl glucoside, sodium dodecylbenzene sulfonate, sodium lauryl sulfate, polyoxyethylene octyl phenol ether-10 and tween-80.
Further, in the step 3), the stirring speed is controlled to be 500-1000 r/min.
Further, in the step 4), the inert gas is at least one of nitrogen or argon.
Further, in the step 4), the temperature rising speed of the PSO in the tube furnace is 10 ℃/min.
The invention has the beneficial effects that:
1. the invention creatively selects oxalic acid as an activating agent, changes the adding step of the activating agent, and particularly creatively applies the activating agent to emulsion to prepare resin compared with the prior art that resin is taken as an activating object, namely, oxalic acid is firstly mixed with silicone-acrylate emulsion, the oxalic acid is fully contacted with colloidal particles and is solidified into resin, then the resin is carbonized at high temperature, and in the high-temperature carbonization process, gas decomposed by the oxalic acid uniformly escapes from the resin to form a porous carbon material; through the improvement of the sequence of the process steps and the use of the activating agent oxalic acid, the two cooperate to achieve the good pore-forming effect, and meanwhile, no residue is generated due to the high-temperature decomposition of oxalic acid, so that the waste of energy and the generation of waste liquid in the subsequent material treatment are avoided, and the process has good environmental protection significance;
2. the activating agent oxalic acid is firstly mixed with the emulsion, instead of mixing the activating agent with resin or other carbon materials, so that the contact chance of each colloidal particle with oxalic acid can be increased, the activating efficiency is higher, the formation of a pore-forming effect is facilitated, and the prepared porous carbon has a high specific surface area and a compact pore structure;
3. organosilicon, styrene and acrylic ester are used as monomers in the emulsion to prepare the silicone-styrene-acrylic emulsion, and the silicone-styrene-acrylic emulsion is mixed with oxalic acid to prepare a resin matrix, so that the prepared porous carbon has the advantage of low moisture absorption rate, namely good hydrophobicity, the application range of the porous carbon is expanded, and the porous carbon is especially applied to some fields with high requirements on hydrophobic performance;
4. the preparation method has simple process, wide carbon source and potential for product industrialization.
Drawings
FIG. 1 is an SEM photograph of the porous carbon material prepared in example 1;
FIG. 2 is an SEM image of the porous carbon material prepared in example 2;
FIG. 3 is an SEM photograph of the porous carbon material prepared in example 3;
FIG. 4 is an SEM image of the porous carbon material prepared in example 4;
FIG. 5 is an SEM image of the porous carbon material prepared in example 5;
FIG. 6 is an SEM image of the porous carbon material prepared in example 6;
FIG. 7 is an SEM image of the porous carbon material prepared in example 7;
FIG. 8 is an SEM photograph of the porous carbon material prepared in example 8.
Detailed Description
In order to make the objects, schemes and product advantages of the present invention more concrete and clear, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the following examples are intended only to illustrate the present invention in detail, and are not intended to limit the scope of the present invention in any way.
The laboratory instruments and test equipment referred to in the following examples are, unless otherwise specified, laboratory conventional instrumentation; the experimental raw materials and reagents are purchased from conventional chemical reagents companies, if not specifically mentioned.
Example 1
The preparation method of the hydrophobic porous carbon material of the present example includes the following steps:
(1) pre-emulsifying 2g of dimethyldivinyl silane, 40g of styrene, 10g of ethyl acrylate, 0.2g of dodecyl glucoside, 0.2g of tween-80 and 60g of deionized water in a four-neck flask, heating to 85 ℃ under the atmosphere of nitrogen, slowly and dropwise adding 0.2g of potassium persulfate aqueous solution (5% w/w) for emulsion polymerization, and keeping the temperature for 2 hours to obtain silicon propyl benzene latex (SSAL);
(2) dissolving 8g of Oxalic Acid (OA) in 35mL of absolute ethanol to prepare an OA solution;
(3) mixing 40g of SSAL with all OA solution, stirring for 12h to form a new emulsion system, and carrying out forced air drying at 50 ℃ for 24h to obtain a resin matrix (PSO);
(4) under the inert atmosphere, the PSO is heated to 700 ℃ in a tube furnace at a speed of 10 ℃/min, then the temperature is kept for 1h to obtain a porous carbon product, and the porous carbon product is ground to obtain the hydrophobic porous carbon material.
Example 2
The preparation method of the hydrophobic porous carbon material of the present example includes the following steps:
(1) pre-emulsifying 3g of dimethyldivinyl silane, 40g of styrene, 10g of butyl acrylate, 0.8g of sodium dodecyl sulfate, 0.4g of polyoxyethylene octyl phenol ether-10 and 100g of deionized water in a four-neck flask, heating to 88 ℃ under the argon atmosphere, slowly dropwise adding 0.4g of potassium persulfate aqueous solution (5% w/w) for emulsion polymerization, and preserving heat for 4 hours to obtain silicon propyl benzene latex (SSAL);
(2) dissolving 10g of Oxalic Acid (OA) in 40mL of absolute ethanol to prepare an OA solution;
(3) mixing 20g of SSAL with all OA solution, stirring for 12h to form a new emulsion system, and carrying out forced air drying at 70 ℃ for 30h to obtain a resin matrix (PSO);
(4) under the inert atmosphere, the PSO is heated to 800 ℃ in a tube furnace at a speed of 10 ℃/min, and then the temperature is kept for 2h to obtain a porous carbon product, and the porous carbon product is ground to obtain the hydrophobic porous carbon material.
Example 3
The preparation method of the hydrophobic porous carbon material of the embodiment comprises the following steps:
(1) pre-emulsifying 4g of dimethyl divinyl silane, 40g of styrene, 10g of isooctyl acrylate, 0.8g of sodium dodecyl sulfate, 0.5g of polyoxyethylene octyl phenol ether-10 and 100g of deionized water in a four-neck flask, heating to 85 ℃ under the atmosphere of nitrogen, slowly dropwise adding 0.3g of potassium persulfate aqueous solution (5% w/w) for emulsion polymerization, and preserving heat for 4 hours to obtain silicon propyl benzene latex (SSAL);
(2) dissolving 20g of Oxalic Acid (OA) in 80mL of absolute ethanol to prepare an OA solution;
(3) mixing 20g of SSAL with all OA solution, stirring for 24h to form a new emulsion system, and carrying out forced air drying at 80 ℃ for 30h to obtain a resin matrix (PSO);
(4) under the inert atmosphere, the PSO is heated to 850 ℃ at a speed of 10 ℃/min in a tube furnace, then the temperature is kept for 2h to obtain a porous carbon product, and the porous carbon product is ground to obtain the hydrophobic porous carbon material.
Example 4
The preparation method of the hydrophobic porous carbon material of the present example includes the following steps:
(1) pre-emulsifying 4g of vinyltrimethoxysilane, 40g of styrene, 15g of butyl acrylate, 1g of dodecyl glucoside, 0.5g of polyoxyethylene octyl phenol ether-10 and 100g of deionized water in a four-neck flask, heating to 80 ℃ under the atmosphere of nitrogen, slowly dropwise adding 0.3g of potassium persulfate aqueous solution (5% w/w) for emulsion polymerization, and keeping the temperature for 4.5 hours to obtain silicon propyl benzene latex (SSAL);
(2) dissolving 40g Oxalic Acid (OA) in 150mL absolute ethyl alcohol to prepare an OA solution;
(3) mixing 20g of SSAL with all OA solution, stirring for 24h to form a new emulsion system, and carrying out forced air drying at 88 ℃ for 24h to obtain a resin matrix (PSO);
(4) under the inert atmosphere, the PSO is heated to 800 ℃ in a tube furnace at the speed of 10 ℃/min, then the temperature is kept for 1h, a porous carbon product is obtained, and the hydrophobic porous carbon material is obtained by grinding.
Example 5
The preparation method of the hydrophobic porous carbon material of the present example includes the following steps:
(1) pre-emulsifying 5g of vinyltrimethoxysilane, 40g of styrene, 15g of acrylate, 0.5g of dodecyl glucoside, 1.0g of sodium dodecyl sulfate, 0.7g of Tween-80 and 110g of deionized water in a four-neck flask, heating to 83 ℃ under the argon atmosphere, slowly and dropwise adding 1.0g of potassium persulfate aqueous solution (5% w/w) for emulsion polymerization, and keeping the temperature for 5 hours to obtain silicon propyl benzene latex (SSAL);
(2) dissolving 40g Oxalic Acid (OA) in 150mL absolute ethyl alcohol to prepare an OA solution;
(3) mixing 40g of SSAL with all OA solution, stirring for 24h to form a new emulsion system, and carrying out forced air drying at 60 ℃ for 36h to obtain a resin matrix (PSO);
(4) under the inert atmosphere, the PSO is heated to 850 ℃ at a speed of 10 ℃/min in a tube furnace, then the temperature is kept for 2h to obtain a porous carbon product, and the porous carbon product is ground to obtain the hydrophobic porous carbon material.
Example 6
The preparation method of the hydrophobic porous carbon material of the present example includes the following steps:
(1) pre-emulsifying 6.5g of dimethoxymethylvinylsilane, 40g of styrene, 10g of acrylate, 0.4g of sodium dodecyl benzene sulfonate, 0.4g of sodium dodecyl sulfate, 0.4g of polyoxyethylene octylphenol ether-10 and 100g of deionized water in a four-neck flask, heating to 80 ℃ under the atmosphere of nitrogen, slowly dropwise adding 0.3g of potassium persulfate aqueous solution (5% w/w) for emulsion polymerization, and preserving heat for 3 hours to obtain silicon propyl benzene latex (SSAL);
(2) dissolving 60g of Oxalic Acid (OA) in 180mL of absolute ethanol to prepare an OA solution;
(3) mixing 20g of SSAL with all OA solution, stirring for 24h to form a new emulsion system, and carrying out forced air drying at 80 ℃ for 24h to obtain a resin matrix (PSO);
(4) under the inert atmosphere, the PSO is heated to 850 ℃ at a speed of 10 ℃/min in a tube furnace, then the temperature is kept for 1h to obtain a porous carbon product, and the porous carbon product is ground to obtain the hydrophobic porous carbon material.
Example 7
The preparation method of the hydrophobic porous carbon material of the present example includes the following steps:
(1) pre-emulsifying 8g of dimethoxymethylvinylsilane, 40g of styrene, 5g of acrylate, 1g of sodium dodecyl sulfate, 0.4g of polyoxyethylene octylphenol ether-10 and 100g of deionized water in a four-neck flask, heating to 85 ℃ under the atmosphere of nitrogen, slowly dropwise adding 0.3g of potassium persulfate aqueous solution (5% w/w) for emulsion polymerization, and keeping the temperature for 4 hours to obtain silicon propyl benzene latex (SSAL);
(2) dissolving 60g of Oxalic Acid (OA) in 180mL of absolute ethanol to prepare an OA solution;
(3) mixing 20g of SSAL with all OA solution, stirring for 24h to form a new emulsion system, and carrying out forced air drying at 88 ℃ for 20h to obtain a resin matrix (PSO);
(4) under the inert atmosphere, the PSO is heated to 900 ℃ in a tube furnace at the speed of 10 ℃/min, and then the temperature is kept for 2h to obtain a porous carbon product, and the porous carbon product is ground to obtain the hydrophobic porous carbon material.
Example 8
The preparation method of the hydrophobic porous carbon material of the present example includes the following steps:
(1) pre-emulsifying 10g of dimethoxymethylvinylsilane, 40g of styrene, 20g of acrylate, 2.0g of sodium dodecyl sulfate, 1.0g of polyoxyethylene octylphenol ether-10, 1.0g of tween-80 and 160g of deionized water in a four-neck flask, heating to 95 ℃ under the atmosphere of nitrogen, slowly dropwise adding 2g of potassium persulfate aqueous solution (5% w/w) for emulsion polymerization, and keeping the temperature for 8 hours to obtain silicon propyl benzene latex (SSAL);
(2) dissolving 100g of Oxalic Acid (OA) in 300mL of absolute ethanol to prepare an OA solution;
(3) mixing 20g of SSAL with all OA solution, stirring for 24h to form a new emulsion system, and carrying out forced air drying at 88 ℃ for 48h to obtain a resin matrix (PSO);
(4) under the inert atmosphere, the temperature of PSO is increased to 950 ℃ at a speed of 10 ℃/min in a tube furnace, then the temperature is preserved for 3.5h to obtain a porous carbon product, and the porous carbon product is ground to obtain the hydrophobic porous carbon material.
Comparative example 1
The preparation method of the hydrophobic porous carbon material of this comparative example is the same as example 5, except that no organosilicon is added to the raw materials. The method comprises the following steps:
(1) pre-emulsifying 40g of styrene, 15g of acrylate, 0.5g of dodecyl glucoside, 1.0g of sodium dodecyl sulfate, 0.7g of tween-80 and 110g of deionized water in a four-neck flask, heating to 83 ℃ under the atmosphere of nitrogen, slowly dropwise adding 1.0g of potassium persulfate aqueous solution (5% w/w) for emulsion polymerization, and keeping the temperature for 5 hours to obtain silicon propyl benzene latex (SSAL);
(2) dissolving 40g Oxalic Acid (OA) in 150mL absolute ethyl alcohol to prepare an OA solution;
(3) mixing 40g of SSAL with all OA solution, stirring for 24h to form a new emulsion system, and carrying out forced air drying at 60 ℃ for 36h to obtain a resin matrix (PO);
(4) and under the inert atmosphere, raising the temperature of PO in a tubular furnace to 850 ℃ at a speed of 10 ℃/min, then preserving the heat for 2h to obtain a porous carbon product, and grinding to obtain the porous carbon material.
Comparative example 2
The preparation method of the hydrophobic porous carbon material of the present comparative example is the same as that of example 5, except that oxalic acid, which is an activator, is replaced by potassium oxalate, and the solvent, anhydrous ethanol, is replaced by deionized water. The method comprises the following steps:
(1) pre-emulsifying 5g of vinyltrimethoxysilane, 40g of styrene, 15g of acrylate, 0.5g of dodecyl glucoside, 1.0g of sodium dodecyl sulfate, 0.7g of Tween-80 and 110g of deionized water in a four-neck flask, heating to 83 ℃ under the atmosphere of nitrogen, slowly and dropwise adding 1.0g of potassium persulfate aqueous solution (5% w/w) for emulsion polymerization, and keeping the temperature for 5 hours to obtain silicon propyl benzene latex (SSAL);
(2) dissolving 40g of potassium oxalate in 150mL of deionized water to prepare a potassium oxalate solution;
(3) mixing 40g of SSAL with all potassium oxalate solution, stirring for 24h to form a new emulsion system, and carrying out forced air drying at 60 ℃ for 36h to obtain a resin matrix (PSOK);
(4) under the inert atmosphere, PSOK is heated to 850 ℃ in a tube furnace at the speed of 10 ℃/min, and then heat preservation is carried out for 2h to obtain a porous carbon product, and the porous carbon product is ground to obtain the hydrophobic porous carbon material.
Comparative example 3
The hydrophobic porous carbon material of this comparative example was prepared in the same manner as in example 5, except that oxalic acid, the activator, was replaced with potassium hydroxide, and the solvent, anhydrous ethanol, was replaced with deionized water. The method comprises the following steps:
(1) pre-emulsifying 5g of vinyltrimethoxysilane, 40g of styrene, 15g of acrylate, 0.5g of dodecyl glucoside, 1.0g of sodium dodecyl sulfate, 0.7g of Tween-80 and 110g of deionized water in a four-neck flask, heating to 83 ℃ under the atmosphere of nitrogen, slowly and dropwise adding 1.0g of potassium persulfate aqueous solution (5% w/w) for emulsion polymerization, and keeping the temperature for 5 hours to obtain silicon propyl benzene latex (SSAL);
(2) dissolving 40g of KOH in 150mL of deionized water to prepare a KOH solution;
(3) mixing 40g of SSAL with all KOH solution, stirring for 24h to form a new emulsion system, and carrying out forced air drying at 80 ℃ for 36h to obtain a resin matrix (PSK);
(4) and (3) raising the PSK to 850 ℃ at a speed of 10 ℃/min in a tube furnace under an inert atmosphere, then preserving the heat for 2h to obtain a porous carbon product, and grinding to obtain the hydrophobic porous carbon material.
Comparative example 4
The method of preparing a hydrophobic porous carbon material of this comparative example was the same as example 5, except that the addition of oxalic acid as an activator was changed, i.e., the resin matrix was prepared by emulsion polymerization, and then the oxalic acid was solid-mixed with the crushed resin matrix and carbonized at high temperature. The method comprises the following steps:
(1) pre-emulsifying 5g of vinyltrimethoxysilane, 40g of styrene, 15g of acrylate, 0.5g of dodecyl glucoside, 1.0g of sodium dodecyl sulfate, 0.7g of Tween-80 and 110g of deionized water in a four-neck flask, heating to 83 ℃ under the atmosphere of nitrogen, slowly and dropwise adding 1.0g of potassium persulfate aqueous solution (5% w/w) for emulsion polymerization, and keeping the temperature for 5 hours to obtain silicon propyl benzene latex (SSAL);
(2) drying 40g SSAL in an oven by blowing at 80 ℃ for 36h to obtain a resin matrix (PS), and crushing;
(3) uniformly mixing 40g of Oxalic Acid (OA) and PS solid to obtain an OA/PS composite material;
(4) and under an inert atmosphere, heating the OA/PS composite material to 850 ℃ at a speed of 10 ℃/min in a tubular furnace, then preserving heat for 2h to obtain a porous carbon product, and grinding to obtain the hydrophobic porous carbon material.
Comparative example 5
The preparation method of the hydrophobic porous carbon material of this comparative example is the same as that of example 5, except that the addition step of the activator oxalic acid was changed, that is, the resin matrix was prepared by emulsion polymerization, and then the oxalic acid solution was solid-liquid mixed with the crushed resin matrix and carbonized at high temperature. The method comprises the following steps:
(1) pre-emulsifying 5g of vinyltrimethoxysilane, 40g of styrene, 15g of acrylate, 0.5g of dodecyl glucoside, 1.0g of sodium dodecyl sulfate, 0.7g of Tween-80 and 110g of deionized water in a four-neck flask, heating to 83 ℃ under the atmosphere of nitrogen, slowly and dropwise adding 1.0g of potassium persulfate aqueous solution (5% w/w) for emulsion polymerization, and keeping the temperature for 5 hours to obtain silicon propyl benzene latex (SSAL);
(2) drying 40g SSAL in an oven by blowing at 80 ℃ for 36h to obtain a resin matrix (PS), and crushing;
(3) dissolving 40g of Oxalic Acid (OA) in 150mL of absolute ethyl alcohol to prepare an OA solution, mixing the OA solution with PS solid and liquid, and carrying out forced air drying for 36h at 80 ℃ in an oven to obtain an OA/PS composite material;
(4) and under an inert atmosphere, heating the OA/PS composite material to 850 ℃ at a speed of 10 ℃/min in a tubular furnace, then preserving heat for 2h to obtain a porous carbon product, and grinding to obtain the hydrophobic porous carbon material.
The porous carbon materials prepared in the above examples and comparative examples were tested for specific surface area, total pore volume, micropore volume and moisture absorption rate, and the test standards refer to GB/T7702.20-2008 "determination of specific surface area of coal granular activated carbon test method", GB/T21650.1-2008 "determination of pore size distribution and porosity of solid material by mercury intrusion method", and GB/T169913-.
TABLE 1 Properties of porous carbon materials prepared in examples and comparative examples
| BET/(m²/g) | Total pore volume/(cm/g) | Microporous capacity/(cm/g) | Moisture absorption rate/%) | |
| Example 1 | 1826 | 1.41 | 0.83 | 22.3 |
| Example 2 | 1820 | 1.44 | 0.79 | 20.2 |
| Example 3 | 1897 | 1.48 | 0.92 | 18.9 |
| Example 4 | 1941 | 1.56 | 0.84 | 18.1 |
| Example 5 | 2096 | 1.62 | 0.91 | 16.0 |
| Example 6 | 1853 | 1.46 | 0.89 | 14.6 |
| Example 7 | 1167 | 0.98 | 0.46 | 13.6 |
| Example 8 | 824 | 0.72 | 0.22 | 10.2 |
| Comparative example 1 | 1796 | 1.58 | 0.81 | 36.01 |
| Comparative example 2 | 1956 | 1.61 | 0.81 | 18.3 |
| Comparative example 3 | 2136 | 1.65 | 0.87 | 19.1 |
| Comparative example 4 | 429 | 0.46 | 0.10 | 11.7 |
| Comparative example 5 | 417 | 0.38 | 0.08 | 12.0 |
As can be seen from the data in table 1, the specific surface area of the porous carbon material prepared in the embodiments of the present invention may be as high as 2096 m/g, the total pore volume may be as high as 1.62 cm mansions/g, the microporous pore volume may be as high as 1.62 cm mansions/g, and the porous carbon material has a high specific surface area and a dense pore structure; the moisture absorption rate of the hydrophobic fiber is as low as 10.2%, which is due to the fact that the moisture absorption rate is reduced by the existence of Si-C bonds, and the hydrophobic fiber has good hydrophobic performance. In particular, in example 5, when the ratio of SSAL/OA is 1:1, porous carbon obtained by sintering PSO resin has higher BET, total pore volume and micropore volume; in addition, the carbonization temperature has a great relationship with the porous structure, and when the carbonization temperature is higher than 900 ℃, the BET of the product is reduced, part of the microporous structure is destroyed, and the moisture absorption rate is reduced as in examples 7 and 8; meanwhile, as the content of the organic silicon in the PSO resin increases, the moisture absorption rate of the porous carbon material decreases.
In comparative example 1, no silicone was added, and the obtained porous carbon material had poor hydrophobicity due to lack of Si — C bond and increased moisture absorption rate.
In the comparative example 2 and the comparative example 3, oxalic acid is replaced by potassium hydroxide or potassium salt respectively, so that the obtained porous carbon material has good pore-forming effect, the known strong activators potassium hydroxide and potassium salt have excellent pore-forming effect, the oxalic acid can still achieve BET and pore volume similar to those of potassium hydroxide and sodium oxalate activators, and compared with the potassium hydroxide and sodium oxalate, the porous carbon subjected to pore-forming by oxalic acid does not need to be treated by acid and alkali, so that the subsequent treatment process is reduced, and the preparation process is simple, the carbon source is wide, and the potential of product industrialization is realized.
The BET and pore volume of comparative examples 4 and 5 are significantly reduced because the resin matrix is prepared by emulsion polymerization, and then oxalic acid is mixed with the crushed resin matrix in a solid/solid-liquid manner and carbonized at high temperature, and the oxalic acid is easily decomposed at high temperature.
Claims (6)
1. The preparation method of the hydrophobic porous carbon material is characterized by comprising the following steps of:
1) preparing raw materials of organic silicon, styrene, acrylate, an emulsifier and deionized water, pre-emulsifying in a four-neck flask, heating to 70-95 ℃ under the atmosphere of nitrogen, slowly dropwise adding 0.1-1 part by weight of potassium persulfate to carry out emulsion polymerization, and keeping the temperature for 2-8 hours to obtain silicon propyl benzene latex SSAL;
wherein the raw materials account for the following parts by weight: 1-5 parts of organic silicon, 20 parts of styrene, 5-10 parts of acrylate, 0.2-2 parts of emulsifier and 30-80 parts of deionized water;
the organic silicon is at least one of dimethoxy methyl vinyl silane, dimethyl divinyl silane, vinyl trimethoxy silane, 3- (methacryloyloxy) propyl trimethoxy silane and 2,4, 6-trimethyl-2, 4, 6-trivinyl cyclotrisilazane;
2) dissolving oxalic acid OA in absolute ethyl alcohol to prepare an OA solution;
3) according to SSAL: OA = 1: mixing the SSAL and the OA solution according to the weight ratio of 0.2-5, uniformly stirring to form a new emulsion system, and carrying out forced air drying at 50-90 ℃ for 24-48 h to obtain a resin matrix PSO;
4) in an inert atmosphere, heating PSO in a tube furnace to 700-1000 ℃, then preserving heat for 1-4 h to obtain a porous carbon product, and grinding to obtain the hydrophobic porous carbon material.
2. The method according to claim 1, wherein in the step 1), the acrylate is at least one of ethyl acrylate, butyl acrylate and isooctyl acrylate.
3. The method according to claim 1, wherein in the step 1), the emulsifier is at least one of lauryl glucoside, sodium dodecylbenzenesulfonate, sodium dodecylsulfate, polyoxyethylene octylphenol ether-10, and tween-80.
4. The preparation method according to claim 1, wherein in the step 3), the stirring rate is controlled to be 500 to 1000 r/min.
5. The method according to claim 1, wherein in the step 4), the inert atmosphere is at least one of nitrogen or argon.
6. The method according to claim 1, wherein in the step 4), the temperature rising rate of the PSO in the tube furnace is 10 ℃/min.
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