CN108940229B - Epoxy macroporous/mesoporous polymer material and preparation method thereof - Google Patents
Epoxy macroporous/mesoporous polymer material and preparation method thereof Download PDFInfo
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- CN108940229B CN108940229B CN201710420519.9A CN201710420519A CN108940229B CN 108940229 B CN108940229 B CN 108940229B CN 201710420519 A CN201710420519 A CN 201710420519A CN 108940229 B CN108940229 B CN 108940229B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28095—Shape or type of pores, voids, channels, ducts
Abstract
The invention relates to an epoxy macroporous/mesoporous polymer material and a preparation method thereof, and the epoxy macroporous/mesoporous polymer material is obtained by curing an epoxy resin/organic dispersion system in a solid state and cleaning to remove a dispersant, and the material simultaneously has macropores with the diameter of 1-50 mu m and mesopores with the average pore diameter of 20nm, and the specific surface area of the material reaches 230m2More than 90 percent of porosity and less than 0.1g/mL of apparent density. In the preparation process, trimethylolpropane is used as a dispersing agent, the dispersing effect is achieved by utilizing the moderate affinity of the trimethylolpropane and epoxy resin E-51, the pore is formed by continuous crystallization in the cooling process, and finally the water-soluble trimethylolpropane is cleaned and removed, the pore can be formed by a continuous crystallization mode on the premise of not using a template agent and a surfactant, the epoxy resin is solidified in a solid state, the influence of phase separation on the performance of the material is avoided, on one hand, the continuity of the internal appearance of the epoxy resin is ensured, simultaneously, the extremely unique appearance characteristic is constructed, the material preparation does not depend on special equipment and special conditions, the used unique dispersing agent, namely the trimethylolpropane is low in price, extremely low in volatility, small in pollution and recyclable, and completely meets the requirement of green chemistry.
Description
Technical Field
The invention relates to the technical field of high polymer material synthesis, in particular to an epoxy macroporous/mesoporous polymer material and a preparation method thereof.
Background
A large amount of polymer porous materials are prepared in separation science and are used for chromatographic packing in an integral column mode, the material is required to have uniform pore size distribution as much as possible, and three-dimensional pore channels can be continuously communicated, so that stable flow of liquid in a chromatographic column is facilitated, and the resistance is small. When the porous material is used for adsorption, an inherent contradiction exists between the pore diameter and the specific surface area, and the larger the specific surface area is, but the smaller the pore diameter is; conversely, the larger the pore diameter, the smaller the specific surface area. The magnitude of the adsorption capacity depends not only on the specific surface area as an index of thermodynamics but also on the pore size as an index of kinetics. The larger the pore size, the greater the diffusion rate; conversely, the smaller the pore size, the diffusion of the substance is hindered, so that an adsorbent material having a small pore size such as activated carbon is used in the form of particles as small as possible, thereby increasing the adsorption rate. It is a challenge to the manufacturing technology of materials if the adsorbent material is faced with a range of substances with very different sizes, which will necessarily require as wide a pore size distribution as possible.
The scientific problem of phase separation is generally not isolated in the preparation of polymer porous materials, and the so-called porogen is a substance which cannot be practically compatible with the polymer itself, namely a weak solvent or a precipitant, and the porogen and the polymer are separated to form an independent phase in the polymerization process, namely a porogen mechanism. The size of the pore size is related to the compatibility of the two, the poorer the compatibility (including increasing the incompatibility by means of porogen crystallization) will result in a somewhat larger pore size; when the compatibility is good (e.g., additional surfactant is added), the pore size is reduced due to insufficient phase separation. However, it is difficult to obtain a material having a wide pore size distribution in one preparation reaction regardless of the adjustment of the compatibility.
The invention has the significance of breaking the obstacle, various pore passages with the size of dozens of micrometers and the size of a few nanometers are obtained through one-time preparation reaction by utilizing a special pore-forming agent, the special pore-forming agent is trimethylolpropane, the melt of the special pore-forming agent and epoxy resin E-51 can form a temperature-sensitive solution with the mass ratio of 2/1, the temperature-sensitive solution and the epoxy resin are incompatible when the mass of the pore-forming agent is dozens of times of that of the epoxy resin, ultra-large pores and large pores with the micrometer scale can be manufactured by utilizing crystallization driving phase separation, and the compatibility is recovered when the mass of the pore-forming agent is reduced to 2 times of that of the epoxy resin, so that mesoporous with the nanometer size can be manufactured finally. We find the strong dependence relationship between the compatibility and the composition, so that the preparation of the polymer porous material breaks through the technical obstacle, well reconciles the inherent contradiction between the pore diameter and the surface area, and optimizes the performance and the function of the adsorption material.
Disclosure of Invention
The invention provides an epoxy macroporous/mesoporous polymer material, which is characterized by simultaneously having macropores of 1-50 mu m and mesopores with the average pore diameter of 20nm, and the specific surface area of the polymer material reaches 230m2(ii)/g, the porosity is more than 90%, and the apparent density is less than 0.1 g/mL.
Another technical problem to be solved by the present invention is to provide a specific dispersant, namely trimethylolpropane, used in the preparation of the epoxy group macroporous/mesoporous polymer material, wherein the specific dispersant is a water-soluble organic substance, has a moderate melting point (57-58 ℃), can disperse epoxy resin in a melt thereof without participating in a curing reaction, continuously crystallizes during a cooling process to form crystals with a wide size distribution, the crystals play a pore-forming role after the epoxy resin is cured, and form stable mesopores without using any template agent and surfactant, and the organic compound has low toxicity, can be recycled, does not pollute the environment, and reduces the preparation cost.
The invention also aims to solve the technical problem of the specific operation scheme of the preparation method, which mainly controls the temperature reduction rate and the crystallization rate.
1. The technical scheme adopted by the invention for solving the primary technical problem is as follows: an epoxy macroporous/mesoporous polymer material is a porous material obtained based on an epoxy resin heterogeneous curing mechanism.
The polymer material is very beneficial to have macropores with the diameter of 1-50 mu m and mesopores with the average pore diameter of 20nm, so that air pollutants with different sizes can be adsorbed;
advantageously, the specific surface area of the material is up to 230m2The water-soluble polymer has stronger adsorption capacity;
the material has different porosities of more than 90%, apparent density of less than 0.1g/mL, large size and good mechanical stability.
2. The technical scheme adopted by the invention for solving another technical problem is as follows: a process for preparing the epoxy resin material with big pores and mesopores includes such steps as dispersing epoxy resin in a water-soluble organic fused mass, cooling while crystallizing to form crystals with wide size distribution, and solidifying.
The method has the advantages that the method can manufacture the ultra-large pores, the large pores and the stable mesopores at one time without using any template agent and surfactant;
the organic compound used in the method is water-soluble, low in price and toxicity, can be recycled and does not pollute the environment.
3. The technical scheme adopted by the invention for solving the other technical problem is as follows: the specific method for preparing the epoxy macroporous/mesoporous polymer material by using the dispersant is characterized by comprising the following steps: 1) heating and melting trimethylolpropane to enable the trimethylolpropane to flow into liquid, adding epoxy resin (the trademark E-51), quickly stirring to obtain white dispersion, quickly adding diethylenetriamine, wherein the mass ratio of the trimethylolpropane to the epoxy resin is within the range of 10/1-40/1, and the mass ratio of the epoxy resin to the diethylenetriamine is within the range of 8/1-6/1; 2) cooling with ice water and violently stirring to ensure that the heat is released uniformly, finally obtaining viscous semisolid, quickly pouring the viscous semisolid into a mould, placing the viscous semisolid into a refrigerator for further cooling for 2-3 hours after the viscous semisolid is completely solidified, and freezing to obtain hard white solid; 3) and (3) curing the solid at 45 ℃ for 12-15 hours, soaking the solid product in water, thoroughly washing off trimethylolpropane, and then drying in a vacuum oven at normal temperature to obtain the white stable polymer porous material.
The trimethylolpropane has certain affinity to the epoxy resin, but cannot completely dissolve the epoxy resin, and the state is very favorable for continuous crystallization to form crystals from micrometer scale to nanometer scale, so that a porous structure with extremely wide pore size distribution is manufactured;
the epoxy resin is cured at a temperature lower than the melting point of trimethylolpropane, namely in a solid state, so that the influence of phase separation on the appearance of the product can be completely avoided, and the continuity of the internal appearance of the product and the macroscopic mechanical strength are ensured;
advantageously, the concentration of epoxy resin in the dispersion can be very low, and the resulting porous material has a very low apparent density and a high porosity, with the three-dimensional channels running completely through.
The invention has the advantages that: 1) the epoxy resin-based polymer porous material has wide pore size distribution, high specific surface area, high porosity and good mechanical strength, and is very suitable to be used as an adsorption material for purifying air; 2) the preparation method of the material is very unique and simple to operate, the pores can be formed in a continuous crystallization mode on the premise of not using a template agent and a surfactant, the epoxy resin is cured in a solid state, the influence of phase separation on the performance of the material is avoided, on one hand, the continuity of the internal appearance of the material is ensured, and simultaneously, the extremely unique appearance characteristics are constructed; 3) the material preparation does not depend on special equipment and special conditions, and the used unique dispersant trimethylolpropane has the advantages of low price, extremely low volatility, small pollution, recyclability and complete accordance with the requirement of green chemistry.
Detailed Description
Example 1
Heating 35.0g of trimethylolpropane to completely melt to be transparent fluid, adding 3.5g of epoxy resin E-51, stirring vigorously to obtain viscous liquid, adding 0.44g of diethylenetriamine, cooling with ice water, stirring vigorously to release heat uniformly to obtain viscous semisolid containing a large amount of tiny crystals, pouring the viscous semisolid into a plastic mould, after complete solidification, placing the viscous semisolid into a refrigerator for further cooling and crystallizing for 3 hours to obtain hard white solid, solidifying for 12 hours at 45 ℃, repeatedly soaking in water until the trimethylolpropane is completely removed, and drying at normal temperature in vacuum to obtain the white foam material.
Example 2
60.0g of trimethylolpropane is heated and melted to be transparent and flowable liquid, 3.0g of epoxy resin E-51 is added and stirred for dispersion, 0.44g of diethylenetriamine is added, the mixture is cooled by ice water and stirred vigorously to release heat uniformly to obtain viscous semi-solid containing a large number of micro crystals, the viscous semi-solid is poured into a plastic mould, the viscous semi-solid is placed into a refrigerator for further cooling and crystallization for 3 hours after complete solidification, hard white solid is obtained after freezing, the solid is solidified for 12 hours at the temperature of 45 ℃, the viscous semi-solid is repeatedly soaked in water until the trimethylolpropane is completely removed, and the viscous semi-solid is dried in vacuum at the normal temperature to obtain the white foam material.
Example 3
Heating and melting 90.0g of trimethylolpropane to be transparent fluid, adding 3.0g of epoxy resin E-51, stirring and dispersing, adding 0.50g of diethylenetriamine, continuously stirring to obtain a good dispersion liquid, cooling with ice water and violently stirring to ensure that the heat is released uniformly to obtain viscous semisolid containing a large number of tiny crystals, pouring the viscous semisolid into a plastic mould, placing the viscous semisolid into a refrigerator for further cooling and crystallizing for 4 hours after complete solidification, freezing to obtain hard white solid, solidifying for 14 hours at 45 ℃, repeatedly soaking in water until the trimethylolpropane is completely removed, and drying at normal temperature in vacuum to obtain the white foam material.
Example 4
Heating 80.0g of trimethylolpropane to completely melt the trimethylolpropane until the trimethylolpropane is transparent and can flow liquid, adding 2.0g of epoxy resin E-51, violently stirring the mixture evenly to obtain viscous liquid, adding 0.36 to 0.37g of diethylenetriamine, continuously stirring the mixture to obtain good dispersion liquid, cooling the dispersion liquid by ice water, violently stirring the dispersion liquid to ensure that the dispersion liquid releases heat evenly to obtain viscous semisolid, wherein the micro crystal is poured into a plastic mould, the plastic mould is placed in a refrigerator for further cooling and crystallization for 3 hours after the micro crystal is completely solidified, and hard white solid is obtained after freezing, curing for 15 hours at 45 ℃, then soaking in a very dilute glutaraldehyde aqueous solution (as the amount of diethylenetriamine in the system is large, glutaraldehyde is used for further crosslinking) until the trimethylolpropane is completely removed, reducing with dilute sodium borohydride solution, soaking in clear water, cleaning, and vacuum dewatering to obtain white foamed material.
And (3) analyzing a material structure:
observing the morphology by using a scanning electron microscope, wherein the result is shown in figure 1, the hole wall and the small bulge seen in the figure are not pure epoxy resin-based polymers, and the interior of the figure contains a three-dimensional continuous mesoporous channel; the pore size distribution was measured by mercury pressure method, and the results are shown in FIG. 2, where the pore size distribution is manifold; the pore size distribution of the mesoporous framework was measured by an adsorption-desorption method, and the result is shown in fig. 3, in which the average pore size of the mesopores was 20 nm; the microstructure of the mesoporous material was observed by transmission electron microscopy, and the result is shown in FIG. 4, from which the three-dimensional cage structure was observed; in addition, the specific surface area of the material is up to 230m measured by a BET method2The specific surface area of the material is not greatly related to the dosage of the trimethylolpropane, which shows that the specific surface area is mainly contributed by mesopores, and the distribution of macropores has little influence on the specific surface area. The apparent density of the material has a great relationship with the dosage of the trimethylolpropane, when the dosage of the trimethylolpropane is more than 30 times of that of the epoxy resin, the surface density can reach below 0.1g/mL, and the porosity reaches more than 90%.
Drawings
FIG. 1 is a scanning electron microscope image of the internal morphology of the material under different magnifications.
FIG. 2 pore size distribution by mercury pressure method.
FIG. 3 shows an adsorption-desorption curve and a pore size distribution of mesopores.
FIG. 4 is a transmission electron microscope image of the mesoporous framework.
Claims (2)
1. An epoxy macroporous/mesoporous polymer material is characterized by simultaneously having macropores of 1-50 mu m and mesopores with the average pore diameter of 20nm, and the specific surface area of the epoxy macroporous/mesoporous polymer material reaches 230m2More than g, the porosity is higher than 90%, and the apparent density is lower than 0.1 g/mL;
the epoxy macroporous/mesoporous polymer material is obtained by curing an epoxy resin/organic dispersion system in a solid state and then washing with water to remove a dispersing agent;
the preparation method of the epoxy group macroporous/mesoporous polymer material is characterized in that trimethylolpropane melt is used as a dispersing agent, and continuous crystallization of the trimethylolpropane melt in the cooling process is utilized to form pores, wherein the trimethylolpropane plays the roles of the dispersing agent and the pore-forming agent in sequence.
2. A method for preparing the epoxy-based macroporous/mesoporous polymer material of claim 1, which is characterized by comprising the following steps in sequence:
1) heating and melting trimethylolpropane to enable the trimethylolpropane to flow into liquid, adding epoxy resin E-51, quickly stirring to obtain white dispersion, quickly adding diethylenetriamine, wherein the mass ratio of the trimethylolpropane to the epoxy resin is 10/1-40/1, and the mass ratio of the epoxy resin to the diethylenetriamine is 8/1-6/1;
2) cooling with ice water and violently stirring to ensure that the heat is released uniformly, finally obtaining viscous semisolid, quickly pouring the viscous semisolid into a mould, placing the viscous semisolid into a refrigerator for further cooling for 2-3 hours after the viscous semisolid is completely solidified, and freezing to obtain hard white solid;
3) and (3) curing the solid at 45 ℃ for 12-15 hours, soaking the solid product in water, thoroughly washing off trimethylolpropane, and then drying in a vacuum oven at normal temperature to obtain the white stable polymer porous material.
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