JP4815599B2 - Method for producing mesoporous polymer and apparatus for producing the same - Google Patents

Description

  The present invention relates to a method for producing a polymer in which mesopores are formed (hereinafter referred to as “mesoporous polymer”).

  Mesoporous polymer is a material of adsorbent, gas diffusion electrode, ion exchange resin, electric double layer capacitor and supercapacitor, substance separation, catalyst carrier, gas sensor, water treatment, sewage treatment, wastewater treatment, template synthesis It is suitable for use in the field of environmental engineering, chemical engineering and biotechnology such as creation of nanomaterials.

  As a conventional method for producing a mesoporous polymer, for example, in Patent Documents 1 to 4 and Non-Patent Documents 1 and 2 below, a polymer cluster of resorcinol and formaldehyde is synthesized in an aqueous solvent, and the aqueous solvent is used as an acetone solvent. A method for producing a mesoporous polymer by substitution and supercritical drying with a carbon dioxide supercritical fluid is described.

  Further, as another method for producing a mesoporous polymer, for example, Non-Patent Documents 3 and 4 below describe a method for producing a mesoporous cryogel by a freeze-drying method.

U.S. Pat. No. 4,873,218 U.S. Pat. No. 4,997,804 US Pat. No. 5,081,163 US 5086085 Pekala R.D. W. Alviso C .; T.A. , Kong F .; M.M. , Hulsey S .; S. , J .; Non-Cryst. Solids, 1992, 145, 90-98p Pekala R.D. W. Alviso C .; T.A. Mater. Res. Soc. Symp. Prc. 1990, 180, 791-795. Tamon H. , Ishizka H .; , Yamamoto T .; , Suzuki T. Carbon, 1999, 37, 2049-2055. Yamamoto T. Nishimura T .; , Suzuki T. , Tamon H., et al. Carbon, 2001, 39, 2369-2386.

  However, the manufacturing methods described in Patent Documents 1 to 4 and Non-Patent Documents 1 and 2 require complicated operations such as using a supercritical dry state and cannot be easily performed, resulting in high manufacturing costs. There are challenges.

  In addition, the mesoporous cryogel production method described in Non-Patent Documents 3 and 4 requires a complicated process of low-temperature drying, and when the solvent is sublimated, the mesopores shrink due to the interfacial tension. There is a problem that the capacity of the system decreases.

  In view of the above problems, an object of the present invention is to provide a method for producing a mesoporous polymer that is easier to produce.

  As a result of diligent investigations on the above problems, the present inventors have found that an aromatic low molecule having two or more functional groups and a functional group capable of reacting with the functional group of the aromatic low molecules and having a crosslinkable functional group. Focusing on the fact that a mesoporous polymer can be easily produced by reacting molecules with each other in a thin space, the present invention has been completed.

  That is, the method for producing a mesoporous polymer according to one means of the present invention provides an aromatic low polymer having two or more functional groups between a pair of substrates arranged at a distance of 0.05 mm or more and less than 10 mm. The molecule is allowed to react with the functional group of the aromatic low molecule and a crosslinkable low molecule having a crosslinkable functional group. According to this measure, a strong interfacial tension can be obtained between a pair of substrates by reacting an aromatic small molecule and a crosslinkable small molecule in a narrow space of less than 10 mm, and the mesopores contract due to the interfacial tension. It is thought that it can be prevented. Here, “mesopore” means a pore having a diameter of 2 nm to 50 nm, and “mesoporous polymer” means a polymer having mesopores. In addition, the size of the space is not particularly limited with respect to the width, depth, and planar shape as long as the thickness is 0.5 mm or more and less than 10 mm. For example, the width and depth are each 1 m or less. It is preferably 50 cm or less, more preferably 10 cm or less.

  Moreover, in this means, although not limited, it is more preferable to make it react in the space which has a thickness of 0.1 mm or more and 5 mm or less.

  Further, in this means, the aromatic low molecule is preferably at least one of resorcinol, melamine or epoxy, and the crosslinkable low molecule is at least one of formaldehyde or amine, although not limited thereto. When the aromatic low molecule is resorcinol or melamine, the crosslinkable low molecule is formaldehyde, and when the aromatic low molecule is epoxy, the crosslinkable low molecule is more preferably an amine.

  Moreover, in this means, although not limited, it has a spacer which is arranged between a pair of substrates and has a cut-out space, and in this cut-out space in this spacer, it is crosslinkable with an aromatic small molecule. It is also preferable to react with a low molecule.

  Moreover, although it does not necessarily limit in this means, it is preferable to carry out reaction for 12 hours or more and 140 hours or less.

  As described above, the present invention can provide a method for producing a mesoporous polymer that is easier to produce.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the present invention can be implemented in many different modes and is not construed as being limited to the embodiments and examples shown below.

  The method for producing a mesoporous polymer according to this embodiment includes an aromatic small molecule having two or more functional groups and a fragrance between a pair of substrates arranged at an interval of 0.05 mm or more and less than 10 mm. One of the characteristics is to react a crosslinkable small molecule having a functional group capable of reacting with a group low molecule and having a crosslinkable group.

  The aromatic small molecule having two or more functional groups in the present embodiment is not limited as long as a mesoporous polymer can be formed by reaction, but is at least one of resorcinol, melamine or epoxy. It is preferable that the crosslinkable small molecule having a functional group capable of reacting with a functional group of an aromatic small molecule and having a crosslinkable group is not limited, but is at least one of formaldehyde and amine. Is preferred. In particular, resorcinol and formaldehyde, melamine and formaldehyde, and epoxy and amine are preferable in terms of easier realization of a mesoporous polymer.

  In this embodiment, the reaction between the aromatic low molecule and the crosslinkable low molecule needs to be performed in a solvent. The solvent is not limited as long as it dissolves the above-mentioned aromatic low molecule and crosslinkable low molecule but does not inhibit the reaction. For example, water, ethanol, acetone, and other organic solvents can be preferably used. .

  Further, the concentration of the aromatic low molecule in the solvent in the present embodiment is preferably 4 wt% or more and 66 wt% or less, and more preferably 10 wt% or more and 50 wt% or less. In addition, the concentration of the crosslinkable low molecule in the solvent is preferably 3 wt% or more and 60 wt% or less, and more preferably 5 wt% or more and 25 wt% or less. By making the concentration of the aromatic low molecule 4 wt% or more and the concentration of the crosslinkable low molecule 3 wt% or more, the polymer produced can be formed into a network to form sufficient mesopores, By setting the concentration of molecules to 66 wt% or less and the concentration of crosslinkable low molecules to 60 wt% or less, there is an advantage that a sufficient gap can be formed so that mesopores do not disappear.

  In addition, the reaction between the aromatic low molecule and the crosslinkable low molecule in the present embodiment can be appropriately adjusted and is not limited. However, from the viewpoint of making the reaction time within a practical range, it is 0 degree or more and 100 It is preferable to carry out at a temperature of 25 degrees or less, and more preferably 25 degrees or more and 90 degrees or less. Moreover, the pore diameter and the pore shape can be controlled by controlling the reaction time. In this case, the reaction time is not limited, but is preferably 12 hours or longer and 140 hours or shorter, and more preferably 20 hours or longer and 70 hours or shorter. Moreover, it is also preferable from the viewpoint of the crosslinking reaction of the organic functional unit and the generation of the polymer skeleton to appropriately change the temperature of the reaction with the passage of time.

  In addition, it is also preferable to perform the reaction of the aromatic low molecule and the crosslinkable low molecule in the present embodiment in the presence of a catalyst. Although it does not necessarily limit as a catalyst, For example, alkaline substances, such as sodium carbonate and sodium hydroxide, weak acids, etc. can be used preferably.

  Moreover, in this embodiment, although not limited as long as it has a pair of base | substrate arrange | positioned at intervals of 0.05 mm or more and less than 10 mm, between a pair of board | substrates 1a and 1b and this pair of board | substrates. It can be easily realized by the spacer 2 in which a space 21 that is sandwiched and cut out is formed. This configuration is shown in FIG. By making the space cut out in this way, the pair of substrates 1a, 1b and the spacer 2 can be a highly sealed space, and the evaporation rate of the solvent is suitable for forming mesopores. It can be. On the contrary, if the space is completely sealed, the solvent cannot be evaporated and the solvent remains in the mesopores, which is not preferable. Therefore, the sealing property of the space is preferably such that the solvent gradually evaporates over a period of time that the reaction of the aromatic low molecule and the crosslinkable low molecule is completed.

  The material of the pair of substrates 1a, 1b and spacer is not particularly limited, but is at least one of polymers and composites such as polyethylene terephthalate (PET), polyethylene, polyimide, polyphenylene sulfide, wood material, glass and metal. Can be adopted as appropriate.

  The space 21 from which the spacer 2 is cut out has no particular limitation on the planar shape as long as the thickness is 0.05 mm or more and less than 10 mm, and can be adjusted as appropriate. The thickness is set to 0.05 mm or more from the viewpoint of manufacturing a spacer, and from the viewpoint of facilitating filling of aromatic low molecules and crosslinkable low molecules between substrates, and the thickness is less than 10 mm. This is because it is considered that the interfacial tension between the substrate and the polymer is weakened and the mesopores shrink when the solvent evaporates, and the mesopore capacity decreases.

  As described above, the present embodiment provides a method for producing a mesoporous polymer that is easier to produce.

Example 1
First, two polyimide substrates of 5 cm × 5 cm × 1 mm were prepared, and a polyimide spacer having a thickness of 3 cm × 3 cm × 0.5 mm was fixed on one polyimide substrate with an adhesive. Thereby, a recess of 3 cm × 3 cm × 0.5 mm was formed.

  Next, a mixed solution of 0.050 mol of resorcinol, 0.27 mol of formaldehyde, 0.72 mol of water, and 0.0001 mol of sodium carbonate was prepared, and this mixed solution was filled in the recess.

  Then, this was covered with another polyimide substrate and not immediately dried, and reacted at room temperature (300K) for 1 day, 333K for 1 day, and 353K for 1 day. Thereafter, the polyimide substrate used as a lid was carefully peeled off to obtain a brown solid. The water was sufficiently evaporated, and the solid matter was dried.

  And the nitrogen adsorption isotherm of the said solid substance obtained by the present Example is obtained with a nitrogen adsorption isotherm measuring device (manufactured by Quantachrome, Autosorb-1), and the Dollimore-Heal method (hereinafter referred to as “DH method”). Using this, the distribution of mesopores was determined. FIG. 2 shows the nitrogen adsorption isotherm measured here, and FIG. 3 shows the result of the distribution of mesopores obtained. Moreover, the SEM photograph of the said solid substance is also shown in FIG.

As a result, it was confirmed that the solid material was a mesoporous polymer. The pore structure of the mesoporous polymer obtained by this example is shown in Table 1 below. Here, the specific surface area is a value obtained by analyzing the nitrogen adsorption isotherm by the BET method, and the mesopore diameter, mesopore volume, micropore diameter, and micropore volume are DH method and Dubinin-Radushkevich ( DR) is a value obtained by analysis.

(Example 2)
In the present Example, it carried out like Example 1 except having changed 0.00025 mol of the amount of sodium carbonate as a catalyst. As a result, the same result as in Example 1 was obtained. In addition, the SEM photograph of the obtained solid substance is shown in FIG.

(Example 3)
In this example, the same procedure as in Example 1 was performed, except that the spacer thickness was changed to 1 mm, 2 mm, and 5 mm, respectively. It was found by measurement of nitrogen adsorption isotherm of the obtained solid material that there were different pore diameters and pore capacities.

(Comparative example)
Here, it carried out like Example 1 except having changed into thickness 10mm of a spacer. As a result, a brown solid was obtained, but the mesopores were shrunk by nitrogen adsorption isotherm measurement, resulting in a polymer having a very small mesopore capacity.

  The mesoporous polymer according to the present invention has wide industrial applicability as a material for adsorbents, gas diffusion electrodes, ion exchange resins, electric double layer capacitors and supercapacitors, for example.

It is a figure of the apparatus used for the manufacturing method of the mesoporous polymer which concerns on embodiment. 2 is a graph showing a nitrogen adsorption isotherm of a mesoporous polymer produced according to Example 1. FIG. 1 is a diagram showing a mesopore size distribution of a mesoporous polymer produced according to Example 1. FIG. 2 is an electron microscope (SEM) photograph of a mesoporous polymer produced according to Example 1. FIG. 2 is an electron microscope (SEM) photograph of a mesoporous polymer produced according to Example 2.

Explanation of symbols

1a, 1b ... substrate, 2 ... spacer, 21 ... cut-out space

Claims (4)

In a space formed by a pair of substrates and a spacer, the distance between the pair of substrates being 0.05 mm or more and less than 10 mm and having high sealing performance, a solvent, 4 wt% to 66 wt% resorcinol, and 3 wt% to 60 wt% Filled with the following mixed solution containing formaldehyde,
  A method for producing a mesoporous polymer, wherein the resorcinol and formaldehyde are reacted in the space. The method for producing a mesoporous polymer according to claim 1, wherein a distance between the pair of substrates is 0.1 mm or more and 5 mm or less. The method for producing a mesoporous polymer according to claim 1, wherein the reaction is performed for 12 hours or more and 140 hours or less.   Between a pair of substrates arranged at a distance of 0.05 mm or more and less than 10 mm on which spacers having cut-out spaces are arranged, a solvent, 4 wt% to 66 wt% of resorcinol and 3 wt% to 60 wt% of formaldehyde Filling a mixed solution containing
  A method for producing a mesoporous polymer, wherein the resorcinol and formaldehyde are reacted in the cut-out space.