JP4708729B2 - MOLECULAR ADSORBENT, ITS MANUFACTURING METHOD, AND GAS STORAGE DEVICE - Google Patents

Description

  The present invention relates to a molecular adsorbent using a porous body in which polyacetylene derivatives are aggregated, a method for producing the same, and a gas storage device.

Conventionally, polyacetylene derivatives are known to exhibit specific physical properties, and various reports on the specific physical properties have been made so far. For example, Patent Document 1 describes a gas separation membrane comprising a propiolic acid ester polymer represented by the general formula HC≡C—CO ₂ —R (where R is an alkyl group having 1 to 18 carbon atoms, etc.). ing. Patent Document 2 describes a polymer in which the molecular chain has a regular helical structure, and the density of the helical structure is reversibly changed by physical stimulation such as light and heat. Patent Document 3 describes a polyacetylene derivative having a pseudo-hexagonal (Pseudo-hexagonal) structure and having a superracene conjugated structure with π electrons based on a double bond.
JP-A-9-173759 JP 2004-27182 A JP 2004-115628 A

  However, Patent Document 1 discloses that a gas separation membrane made of a polyacetylene derivative selectively permeates a specific gas such as oxygen, but does not disclose a mechanism for selectively permeating oxygen. Therefore, Patent Document 1 has no suggestion as to whether the gas separation membrane has a molecular adsorption ability or a gas storage ability.

  Patent Document 2 discloses that a polymer of propiolic acid ester, that is, a polyacetylene derivative is a color variable material, a material constituting an electron supply layer of an organic EL device, a light shielding material, an organic semiconductor, a nonlinear optical material, a magnetic material, or a conductive material. It is described that it is suitable for various optical applications such as the above and electronics applications. However, Patent Document 2 has no suggestion about using a polyacetylene derivative as a molecular adsorbent.

  Further, Patent Document 3 describes that when a porous body in which a polyacetylene derivative is aggregated is exposed to a vapor of chloroform or toluene for a short time, its appearance changes from yellow to black. However, Patent Document 3 does not disclose the discoloration mechanism. Therefore, Patent Document 3 also has no suggestion as to whether or not the porous body in which the polyacetylene derivative is aggregated has molecular adsorption ability and further gas storage ability.

  This invention is made | formed in view of this point, and it aims at providing the molecular adsorption material which can adsorb | suck and store the molecule | numerator of various magnitude | sizes using a polyacetylene derivative, its manufacturing method, and a gas storage apparatus. .

  The molecular adsorbent according to the present invention contains a porous body in which a polyacetylene derivative having a cis-transoid structure in which the main chain is in the form of a helix and the side chain is located outside the main chain helix is aggregated. is there.

  The molecular adsorbent according to the present invention is the molecular adsorbent according to the present invention, wherein the polyacetylene derivative is methyl polypropiolate and adsorbs hydrogen molecules.

  In the method for producing a molecular adsorbent according to the present invention, a porous body is formed by aggregating a polyacetylene derivative having a cis-transoid structure in which the main chain is in the form of a helix and the side chain is located outside the main chain helix. In doing so, the average pore size of the porous body is adjusted by adjusting the size of the side chain.

  In the method for producing a molecular adsorbent according to the present invention, a porous material obtained by aggregating a polyacetylene derivative having a cis-transoid structure in which a main chain is in the form of a helix and a side chain is located outside the main chain helix. The average pore size of the porous body is adjusted by exposure to toluene, tetrahydrofuran or alcohol.

  The gas storage device according to the present invention comprises the molecular adsorbent according to the present invention.

  In the gas storage device according to the present invention, in the above invention, the polyacetylene derivative is methyl polypropiolate, and adsorbs and stores hydrogen molecules.

  According to the present invention, by adjusting the size of the side chain bonded to the helical main chain to produce a porous body in which the polyacetylene derivative is aggregated, or by exposing the porous body to chloroform or the like. The average pore diameter of the porous body can be adjusted.

  In addition, according to the present invention, by adjusting the average pore size of the porous body in which the polyacetylene derivative is aggregated, desired molecules can be selectively adsorbed on the pores formed in and on the surface of the porous body. Can do.

  Furthermore, according to the present invention, a molecular adsorbent that selectively adsorbs and stores specific molecules in the pores of the porous body and on the surface, and a gas storage device using this molecular adsorbent can be obtained.

  As a result of intensive studies on the physical properties of polyacetylene derivatives having a cis-transoid structure, the present inventors have determined that the porous body in which the polyacetylene derivatives are aggregated has a molecular adsorption function and adjusts the average pore size of the porous body. As a result, it was found that the molecule to be adsorbed can be selected, and the present invention has been completed. Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings as appropriate.

  The molecular adsorbent according to the present invention includes a porous body in which a polyacetylene derivative having a cis-transoid structure in which a main chain is in a helical shape and a side chain is located outside the main chain helix is aggregated. The FIG. 1 simply shows the structure of the porous body in which the polyacetylene derivative is aggregated. As shown in FIG. 1, in this porous body, adjacent helical chains are aggregated with their helical axes parallel to each other, and have a pseudo-hexagonal or orthorhombic crystal structure. Moreover, in this porous body, since adjacent helical chains are excluded from each other by their side chains, there are voids, that is, pores between the helical chains as well as the hollow portions of the helical chains. Therefore, in this porous body, the larger the side chain, the larger the interval between the helical chains and the larger the average pore diameter. This helical chain is deformed depending on the size of the side chain, its electrical characteristics, etc., but has a 3/1 helical structure that extends the side chain about every 120 ° on the projected view. 3 to 5 mm.

  When molecules of an appropriate size enter the pores in the porous body, the molecules are fixed or adsorbed on the pores. That is, if the molecule is too large relative to the average pore size of the porous body, the molecule cannot enter the pores and is not adsorbed by the porous body. In addition, if the molecule is too small relative to the average pore size of the porous body, the molecule can enter the pores, but can easily escape from the pores. As a result, only a small amount is adsorbed to the porous body. . Therefore, if the average pore size of the porous body is adjusted according to the size of the molecule to be adsorbed, only the target molecule can be selectively adsorbed on the porous body.

  As a means for adjusting the average pore diameter of the porous body, firstly, means for selecting a side chain having a size suitable for the size of the molecule to be adsorbed can be mentioned. Further, as a second means, there is a means for increasing the average pore diameter by exposing the porous body to a vapor or solvent of chloroform, toluene, tetrahydrofuran or alcohol.

The molecule adsorbed on the molecular adsorbent according to the present invention is not particularly limited, but is a gas that is easily scattered and difficult to handle, for example, hydrogen (H ₂ ), helium (He), oxygen (O ₂ ). , Argon (Ar), krypton (Kr) and xenon (Xe). In order to selectively adsorb hydrogen to the porous body, it is preferable to adjust the average pore diameter to 1 to 2 nm. Similarly, helium and oxygen are 1 to 2 nm, argon is 3 to 4 nm, and krypton is 4 to 6 nm. Or, in the case of xenon, it is preferable to adjust to 5 to 7 nm.

  The average pore size of the porous body is calculated by analyzing X-ray diffraction and X-ray reflection spectrum data. Therefore, the average pore diameter of the porous body is approximately the average distance between the helical axes of adjacent helical chains. Further, as will be described later in Examples, interaction between adsorbed molecules called SF (Saito-Foley Model) method, and electrostatic attractive force / repulsion between adsorbed molecules and atoms on the surface of pore walls The average pore diameter of this porous body can also be calculated using a method for evaluating the pore distribution from the calculation of the interaction (electrostatic attraction / repulsion interaction). Further, by analyzing NMR (Nuclear Magnetic Resonance) spectrum data of a porous body on which molecules are adsorbed, the average pore diameter of the porous body can be calculated.

  Here, in this porous body, pores are formed in the hollow part of the helical chain and the gap between adjacent helical chains, and the hollow part of the helical chain is compared with the gap between adjacent helical chains. Since it is small, it is presumed that most molecules are adsorbed in the voids between the helical chains. However, it is estimated that hydrogen molecules can enter the hollow part of the helical chain.

In order to adjust the average pore size of this porous body to 1 to 2 nm suitable for adsorption of hydrogen molecules, a carboxy group (methyl ester: − Preferably, COOCH ₃ ) is selected and the second means is not used. Similarly, in order to adjust to 5 to 7 nm suitable for xenon, it is preferable to select paraphenol ether in the side chain using the first means and use the second means.

  Regarding the first means, the size of the side chain is determined mainly based on the length thereof. However, if there are many branches in the side chain or if the conformation of the side chain is likely to transition, calculating the length based on the number of carbons in the side chain and estimating its size will cause an error from the verification data. There is a tendency to grow. Therefore, in this case, it is preferable to estimate the size of the side chain based on the verification data.

  A porous material exposed to chloroform, toluene, tetrahydrofuran or alcohol vapor or solvent is dissolved in a large amount of chloroform or toluene, and an alcohol such as methanol or ethanol or triethylamine which is a poor solvent for the porous material in the solution. When the porous body is precipitated by adding (TEA) or the like, the average pore diameter of the porous body is restored to the size before exposure. Therefore, if the average pore diameter is restored using the poor solvent after the chloroform or toluene vapor exposure, the porous body can be reused for adsorption of other molecules.

  The polyacetylene derivative constituting this porous body is produced by polymerizing or copolymerizing substituted acetylenes represented by the following general formulas (1) and (2).

HC≡C—CO ₂ —R (1)
HC≡C—Ar—O—R (2)

  In the general formulas (1) and (2), “—R” that becomes a side chain after polymerization is not limited to an alkyl group. Further, methods for synthesizing these substituted acetylenes are described in detail in “Y. Mawatari, M. Tabata et al., Macromolecules, 34, 3776-3782 (2001)”.

  As "-R", that is, the side chain in the general formulas (1) and (2), a linear or branched alkyl group having 1 to 18 carbon atoms is preferable. Specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-amyl group, iso-amyl group, n-pentyl group, 4-methyl-2-pentyl group, neopentyl group, 1,1-dimethyl-2-ethylpropyl group, n-hexyl group, 2-ethylhexyl group, 2,4,4-trimethyl-2-pentyl group, Examples include n-heptyl group, n-octyl group, n-decyl group, stearyl group and the like.

  In addition, “—R” in the general formulas (1) and (2) may be a cycloalkyl group, preferably a cycloalkyl group having 4 to 12 carbon atoms, and more preferably a cycloalkyl group having 5 to 10 carbon atoms. Specific examples include cyclopentyl propiolate, cyclohexyl propiolate, cycloheptyl propiolate, cyclooctyl propiolate and the like. Moreover, a part of this cycloalkyl group may be substituted, and examples thereof include propiolic acid (4-tert-butyl) -cyclohexyl, propiolic acid (2-isopropyl-5-methyl) -cyclohexyl and the like.

  Further, “—R” in the general formulas (1) and (2) may be an aryl group, and examples thereof include a phenyl group, a biphenyl group, and a naphthyl group. Among them, 2-methyl-phenyl propiolate or propiolic acid 4 -Tert-butyl-phenyl and the like are preferable.

  In addition, “—R” in the general formulas (1) and (2) may be a part or all of hydrogen in the alkyl group, cycloalkyl group or aryl group substituted with halogen, for example, substituted with fluorine atom. 2,2,2-trifluoroethyl group, n-perfluorobutyl-2-ethyl group, n-perfluorooctyl-2-ethyl group, 4-trifluoromethyl-cyclohexyl group, 2-trifluoromethyl-phenyl It may be a group or a 2,4-bis (trifluoromethyl) phenyl group.

  Furthermore, “—R” in the general formulas (1) and (2) may have a hydrophilic group. Examples of the hydrophilic group include a hydroxyl group, a carboxyl group, a sulfoxide group, and an amino group.

This porous body can be obtained by polymerizing or copolymerizing the substituted acetylene using a known polymerization method. In this polymerization, it is preferable to use a rhodium (Rh) complex as a catalyst. Examples of the Rh complex include [Rh (norbornadiene) Cl] ₂ , [Rh (cyclooctadiene) Cl] _{2, and} [Rh (bis-cyclooctene) Cl] _2. Among them, [Rh (norbornadiene) Cl] ₂ is preferable. It is. A metal catalyst such as tungsten (W) or molybdenum (Mo) may be used.

  In this polymerization, it is preferable to use a poor solvent having low solubility of the polyacetylene derivative such as alcohol, amine, acetonitrile, ether, acetate, acetone, water or n-hexane. Alternatively, the substituted acetylene may be polymerized at room temperature for several hours using a mixed solvent such as alcohol containing amine, toluene, chloroform, dimethylformamide, dimethyl sulfoxide, or supercritical liquid carbon dioxide.

  Since the polyacetylene derivative polymerized in this manner aggregates and precipitates in a solvent, a porous body can be obtained by collecting the precipitate and drying it. The obtained porous body can be used as a molecular adsorbent as it is, but natural or synthetic fibers such as cellulose acetate, polyamide, polyester, polycarbonate, polysulfone, polyethersulfone, polyolefin, polytetrafluoroethylene derivative or paper Alternatively, it may be combined with inorganic fibers such as glass or alumina. Also. Examples of the shape of the molecular adsorbent include bulk bodies, woven fabrics, nonwoven fabrics, and molecular thin films.

  Thus, since the molecular adsorbent according to the present invention can selectively adsorb and store molecules to be adsorbed, it is suitable for a gas storage container that is easily scattered and dangerous and difficult to handle. In addition, the molecular adsorbent according to the present invention is automatically adsorbed only by bringing it into contact with the molecule to be adsorbed, and the adsorbed molecule is easily detached from the pores simply by applying heat or vibration. Is very easy. In addition, the molecular adsorbent according to the present invention is heavy, as seen in hydrogen storage alloys such as palladium alloys, and requires special operations to dissociate the adsorbed hydrogen molecules, causing problems such as alloy powdering. Does not occur. Therefore, if the molecular adsorbent according to the present invention is used as, for example, a vehicle seat structure material, even hydrogen molecules that require handling can be safely stored and transported. Therefore, if the molecular adsorbent according to the present invention is used as a constituent material for a gas storage container or a machine part, a gas storage device that is lightweight, safe, and easy to use repeatedly can be obtained.

  In addition, the molecular adsorbent according to the present invention repeats the adsorption and desorption of molecules, so that its crystallinity increases and the pore structure becomes stronger and the amount of adsorbed molecules increases. It has the feature to do.

  Hereinafter, the molecular adsorbent and the production method thereof according to the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

Example 1
20 mmol of polymerization catalyst [Rh (norbornadiene) Cl] ₂ was put into a two-port U-shaped tube with a sealing seal made of silicon rubber from one of the ports, and nitrogen substitution was sufficiently performed through dry nitrogen gas. . Further, a dry tetrahydrofuran solution containing a predetermined amount of methanol was added to the polymerization solvent from the same mouth as before using a syringe. Further, 4 ml of methyl propiolate (manufactured by Tokyo Chemical Industry Co., Ltd.) purified by a vacuum distillation method was injected from a mouth different from the previous one using a syringe so that methyl propiolate did not touch the polymerization catalyst. And after immersing this U-shaped tube in a constant temperature bath of 40 ° C., the contents were sufficiently mixed and then methyl propiolate was polymerized. After 24 hours from the start of polymerization, the content of the U-tube was poured into a large amount of methanol to precipitate methyl polypropiolate. This precipitate was recovered and purified by reprecipitation in a tetrahydrofuran-methanol system, and then dried under reduced pressure to produce a bulk body (porous body) in which methyl polypropiolate was aggregated.

  In addition, a bulk product in which ethyl polypropiolate was aggregated was produced in the same manner except that ethyl propiolate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of the methyl propiolate.

  The amount of adsorbed hydrogen molecules per unit weight of the thus-produced methyl polypropiolate bulk and ethyl polypropiolate bulk was measured as follows.

[Measurement of hydrogen molecule adsorption]
The amount of adsorbed hydrogen molecules on the methyl polypropiolate bulk and the ethyl polypropiolate bulk was measured by a constant volume method using BELSORP28SA manufactured by Nippon Bell Co., Ltd. Specifically, after the bulk body of methyl polypropiolate and the bulk body of ethyl polypropiolate were left in separate chambers filled with helium at room temperature for a predetermined time, the respective chambers were evacuated. It should be noted that helium is not adsorbed on the bulk of methyl polypropiolate and the bulk of ethyl polypropiolate. Then, a predetermined amount of hydrogen is injected into the vacuum chamber, and the pressure immediately after the injection and the pressure at the time of 300 s (equilibrium) are measured. Based on the difference between these measured values, the methyl polypropiolate The hydrogen gas capacity (0 °, 101.3 kPa equivalent) per unit weight adsorbed on the bulk body and the bulk body of ethyl polypropiolate was calculated. The hydrogen injection and adsorption amount calculation were repeated until the pressure in each chamber reached 101.3 kPa (maximum pressure).

  Subsequently, after reaching the maximum pressure, while evacuating a predetermined amount of hydrogen filled in each chamber, the pressure immediately after the evacuation and the pressure at the time of 300 s after the evacuation (at equilibrium) are measured. The hydrogen gas capacity per unit weight (0 °, 101.3 kPa equivalent value) adsorbed on the bulk of methyl polypropiolate and the bulk of ethyl polypropiolate was calculated.

  FIG. 2 is a graph showing a series of measurement results in the measurement of the hydrogen molecule adsorption amount. In FIG. 2, “◯” indicates the amount of hydrogen molecule adsorption from the time of evacuation until the maximum pressure is reached for the bulk polymethyl methyl propiolate. Similarly, “●” indicates from the maximum pressure to the completion of pressure reduction for the methyl polypropiolate bulk, and “△” indicates from the time of evacuation until the maximum pressure is reached for the ethyl polypropiolate bulk. Indicates the hydrogen molecule adsorption amount from the maximum pressure to the completion of the pressure reduction for the bulk of ethyl polypropiolate.

  Table 1 shows the amount of adsorbed hydrogen molecules at the time of evacuation (before adsorption), at the maximum pressure and at the time of completion of decompression (after decompression) for each of the bulk of methyl polypropiolate and the bulk of ethyl polypropiolate. The hydrogen gas capacity per unit weight of the bulk body (0 °, 101.3 kPa equivalent) is shown.

  As apparent from FIG. 2 and Table 1, the hydrogen molecule adsorption amount of the methyl polypropiolate bulk is 5 times or more that of ethyl polypropiolate. Here, in view of the fact that methyl polypropiolate and ethyl polypropiolate differ only in the size of the side chain, most of the hydrogen molecules adsorbed on the porous polymethylated polypropiolate are adjacent to each other. Presumed to be adsorbed in the voids between the helical chains. That is, it can be seen from the measurement result of the hydrogen molecule adsorption amount that the molecule to be adsorbed on the porous body in which the polyacetylene derivative is aggregated can be selected by adjusting the size of the side chain of the polyacetylene derivative.

  Further, as is apparent from FIG. 2 and Table 1, the bulk of methyl polypropiolate and the bulk of ethyl polypropiolate contain a considerable amount of hydrogen molecules even when the pressure is reduced from the maximum pressure to almost vacuum. Adsorbed. From this, it can be seen that the porous body in which the polyacetylene derivative is aggregated not only holds the molecules in the surface and internal voids but also holds and fixes them firmly.

  In addition, since hydrogen molecules are adsorbed at a ratio of approximately 8 ml / g (0 °, 101.3 kPa equivalent) to the porous body in which methyl polypropiolate is aggregated, the hydrogen molecules adsorbed on the porous body The weight percentage is 0.07%. Further, referring to the slope of the graph shown in FIG. 2, when hydrogen molecules are adsorbed at 5 MPa on a porous body in which methyl polypropiolate is aggregated, the weight percentage becomes 3.5%. Incidentally, the weight percentage of hydrogen molecules packed in a commercially available steel pressure vessel at 20 MPa is about 1%, and the weight percentage of hydrogen molecules stored in a hydrogen storage alloy such as a palladium alloy at 1 MPa is 2%. It is reported.

(Example 2)
In this Example, micropore distribution measurement and specific surface area measurement by the BET (Brunauer-Emmett-Teller) method were performed on methyl polypropiolate, ethyl polypropiolate, and propyl polypropiolate. In addition, the sample used for these measurements was produced | generated by the method similar to the production | generation method of the bulk body (porous body) which the methyl polypropiolate aggregated in the said Example 1.

[Micropore distribution measurement] and [BET specific surface area measurement]
The three types of porous bodies produced in this example were subjected to dead volume correction with helium gas using a fully automatic gas adsorption amount measuring device AUTOSORB-1MP manufactured by Quantachrome, and then the nitrogen gas was heated to 77.degree. It was made to adsorb | suck at 4K and the micropore (pore diameter 2nm or less) distribution by SF method was measured. In this measurement, it was 1.04 nm for methyl polypropiolate, but no sharp distribution was observed in the micropore region for ethyl polypropiolate and propyl polypropiolate. Incidentally, in this example, the distribution of mesopores (pore diameter 2 to 50 nm) and macropores (pore diameter 50 nm or more) was not measured.

  Moreover, after performing dead volume correction | amendment with helium gas about said three types of porous bodies using said fully automatic gas adsorption amount measuring apparatus AUTOSORB-1MP, nitrogen gas is adsorbed at the temperature of 77.4K. The specific surface area was measured by the BET method.

  The measurement results of the micropore distribution by the SF method and the measurement results of the BET specific surface area are shown together in “Table 2” below.

  From the measurement result by the SF method in this example, micropores having a pore diameter of 2 nm or less are not formed so much in the porous material aggregated with ethyl polypropiolate and the porous material aggregated with propylpolypropiolate. I understand that. Furthermore, considering the measurement results in this example and the hydrogen molecule adsorption amount shown in Table 1, it can be seen that hydrogen molecules are selectively adsorbed to micropores having a pore diameter of 2 nm or less.

(Example 3)
In this example, it was confirmed how the average pore diameter of the porous body in which the polyacetylene derivative was aggregated changed when the substituted acetylene having a halogen-substituted side chain was polymerized. In this example, chlorine (Cl), bromine (Br) and iodine (I) were used as halogens.

  First, 2-halogenated ethyl alcohol and propiolic acid are subjected to a dehydration reaction in the presence of p-toluenesulfonic acid, and further distilled under reduced pressure to produce ethyl propiolate halide (hereinafter referred to as “XEPA”, “X”). Produced a halogen). This XEPA was polymerized under the same conditions as in Example 1 to produce poly (XEPA).

And the physical property of each produced | generated poly (XEPA) was measured as follows. The number average molecular weight (Mn) was measured using GPC900-1 manufactured by JASCO, equipped with two K-806L columns and an RI detector. Further, using a JEOL Ltd. JNM-A400II, and chloroform -d ₁ and tetramethylsilane was analyzed by ¹ H-NMR as the solvent. Moreover, the diffuse reflection ultraviolet spectrum was measured using JASCO V570 equipped with ISV-469. Further, electron spin resonance ESR was measured using FEIXG manufactured by JEOL. Further, an X-ray diffraction pattern was recorded using JDX-300 manufactured by JOEL. The measurement results and the analysis results are summarized in “Table 3” below.

  In this example, for polypropiolic acid brominated ethyl poly (BrEPA) and polypropiolic acid iodinated ethyl poly (IEPA), the X-ray diffraction pattern could not be clearly recorded. The pore size could not be calculated. However, in view of the average pore size of ethyl polypropiolate poly (EPA) and polychlorinated ethyl polypropiolate poly (ClEPA), the porous body is formed by bonding atoms with a large atomic radius to the side chain of the polyacetylene derivative. It can be seen that the average pore diameter increases. Therefore, it can be seen from the measurement results and analysis results of this example that the larger the side chain of the polyacetylene derivative, the larger the average pore size of the porous body in which the polyacetylene derivative is aggregated.

Example 4
In this example, by gradually increasing the side chain, the average pore size of the aggregated porous body of the polyacetylene derivative is changed, and by exposing this porous body to chloroform vapor, It was confirmed how the average pore diameter changed.

First, using a method described in “Tabata et al., Chem. Phys, 1999.200, 265”, paramethoxyphenylacetylene (hereinafter referred to as “p-MeOPA”), paraethoxyphenylacetylene (hereinafter referred to as “p-EtOPA”). )), Pn-butoxyphenylacetylene (hereinafter, “pn-BuOPA”), pn-hexyloxyphenylacetylene (hereinafter, “pn-HexOPA”), pn-octoxyphenylacetylene (Hereinafter, “pn-OctOPA”), pn-decaneoxyphenylacetylene (hereinafter, “pn-C ₁₀ OPA”), pn-dodecanoxyphenylacetylene (hereinafter, “p-n-”). C ₁₂ OPA ”) and pn-tetradecanoxyphenylacetylene (hereinafter“ pn-C ₁₄ OPA ”). And these produced | generated acetylene derivatives were superposed | polymerized on the same conditions as Example 1, respectively, and the porous body which the polyacetylene derivative from which the magnitude | size of a side chain differs was each produced | generated.

And the physical property of these porous bodies was measured as follows. Using a gel permeation chromatography (GPC900 manufactured by JASCO) equipped with two Kdex-806L columns manufactured by Shodex, the ratio (Mw / Mn) of Mn and weight-average molecular weight (Mw) to Mn It was measured. In addition, ¹ H-NMR was measured using JNM-A JNM-A 400 MHz with chloroform-d ₁ as a solvent. Moreover, the Raman spectrum was measured with 514.5 nm argon laser using JASCO TSR-401. Moreover, the diffuse reflection ultraviolet-near infrared spectrum was measured using JASCO V570. Further, an X-ray diffraction pattern was recorded using JDX-3500 manufactured by JOEL.

  Furthermore, after these porous bodies were exposed to chloroform vapor, X-ray diffraction patterns were recorded again using JDX-3500 manufactured by JOEL. The measurement results and the analysis results thereof are summarized in “Table 4” below.

  As is apparent from Table 4, it can be seen that the average pore diameter of the porous body increases as the side chain of the polyacetylene derivative increases. Therefore, from the analysis results of this example, it can be seen that the larger the side chain of the polyacetylene derivative, the larger the average pore size of the porous body aggregated with the polyacetylene derivative.

  Further, as is apparent from Table 4, it can be seen that when the porous body in which the polyacetylene derivative is aggregated is exposed to the vapor of chloroform, the average pore diameter is increased. Therefore, it can be seen from the analysis results of this Example that the average pore size of the porous body can be adjusted by exposing the porous body in which the polyacetylene derivative is aggregated with the vapor of chloroform or toluene.

(Example 5)
In this example, a ¹²⁹ Xe NMR spectrum shows how the average pore diameter of a porous body aggregated with a polyacetylene derivative whose side chain is paraphenol ether changes when immersed in a toluene solvent. It was confirmed by measuring.

First, a poly (ps2MBPA) aggregated porous body having the structure shown in FIGS. 3 and 4 was produced by a known means, and a part of the produced porous body was separated and immersed in a toluene solvent. Then, the porous body before the solvent treatment and the porous body after the solvent treatment are individually put in an NMR tube (Type513-7 JYH-7, manufactured by Wilmad, with Teflon (registered trademark) valve, outer diameter 10 mm), These NMR tubes were degassed and then cooled with liquid nitrogen. During this cooling, xenon (solid during cooling) was charged into these NMR tubes so that the internal pressure when returning to room temperature was 0.5 MPa. And after returning these NMR tubes to room temperature and allowing them to stand for 24 hours, using GX400NMR manufactured by JEOL Ltd., a single pulse method of irradiating a 30 ° pulse, without spinning, an observation frequency of 110.4 MHz, the number of integrations It was set to about 3000 times, and ¹²⁹ Xe NMR spectra of the porous body before the solvent treatment and the porous body after the solvent treatment were measured. FIG. 3 shows the spectrum of the porous body before the solvent treatment, and FIG. 4 shows the spectrum of the porous body after the solvent treatment.

  In FIG. 3, the spectrum peak appears at 204 ppm, while in FIG. 4, it appears at 196 ppm. Here, since the chemical shift of the gas phase has a proportional relationship with the pressure, it is necessary to add a correction depending on the pressure to the actually measured values of these spectra. Specifically, a correction of 0.54 ppm per 0.1 MPa is necessary. Therefore, in this embodiment, since the internal pressure in the NMR tube is 0.5 MPa, it is necessary to add 0.54 × 5 = 2.7 ppm to the actual measurement value as a correction value. As a result, the peak of the spectrum for the porous body before the solvent treatment appears at 206.7 ppm, and the peak of the spectrum for the porous body after the solvent treatment appears at 198.7 ppm. On the basis of this corrected spectrum, assuming that all of these porous bodies are amorphous, the average pore diameter is 5.12 mm before solvent treatment and 5.32 mm after solvent treatment.

  Here, in the spectra shown in FIG. 3 and FIG. 4, the peak appearing near 200 ppm corresponds to xenon adsorbed on the porous body, while the peak appearing near 0 ppm corresponds to gas phase xenon. Is. Therefore, it can be seen from the spectra shown in FIGS. 3 and 4 that when the average pore size is increased by the toluene solvent treatment, more xenon is adsorbed on the porous body.

Further, from the ¹²⁹ Xe NMR spectrum shown in FIGS. 3 and 4, the porous body before the solvent treatment is binary sorbed, that is, xenon is absorbed in both the vicinity of the main chain and the vicinity of the side chain. It is considered to be relatively amorphous with the chains and side chains intermingled. On the other hand, the porous body after the solvent treatment is rubbery and has a dense main chain, and there is a free volume near the alkyl group at the end of the side chain. It is thought that the length is relatively uniform.

(Reference example)
In this reference example, it was confirmed what kind of change appears in the physical properties of the porous body by pressurizing the porous body in which the polyacetylene derivative is aggregated. In this reference example, phenylacetylene was polymerized by a known means to produce polyphenylacetylene. And the physical property of the produced | generated polyphenylacetylene was measured with the same apparatus and conditions as Example 4. FIG.

  Furthermore, after pressurizing the produced polyphenylacetylene at 10 MPa and 20 MPa, their physical properties were measured again with the same apparatus and conditions as in Example 4. The measurement results and the analysis results are summarized in “Table 5” below.

  As is apparent from Table 5, the higher the pressure for pressurizing the porous body in which polyphenylacetylene is aggregated, the Mw / Mn of the porous body approaches 1 and the crystallinity of the porous body decreases. I know that In addition, it shows that the dispersion | variation in the molecular weight of a polyacetylene derivative became small, so that Mw / Mn was close to 1.

  The molecular adsorbent according to the present invention includes a gas storage device, a color variable material, a material constituting an electron supply layer of an organic EL device, a light shielding material, a heat ray shielding material, a lithium battery material, a thermoelectric element, a solar cell material, It can be used for organic semiconductors, nonlinear optical materials, magnetic materials, conductive materials, and the like.

The figure which shows simply the structure of the porous body which the polyacetylene derivative of this invention aggregated The figure which shows the measurement result of the hydrogen molecule adsorption amount in Example 1 which concerns on this invention The figure which shows ¹²⁹ Xe NMR spectrum about the porous body before the solvent process in Example 5 which concerns on this invention The figure which shows ¹²⁹ Xe NMR spectrum about the porous body after the solvent process in Example 5 which concerns on this invention

Claims (7)

  A molecular adsorbent comprising a porous body in which a polyacetylene derivative having a cis-transoid structure in which a main chain is in a helical form and a side chain is located outside a main chain helix is aggregated. The molecular adsorbent according to claim 1, wherein the polyacetylene derivative is obtained by polymerizing or copolymerizing substituted acetylene using a rhodium (Rh) complex as a catalyst. The polyacetylene derivative is Poripuropioru methyl, claim 1 or 2 molecules adsorbing material according to adsorb hydrogen molecules.   The size of the side chain is adjusted when a porous body is formed by aggregating a polyacetylene derivative having a cis-transoid structure in which the main chain is helical and the side chain is located outside the main chain helix. By doing this, the manufacturing method of the molecular adsorbent which adjusts the average pore diameter of the said porous body.   By exposing a porous material in which a polyacetylene derivative having a cis-transoid structure in which the main chain is in the form of a spiral and the side chain is located outside the main chain, to a chloroform, toluene, tetrahydrofuran or alcohol, A method for producing a molecular adsorbent for adjusting an average pore size of the porous body. A gas storage device comprising the molecular adsorbent according to any one of claims 1 to 3 . The gas storage device according to claim 6, wherein the polyacetylene derivative is methyl polypropiolate and adsorbs and stores hydrogen molecules.

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