KR20090098242A - Crystalline polymorph of cucurbituril compounds, its preparation method, and methods of storing, separating and removing gas using crystalline polymorph of cucurbituril compounds - Google Patents

Abstract

A crystalline polymorph of cucurbituril compound and a method for storing, separating and removing gas using the same are provided to ensure thermally stable structure of the polymorph and dip gas. A crystalline polymorph of cucurbituril compound of the chemical formula 1 contains cavity which is surrounded with plural cucurbituril compounds. A method for manufacturing the crystalline polymorph of the cucurbituril compound comprises: a step of making the cucurbituril compound under the acidic condition; and a step of vacuum drying the crystalline polymorph at 50°C~300°C for 30 minutes to 96 hours to activate.

Description

Crystalline polymorph of a cucurbituryl compound, a method for preparing the same, and a method for storing, separating and removing a gas using the crystalline polymorph of a cucurbituryl compound. {Crystalline polymorph of cucurbituril compounds, its preparation method, and methods of storing, separating and removing gas using crystalline polymorph of cucurbituril compounds}

The present invention relates to a crystalline polymorph of a cucurbituryl compound, and more particularly, to a crystalline polymorph of a cucurbituryl compound capable of supporting a gas in a cavity contained therein while having a thermally very stable structure, the cucurbituryl compound A structure in which a gas is supported on a crystalline polymorph of ethylene, a method for preparing a crystalline polymorph of the cucurbituryl compound, a gas storage method for supporting a gas into a cavity contained in a crystalline polymorph of the cucurbituryl compound, and a crystal of the cucurbituryl compound A method of selectively separating a gas to selectively support only a specific gas in a gas mixture into a cavity included in a sex polymorph, and a method of selectively removing a specific gas into a cavity included in a crystalline polymorph of the cucurbituril compound to remove a gas. A method for the selective removal of certain gases.

Porous materials are regularly distributed with pores in the multidimensional framework, and can selectively adsorb gas molecules or small organic molecules according to the three-dimensional and chemical environment of the pores, and can be used for the purpose of catalyst, ion exchange, and mixture separation. [A) S. Kitagawa, R. Kitaura, S.-i. Noro, Angew . Chem . 2004, 116 , 2388-2430; Angew. Chem . Int . Ed. 2004, 43 , 2334-2375; b) JLC Rowsell, OM Yaghi, Angew . Chem . 2005, 117 , 4748-4758; Angew . Chem . Int . Ed. 2005, 44 , 4670-4679; c) G. Ferey, Chem . Soc . Rev. 2008, 37 , 191-214.

Cucurbituril [6] is a cyclic oligomer formed by linking six glycoryl monomers with methylene bridges, synthesized from inexpensive compounds such as glycoril and formaldehyde. ( J. Am. Chem . Soc . , 1981, 103 , 7367-7368) published by WA Freeman et al .

Cooker bituril [6] has a chemical formula of C ₃₆ H ₃₆ N ₂₄ O ₁₂ and is a compound having a pupil therein. Cucurbituril homologues and derivatives are described in the articles published by Kim (K. Kim) et al . ( J. Am. Chem . Soc . , 2000, 122 , 540-541) and ( J. Am. Chem . 2003, 125 , 10186-10187), or by a co-author published by Day (A. Day) et al . ( J. Org . Chem . , 2001, 66 , 8094-8100). . In addition, methods for adsorbing gaseous or volatile compounds to cucurbituril homologues and derivatives have been studied (US Pat. No. 6,869,466). These existing technologies only cover adsorption and storage of indiscriminate gases.

The technical problem to be achieved by the present invention is to provide a crystalline polymorph of a cucurbituril compound.

Another object of the present invention is to provide a structure in which a gas is supported on a crystalline polymorph of a cucurbituril compound.

Another technical problem to be achieved by the present invention is to provide a method for preparing a crystalline polymorph of a cucurbituril compound.

Another object of the present invention is to provide a gas storage method for supporting a gas into a cavity included in a crystalline polymorph of a cucurbituril compound.

Another technical problem to be achieved by the present invention is to provide a method for selectively separating a gas selectively supporting only a specific gas in a gas mixture into a cavity included in the crystalline polymorph of the cucurbituril compound.

Another technical problem to be achieved by the present invention is to provide a method for selectively removing a specific gas to remove the gas by selectively supporting a specific gas into the cavity included in the crystalline polymorph of the cucurbituril compound.

The present invention provides a first aspect for achieving the above object,

It provides a crystalline polymorph of a cucurbituril compound represented by the following formula (1) comprising a cavity. The cavity is surrounded by a plurality of adjacent cucurbituril compounds:

<Formula 1>

Wherein n A ₁ and n A ₂ are each independently hydrogen, a hydroxy group, a substituted or unsubstituted C 1 -C 30 alkyloxy group, a substituted or unsubstituted C 1 -C 30 alkene. Nyloxy group, substituted or unsubstituted C1-C30 alkynyloxy group, substituted or unsubstituted C2-C30 carbonylalkyloxy group, substituted or unsubstituted C1-C30 thioalkyloxy group, substituted Or an unsubstituted C1-C30 alkylthioloxy group, a substituted or unsubstituted C1-C30 hydroxyalkyloxy group, a substituted or unsubstituted C1-C30 alkylsilyloxy group, a substituted or unsubstituted C1-C30 aminoalkyloxy group, substituted or unsubstituted C1-C30 aminoalkylthioalkyloxy group, substituted or unsubstituted C5-C30 cycloalkyloxy group, substituted or unsubstituted C5-C30 Heterocycloalkyloxy groups, substituted or unsubstituted C6-C30 aryloxy groups, substituted or unsubstituted C6-C20 Alkyloxy group, substituted or unsubstituted C4-C30 heteroaryloxy group, substituted or unsubstituted C4-C20 heteroarylalkyloxy group, substituted or unsubstituted C1-C30 alkylthio group, substitution Or unsubstituted C1-C30 alkenylthio group, substituted or unsubstituted C1-C30 alkynylthio group, substituted or unsubstituted C2-C30 carbonylalkylthio group, substituted or unsubstituted C1 -C30 thioalkylthio group, substituted or unsubstituted C1-C30 hydroxyalkylthio group, substituted or unsubstituted C1-C30 alkylsilylthio group, substituted or unsubstituted C1-C30 amino Alkylthio group, substituted or unsubstituted C1-C30 aminoalkylthioalkylthio group, substituted or unsubstituted C5-C30 cycloalkylthio group, substituted or unsubstituted C5-C30 heterocycloalkyl tee Or substituted or unsubstituted C6-C30 arylthio groups, substituted or unsubstituted C6-C20 arylal Thio group, substituted or unsubstituted C4-C30 heteroarylthio group, substituted or unsubstituted C4-C20 heteroarylalkylthio group, substituted or unsubstituted C1-C30 alkylamine group, substituted Or unsubstituted C1-C30 alkenylamine group, substituted or unsubstituted C1-C30 alkynylamine group, substituted or unsubstituted C2-C30 carbonylalkylamine group, substituted or unsubstituted C1-C30 thioalkylamine group, substituted or unsubstituted C1-C30 hydroxyalkylamine group, substituted or unsubstituted C1-C30 alkylsilylamine group, substituted or unsubstituted C1-C30 Aminoalkylamine groups, substituted or unsubstituted C1-C30 aminoalkylthioalkylamine groups, substituted or unsubstituted C5-C30 cycloalkylamine groups, substituted or unsubstituted C5-C30 heterocycloalkyl Amine group, substituted or unsubstituted C6-C30 arylamine group, substituted or unsubstituted C6-C20 arylalkylamine Group, a substituted or unsubstituted C4-C30 heteroarylamine group and a substituted or unsubstituted C4-C20 heteroarylalkylamine group, wherein at least n A ₁ and n A ₂ One is not hydrogen and n is an integer from 4 to 12.

The present invention provides a second aspect for achieving the above object,

A crystalline polymorph of a cucurbituril compound represented by Formula 1, comprising a cavity, and a structure supporting a gas into the cavity, wherein the cavity is surrounded by a plurality of adjacent cucurbituryl compounds. do.

The present invention in a third aspect to achieve the above object,

Forming the crystalline polymorph of the cucurbituril compound by preparing the cucurbituril compound under acidic conditions and activating the crystalline polymorph of the formed cucurbituril compound by vacuum drying at 50 ° C to 300 ° C for 30 minutes to 96 hours. A method for preparing a crystalline polymorph of a cucurbituryl compound comprising: the cucurbituryl compound is represented by Formula 1, wherein the crystalline polymorph of the cucurbituryl compound includes a cavity, and the cavity is surrounded by a plurality of adjacent cucurbituryl compounds Provided are a method for producing a crystalline polymorph of a cucurbituril compound.

The present invention provides a fourth aspect for achieving the above object,

A gas storage method for supporting a gas into a cavity included in a crystalline polymorph of the cucurbituril compound represented by Formula 1, wherein the cavity is surrounded by a plurality of adjacent cucurbituryl compounds.

In a fifth aspect of the present invention,

A selective separation method of a gas for selectively supporting only a specific gas in a gas mixture into a cavity included in a crystalline polymorph of the cucurbituril compound represented by Formula 1, wherein the cavity is surrounded by a plurality of adjacent cucurbituryl compounds It provides a method for selective separation of a particular gas.

In a sixth aspect of the present invention,

A selective removal method of a specific gas to selectively remove a specific gas into a cavity contained in the crystalline polymorph of the cucurbituril compound represented by Formula 1, wherein the cavity is surrounded by a plurality of adjacent cucurbituryl compound molecules A method of selective removal of a particular gas is provided.

The crystalline polymorph of the cucurbituril compound represented by Chemical Formula 1 according to the present invention may support a gas in a cavity contained therein while having a thermally very stable structure.

Hereinafter, the present invention will be described in more detail.

The present invention provides a crystalline polymorph of a cucurbituril compound represented by the following formula (1).

Wherein n A ₁ and n A ₂ are each independently hydrogen, a hydroxy group, a substituted or unsubstituted C 1 -C 30 alkyloxy group, a substituted or unsubstituted C 1 -C 30 alkene. Nyloxy group, substituted or unsubstituted C1-C30 alkynyloxy group, substituted or unsubstituted C2-C30 carbonylalkyloxy group, substituted or unsubstituted C1-C30 thioalkyloxy group, substituted Or an unsubstituted C1-C30 alkylthioloxy group, a substituted or unsubstituted C1-C30 hydroxyalkyloxy group, a substituted or unsubstituted C1-C30 alkylsilyloxy group, a substituted or unsubstituted C1-C30 aminoalkyloxy group, substituted or unsubstituted C1-C30 aminoalkylthioalkyloxy group, substituted or unsubstituted C5-C30 cycloalkyloxy group, substituted or unsubstituted C5-C30 Heterocycloalkyloxy groups, substituted or unsubstituted C6-C30 aryloxy groups, substituted or unsubstituted C6-C20 Alkyloxy group, substituted or unsubstituted C4-C30 heteroaryloxy group, substituted or unsubstituted C4-C20 heteroarylalkyloxy group, substituted or unsubstituted C1-C30 alkylthio group, substitution Or unsubstituted C1-C30 alkenylthio group, substituted or unsubstituted C1-C30 alkynylthio group, substituted or unsubstituted C2-C30 carbonylalkylthio group, substituted or unsubstituted C1 -C30 thioalkylthio group, substituted or unsubstituted C1-C30 hydroxyalkylthio group, substituted or unsubstituted C1-C30 alkylsilylthio group, substituted or unsubstituted C1-C30 amino Alkylthio group, substituted or unsubstituted C1-C30 aminoalkylthioalkylthio group, substituted or unsubstituted C5-C30 cycloalkylthio group, substituted or unsubstituted C5-C30 heterocycloalkyl tee Or substituted or unsubstituted C6-C30 arylthio groups, substituted or unsubstituted C6-C20 arylal Thio group, substituted or unsubstituted C4-C30 heteroarylthio group, substituted or unsubstituted C4-C20 heteroarylalkylthio group, substituted or unsubstituted C1-C30 alkylamine group, substituted Or unsubstituted C1-C30 alkenylamine group, substituted or unsubstituted C1-C30 alkynylamine group, substituted or unsubstituted C2-C30 carbonylalkylamine group, substituted or unsubstituted C1-C30 thioalkylamine group, substituted or unsubstituted C1-C30 hydroxyalkylamine group, substituted or unsubstituted C1-C30 alkylsilylamine group, substituted or unsubstituted C1-C30 Aminoalkylamine groups, substituted or unsubstituted C1-C30 aminoalkylthioalkylamine groups, substituted or unsubstituted C5-C30 cycloalkylamine groups, substituted or unsubstituted C5-C30 heterocycloalkyl Amine group, substituted or unsubstituted C6-C30 arylamine group, substituted or unsubstituted C6-C20 arylalkylamine Group, a substituted or unsubstituted C4-C30 heteroarylamine group and a substituted or unsubstituted C4-C20 heteroarylalkylamine group, wherein at least n A ₁ and n A ₂ One is not hydrogen and n is an integer from 4 to 12.

The term "substituted" used in the definition of a substituent in the formula of the present invention means substituted with any substituent, and as examples of the substituent, an alkyl group of C1-C5, an alkoxy group of C1-C5, of C5-C6 Aryl group, C2-C6 heteroaryl group, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, etc. are mentioned.

Preferably, the n A ₁ and n A ₂ may be independently selected from hydrogen, a hydroxyl group, methyl, ethyl, and the like. Also preferably, any two or more of n A ₁ and n A ₂ may be connected. For example, any adjacent two of n A ₁ and n A ₂ may be joined to form a cyclohexyl.

The crystalline polymorph is a porous material comprising a cavity.

The crystalline polymorph according to the present invention has a crystalline skeletal structure formed by three-dimensional stacking of cucurbituryl compound molecules represented by the formula (1), and thus forms the crystalline structure and has the same pattern regularly distributed at the same time. Forming a cavity. As such, the cavity included in the crystalline polymorph is formed by being surrounded by a plurality of adjacent cucurbituril compounds.

On the other hand, as known, the cucurbituril compound forms a cavity inside one molecule, and the cavity is a concept that is distinguished from a cavity formed inside one molecule of the cucurbituril compound. In order to avoid confusion between the above concepts, for convenience, the empty space inside the molecule of the cucurbituryl compound 1 is referred to as a "pores", and as described above, a plurality of cucurbituryl compound molecules are formed while forming a crystalline polymorph through a stacked structure. The empty space is expressed as "joint".

The term "polymorph" refers to a substance capable of forming various structures having different molecular weights, that is, properties of crystals formed, even if the same molecule depends on synthetic conditions.

The cucurbituril compound represented by the formula (1) has a property that the three-dimensional stacked structure of the molecule differs depending on which specific cucurbituryl compound is used or synthesized using its synthesis conditions, in particular, what kind of acid. The crystalline polymorph according to the invention is formed using this property.

As described above, the crystalline polymorph according to the present invention, which is a material having such a three-dimensional structure, is a porous material, and because it forms a cavity crystal in the crystalline polymorph material, the molecules of the cucurbituryl compound represented by the formula (1) are regularly stacked. Is distributed regularly, and its size is constant. Since the crystal structure differs depending on the synthesis conditions, the size and shape of the cavities depend on the kind of the cucurbituril compound and its synthesis conditions, particularly acid conditions. For example, the cavity may be in the form of a channel (see FIG. 1B).

The cucurbituril compound may be obtained by heating glycoryl and paraformaldehyde in an acid, at a high temperature for a predetermined time, then cooling it to room temperature and fractionating crystals. In this case, for example, the crystal structure of the cucurbituryl compound crystalline polymorph is formed differently depending on the type of the acid.

Examples of the type of acid that can be used in synthesizing the cucurbituril compound to form the crystalline polymorph of the cucurbituril compound represented by Formula 1 include hydrochloric acid (HCl), hydrobromic acid (HBr), hydroiodic acid (HI), phosphoric acid ( H ₃ PO ₃ ), p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid (H ₂ SO ₄ ), nitric acid (HNO ₃ ), acetic acid (CH ₃ COOH), carbonic acid (H ₂ CO ₃ ), formic acid (CH ₂ O ₂ ), trifluoromethanesulfonic acid (CF ₃ SO ₃ H), and the like, and mixtures of two or more of these acids may also be used.

When preparing a crystalline polymorph according to the present invention by preparing a cucurbituril compound represented by Formula 1 under hydrochloric acid conditions (see Example 1 below), for example, FIGS. It is a crystal structure obtained by X-ray crystal structure analysis method for a shape. Each shows the three-dimensional honeycomb crystal structure formed by the hexagonal arrangement of cucurbituril [6] and the diameter of the cavity and the cavity in the one-dimensional channel form (6 mm 3).

FIG. 1D shows a crystal structure in which acetylene is adsorbed to the cavity of the one-dimensional channel form of the crystalline polymorph. The parts shown in red, blue, gray and white represent oxygen, nitrogen, carbon and hydrogen, respectively.

The X-ray crystal structures of the crystalline polymorphs in FIGS. 1A, 1B and 1C are as follows: Trigonal, R -3, a = 32.096 (2) ', c = 12.491 (1)', V = 11144 (1 ) ³ , R ₁ = 0.0992, GOF = 1.067.

Looking at the crystal structure in more detail (see FIG. 2), the portal carbonyl group and the CH or CH of cucurbituril [6] are formed while each cucurbituryl [6] molecule forms a twisted square planar arrangement with the four neighboring molecules closest to each other. CH between _two … O is strongly bonded through hydrogen bonding. At this time, the distance from center to center is 10.16 Å, and the angle between planes is 75.6 °. Each cucurbituril [6] molecule acts as a hydrogen bond donor to two trans neighboring molecules using the side CH or CH ₂ , and at the same time as a hydrogen bond acceptor from the other two neighboring molecules. Two portals of each cucurbituril [6] molecule are blocked by two neighboring cucurbituril [6] molecules, so that the water molecules trapped inside the cucurbituril [6] pupil are water molecules within the crystalline polymorphic internal cavity (channel form). More difficult to remove. Thus, a wide range of CH... The arrangement of cucurbituril [6] molecules enhanced by O-hydrogen bonds can be expanded three-dimensionally to form a highly stable supramolecular framework with channel-like cavities, thereby providing excellent stability of the crystalline polymorph of cucurbituril compounds. I can explain.

From a topological point of view, the crystalline polymorph of the cucurbituryl [6] compound is a tilted NbO net if, in FIGS. 3A and 3B, each cucurbituril [6] molecule is four connected nodes connected to each other at about 90 ° angles of the square plane. (Or 6 ⁴ 8 ² net) structure. NbO nets have not been identified so far as supramolecular skeleton structures of organic molecular solids.

As such, when the crystalline polymorph of the cucurbituril compound represented by Chemical Formula 1 is prepared under hydrochloric acid conditions, the cavity may form a channel, and the interval between the channels is about 0.2 nm to 4.0 nm. In addition, the diameter of the channel is about 0.3 nm to 1.0 nm.

As another example, looking at the case of preparing a crystalline polymorph according to the present invention by preparing a cucurbituril compound represented by the formula (1) in sulfuric acid conditions, Figures 4a and 4b is X in such a crystalline polymorph It is a crystal structure obtained by the -line crystal structure analysis method.

The crystallinity of the Figures 4a and 4b are molded as another example of a crystalline polymorph comprising a cucurbituril [6] of the formula 1, Kim (K. Kim) a paper published by the other co-authors (J. Am. Chem . Soc . , 2000, 122 , 540-541), was synthesized in H ₂ SO ₄ : Hexagonal, P -3, a = 15.230 (1) Å, c = 10.379 (1) Iii.

In Figures 4a and 4b one can see the cavities in the one-dimensional channel form, formed by the hexagonal arrangement of cucurbituril [6]. It is also a porous material formed using cucurbituril [6] under H ₂ SO ₄ conditions, and has a three-dimensional molecular stacking structure different from the porous material formed under HCl conditions.

As such, the cucurbituril compound represented by Chemical Formula 1 is a polymorph, which is a structure having the same molecule but different molecular accumulation structure depending on conditions. Therefore, the present invention is not limited only to the case of having a channel-shaped cavity in the case of the hydrochloric acid.

When the crystalline polymorph of the cucurbituril compound represented by Formula 1 is prepared under sulfuric acid conditions, the cavity may form a channel, and the interval between the channels is about 0.2 nm to 4.0 nm. The diameter of the channel is also about 0.6 nm to 1.0 nm.

Preferably, Formula 1 may be represented by the following Formula 2 to 5.

In said formula, n is an integer of 4-12.

In said formula, R is a methyl group (Me) and n is an integer of 4-12.

In said formula, n is an integer of 4-12.

In said formula, n is an integer of 4-12.

Gas may be supported in a cavity included in the crystalline polymorph according to the present invention. Accordingly, the present invention also provides a crystalline polymorph of a cucurbituril compound represented by the following formula (1) including a cavity and a structure in which a gas is carried into the cavity, wherein the cavity is surrounded by a plurality of adjacent cucurbituryl compounds. It provides a structure, characterized in that.

<Formula 1>

Wherein n A ₁ and n A ₂ are each independently hydrogen, a hydroxy group, a substituted or unsubstituted C 1 -C 30 alkyloxy group, a substituted or unsubstituted C 1 -C 30 alkene. Nyloxy group, substituted or unsubstituted C1-C30 alkynyloxy group, substituted or unsubstituted C2-C30 carbonylalkyloxy group, substituted or unsubstituted C1-C30 thioalkyloxy group, substituted Or an unsubstituted C1-C30 alkylthioloxy group, a substituted or unsubstituted C1-C30 hydroxyalkyloxy group, a substituted or unsubstituted C1-C30 alkylsilyloxy group, a substituted or unsubstituted C1-C30 aminoalkyloxy group, substituted or unsubstituted C1-C30 aminoalkylthioalkyloxy group, substituted or unsubstituted C5-C30 cycloalkyloxy group, substituted or unsubstituted C5-C30 Heterocycloalkyloxy groups, substituted or unsubstituted C6-C30 aryloxy groups, substituted or unsubstituted C6-C20 Alkyloxy group, substituted or unsubstituted C4-C30 heteroaryloxy group, substituted or unsubstituted C4-C20 heteroarylalkyloxy group, substituted or unsubstituted C1-C30 alkylthio group, substitution Or unsubstituted C1-C30 alkenylthio group, substituted or unsubstituted C1-C30 alkynylthio group, substituted or unsubstituted C2-C30 carbonylalkylthio group, substituted or unsubstituted C1 -C30 thioalkylthio group, substituted or unsubstituted C1-C30 hydroxyalkylthio group, substituted or unsubstituted C1-C30 alkylsilylthio group, substituted or unsubstituted C1-C30 amino Alkylthio group, substituted or unsubstituted C1-C30 aminoalkylthioalkylthio group, substituted or unsubstituted C5-C30 cycloalkylthio group, substituted or unsubstituted C5-C30 heterocycloalkyl tee Or substituted or unsubstituted C6-C30 arylthio groups, substituted or unsubstituted C6-C20 arylal Thio group, substituted or unsubstituted C4-C30 heteroarylthio group, substituted or unsubstituted C4-C20 heteroarylalkylthio group, substituted or unsubstituted C1-C30 alkylamine group, substituted Or unsubstituted C1-C30 alkenylamine group, substituted or unsubstituted C1-C30 alkynylamine group, substituted or unsubstituted C2-C30 carbonylalkylamine group, substituted or unsubstituted C1-C30 thioalkylamine group, substituted or unsubstituted C1-C30 hydroxyalkylamine group, substituted or unsubstituted C1-C30 alkylsilylamine group, substituted or unsubstituted C1-C30 Aminoalkylamine groups, substituted or unsubstituted C1-C30 aminoalkylthioalkylamine groups, substituted or unsubstituted C5-C30 cycloalkylamine groups, substituted or unsubstituted C5-C30 heterocycloalkyl Amine group, substituted or unsubstituted C6-C30 arylamine group, substituted or unsubstituted C6-C20 arylalkylamine Group, a substituted or unsubstituted C4-C30 heteroarylamine group and a substituted or unsubstituted C4-C20 heteroarylalkylamine group, wherein at least n A ₁ and n A ₂ One is not hydrogen and n is an integer from 4 to 12.

The crystalline polymorph according to the present invention can selectively adsorb gas molecules or small organic molecules according to the three-dimensional and chemical environment of the cavity of the crystalline polymorph formed differently according to the synthesis conditions, catalyst, ion exchange, mixture It can be used for the purpose of separation.

In addition, since the crystalline polymorph according to the present invention is composed of a cucurbituryl compound molecule, the crystalline polymorph according to the present invention also includes a pupil inside the cucurbituril compound. Thus, gas may also be supported into the pupils inside such cucurbituril compound molecules.

Gases that can be supported on the crystalline polymorph according to the present invention are, for example, propene, isobutylene, butadiene, isoprene, terpenes, hydrogen , Nitrogen, oxygen, argon, methane, ethane, propane, butane, isobutane, acetylene, carbon dioxide, xenon, carbon monoxide, SF ₆ , NO, N ₂ O, NO ₂ , H ₂ S, SO ₂ , Cl ₂ , krypton, etc. In addition, two or more mixed gases of these gases may be supported.

The molar ratio of the cucurbituril compound to gas may be about 1: 0.02 to 6. This is much higher than the amount of gas known to be supported using the pores in the conventional cucurbituril compound.

As described above, depending on the crystal structure of the polymorph of the cucurbituril compound represented by the formula (1), a gas that can be supported in a larger amount may be optional.

For example, if the crystalline polymorph of the cucurbituril compound is prepared under hydrochloric or sulfuric acid conditions, in particular in the case of hydrogen, nitrogen, oxygen, argon, methane, acetylene, carbon dioxide or xenon The gas can be adsorbed. Specifically, in this case, the molar ratio of the cucurbituril compound to gas may be 1: 0.03 to 6.

Immediately after the synthesis of the crystalline polymorph, the inventors found that water, which is a guest molecule contained in a cavity, for example, a cavity in the form of a one-dimensional channel, was activated by vacuum drying the crystalline polymorph at 100 ° C. for 2 days. After checking, it was confirmed that the pores of the porous material are no longer included. As a result, it was found that a large amount of gas can be supported in the cavity where the water is missing.

5A and 5B are thermal stability measured by synthesizing a cucurbituril [6] compound under hydrochloric acid condition in which an X-ray crystal structure was identified to form a crystalline polymorph, and activating it by vacuum drying at 100 ° C. for 2 days. Thermogravimetric analysis (TGA) results and evaluation results of Powder-dependent Powder X-Ray Diffraction Patterns according to temperature change. It is shown that the TGA of Figure 5a to maintain the stability up to 350 ℃, looking at the Powder XRD patterns according to the temperature change of Figure 5b has been shown not to lose crystallinity up to 300 ℃. From this it can be seen that the structure according to the invention is thermally very stable.

FIG. 6 is a measurement of Powder XRD patterns (Powder X-Ray Diffraction patterns) measured by synthesizing a cucurbituril [6] compound under hydrochloric acid to form a crystalline polymorph, and activating it by vacuum drying at 100 ° C. for 2 days. Show results. As such, it can be seen that the crystalline polymorph activated at high temperature has a permanent cavity while maintaining its structure from the Powder XRD patterns of FIG. 6. Thus, various gases suitable for such cavities can be collected.

7A and 7B show the synthesis of a cucurbituryl [6] compound under hydrochloric acid to form a crystalline polymorph, which was activated by vacuum drying at 100 ° C. for 2 days, and then subjected to crystalline polymorph adsorbed with acetylene. It is a crystal structure obtained by the -line crystal structure analysis method. Two acetylene molecules per molecule of cucurbituril [6] are shown in the crystalline polymorphic cavity, while the pores inside each cucurbituril [6] molecule are filled with 2.3 water molecules. The acetylene molecules have two irregular arrangements in Fig. 7a: 7b with a 66:34 ratio inside the cavities in the channel form of the crystalline polymorph, both of which have a CC bond length of 1.176 kPa. In more detail, the co-exposed carbonyl group in the form of a channel of the cucurbituril [6] compound has a hydrogen bond interaction with the acid hydrogen atom of acetylene, and in Figs. HC has a distance. The hydrogen bond distance between this cucurbituril [6] and the adsorbed acetylene shows high adsorption enthalpy. The area of the cavities in the form of channels of the crystalline polymorph (1557.8 Å ³ ) can accommodate up to 4.2 acetylene molecules per molecule of cucurbituril [6], which is in accordance with the adsorption isotherm of FIG. 9C. The reason why such a large amount of acetylene can be adsorbed is due to the hydrogen bond interaction between the acetylene and the carbonyl group of cucurbituril [6].

The crystalline polymorph of the cucurbituril compound represented by Formula 1 according to the present invention has a permanent cavity of uniform size, and the cavity can be used to selectively collect a specific gas according to the stacked structure of the molecule. Not only does it have a thermally very stable structure, but also the advantage is that the material for its manufacture is very inexpensive. Compared to the existing metal-organic porous material using a metal, the manufacturing method is easy and environmentally friendly, and thus industrial mass production is possible. In addition, it can be recycled at a relatively low temperature and has an easy recycling feature.

The present invention also provides a method for producing a crystalline polymorph of a cucurbituril compound represented by the following general formula (1). The method for preparing the crystalline polymorph of the cucurbituril compound is a step of forming a crystalline polymorph of the cucurbituryl compound by preparing the cucurbituril compound under acidic conditions and the crystalline polymorph of the formed cucurbituril compound at 50 ° C to 300 ° C for 30 minutes to Activating by vacuum drying for 96 hours. The crystalline polymorph of the cucurbituril compound comprises a cavity as described above, wherein the cavity is surrounded by a plurality of adjacent cucurbituryl compounds.

<Formula 1>

Wherein n A ₁ and n A ₂ are each independently hydrogen, a hydroxy group, a substituted or unsubstituted C 1 -C 30 alkyloxy group, a substituted or unsubstituted C 1 -C 30 alkene. Nyloxy group, substituted or unsubstituted C1-C30 alkynyloxy group, substituted or unsubstituted C2-C30 carbonylalkyloxy group, substituted or unsubstituted C1-C30 thioalkyloxy group, substituted Or an unsubstituted C1-C30 alkylthioloxy group, a substituted or unsubstituted C1-C30 hydroxyalkyloxy group, a substituted or unsubstituted C1-C30 alkylsilyloxy group, a substituted or unsubstituted C1-C30 aminoalkyloxy group, substituted or unsubstituted C1-C30 aminoalkylthioalkyloxy group, substituted or unsubstituted C5-C30 cycloalkyloxy group, substituted or unsubstituted C5-C30 Heterocycloalkyloxy groups, substituted or unsubstituted C6-C30 aryloxy groups, substituted or unsubstituted C6-C20 A arylalkyloxy group, a substituted or unsubstituted C4-C30 heteroaryloxy group, a substituted or unsubstituted C4-C20 heteroarylalkyloxy group, a substituted or unsubstituted C1-C30 alkylthio group, Substituted or unsubstituted C1-C30 alkenylthio group, substituted or unsubstituted C1-C30 alkynylthio group, substituted or unsubstituted C2-C30 carbonylalkylthio group, substituted or unsubstituted C1-C30 thioalkylthio group, substituted or unsubstituted C1-C30 hydroxyalkylthio group, substituted or unsubstituted C1-C30 alkylsilylthio group, substituted or unsubstituted C1-C30 Aminoalkylthio group, substituted or unsubstituted C1-C30 aminoalkylthioalkylthio group, substituted or unsubstituted C5-C30 cycloalkylthio group, substituted or unsubstituted C5-C30 heterocycloalkyl Thiothio, substituted or unsubstituted C6-C30 arylthio group, substituted or unsubstituted C6-C20 arylal Thio group, substituted or unsubstituted C4-C30 heteroarylthio group, substituted or unsubstituted C4-C20 heteroarylalkylthio group, substituted or unsubstituted C1-C30 alkylamine group, substituted Or unsubstituted C1-C30 alkenylamine group, substituted or unsubstituted C1-C30 alkynylamine group, substituted or unsubstituted C2-C30 carbonylalkylamine group, substituted or unsubstituted C1-C30 thioalkylamine group, substituted or unsubstituted C1-C30 hydroxyalkylamine group, substituted or unsubstituted C1-C30 alkylsilylamine group, substituted or unsubstituted C1-C30 Aminoalkylamine groups, substituted or unsubstituted C1-C30 aminoalkylthioalkylamine groups, substituted or unsubstituted C5-C30 cycloalkylamine groups, substituted or unsubstituted C5-C30 heterocycloalkyl Amine group, substituted or unsubstituted C6-C30 arylamine group, substituted or unsubstituted C6-C20 arylalkylah Group, is selected from the group consisting of a substituted or unsubstituted hetero aryl amine group of the unsubstituted C4-C30, and substituted or unsubstituted heteroaryl alkyl amine of unsubstituted C4-C20, wherein n number of A ₁ and n A ₂ of at least One is not hydrogen and n is an integer from 4 to 12.

Examples of the acid used in the above acid conditions include hydrochloric acid (HCl), hydrobromic acid (HBr), hydroiodic acid (HI), phosphoric acid (H ₃ PO ₃ ), p-toluenesulfonic acid, methanesulfonic acid acid), sulfuric acid (H ₂ SO ₄ ), nitric acid (HNO ₃ ), acetic acid (CH ₃ COOH), carbonic acid (H ₂ CO ₃ ), formic acid (formic acid, CH ₂ O ₂ ), trifluoromethanesulfonic acid ( trifluoromethanesulfonic acid, CF ₃ SO ₃ H), and also mixtures of two or more of these acids may be used.

The present invention also provides a gas storage method for supporting a gas into a cavity contained in a crystalline polymorph of a cucurbituril compound represented by Formula 1, wherein the cavity is surrounded by a plurality of adjacent cucurbituryl compounds. to provide.

According to the gas storage method of the present invention, hydrogen, nitrogen, oxygen, methane, acetylene, carbon dioxide, argon, xenon, carbon monoxide, SF ₆ , NO, N ₂ O, NO ₂ , H ₂ S, SO ₂ , Cl ₂ , Gas such as krypton can be stored, and a large amount of gas can be safely stored at room temperature as well as at low temperature. In addition, in particular, in the case of acetylene gas is generally stored using acetone and DMF as a solvent, when the crystalline polymorph of the cucurbituril compound represented by the formula (1) is used as a storage medium, the use of such a solvent is not necessary, the process of recovering gases Contamination from impurities such as acetone or DMF can be avoided.

According to an embodiment of the present invention, when the gas is hydrogen, nitrogen, oxygen or argon, or two or more gas mixtures selected from the group consisting of these gases, the gas may be crystalline of the cucurbituril compound at a temperature of 77K to 150K. Preference is given to contacting the polymorph.

According to another embodiment of the invention, the gas is propene, isobutylene, butadiene, butadiene, isoprene, terpenes, hydrogen, nitrogen, oxygen, argon, methane, Ethane, propane, butane, isobutane, acetylene, carbon dioxide, xenon, carbon monoxide, SF ₆ , NO, N ₂ O, NO ₂ , H ₂ S, SO ₂ , Cl ₂ or krypton, or two selected from the group consisting of these gases In the case of the above-mentioned mixed gas, it is preferable to contact the said gas with the crystalline polymorph of the said cucurbituril compound at the temperature of 196K-325K.

According to the gas storage method according to the present invention, the gas is supported in the cavity of the crystalline polymorph of the three-dimensional skeleton structure and exists stably, thereby storing a large amount of gas. In particular, the structure formed according to the manufacturing method can be utilized for various and selective gas storage and transport using different polymorph structure features.

The present invention also provides a selective separation method of a gas for selectively supporting only a specific gas in a gas mixture into a cavity included in the crystalline polymorph of the cucurbituryl compound represented by Formula 1, wherein the cavity is surrounded by a plurality of adjacent cucurbituryl compounds. It provides a method for the selective separation of a particular gas, characterized in that.

Examples of the gas mixture include acetylene, carbon dioxide or a mixture of acetylene and carbon dioxide, including propene, isobutylene, butadiene, isoprene, terpenes ), Hydrogen, nitrogen, oxygen, argon, methane, ethane, propane, butane, isobutane, xenon, carbon monoxide, SF ₆ , NO, N ₂ O, NO ₂ , H ₂ S, SO ₂ , Cl ₂ or krypton It may be the case further comprising one or more selected from the group.

According to another embodiment of the present invention, there is provided a method of contacting such a gas mixture with the crystalline polymorph of the cucurbituril compound to selectively support only acetylene and carbon dioxide from the gas mixture. In this case, it is preferred to contact the gas mixture with the crystalline polymorph of the cucurbituril compound at a temperature of 196K-325K.

FIG. 8 shows the heat of adsorption for acetylene compared to the heat of adsorption for acetylene of metal formate after synthesis of Cucurbituril [6] to form and activate a crystalline polymorph under acidic conditions. As shown in FIG. 8, when acetylene is supported in the cavity of the cucurbituril [6] compound, the heat of adsorption is generally greater than that of the metal formate porous material which is generally known to adsorb acetylene. Can be used. DG Samsonenko, H. Kim, Y. Sun, G.-H. Kim, H.-S. Lee, K. Kim, Chem . Asian. J. 2007, 2 , 484-488]

In addition, the cucurbituril [6] porous material formed under hydrochloric acid conditions can be recycled at a relatively low temperature (100-130 ° C.) compared to molecular sieve (350 ° C.), and it is easy to recycle.

The present invention also provides a selective removal method of a specific gas to selectively remove a specific gas into a cavity contained in the crystalline polymorph of the cucurbituril compound represented by Formula 1, wherein the cavity is a plurality of adjacent cucurbituril Provided is a method for selective removal of certain gases characterized by being surrounded by compound molecules.

According to another embodiment of the invention, a gas mixture comprising acetylene, carbon dioxide or a mixture of acetylene and carbon dioxide, propene, isobutylene, butadiene, isoprene, terpene terpenes, hydrogen, nitrogen, oxygen, argon, methane, ethane, propane, butane, isobutane, xenon, carbon monoxide, SF ₆ , NO, N ₂ O, NO ₂ , H ₂ S, SO ₂ , Cl ₂ or krypton A gas mixture further comprising at least one selected from the group consisting of the group may be contacted with the crystalline polymorph of the cucurbituril compound to selectively remove only acetylene and / or carbon dioxide from the gas mixture to selectively remove a specific gas. In this case, it is preferred to contact the gas mixture with the crystalline polymorph of the cucurbituril compound at a temperature of 196K-325K.

According to the selective separation or removal method of acetylene or carbon dioxide of the present invention, acetylene or carbon dioxide can be separated from the gas mixture in high purity. In addition, by using the crystalline polymorph of the cucurbituril compound represented by the formula (1) according to the present invention as a filter can be used for the purpose of almost completely removing acetylene or carbon dioxide from the mixed gas.

As such, the method for storing, separating or removing a gas according to the present invention can be very usefully used in industrial fields such as manufacturing, storing, and transporting gas of high purity.

Hereinafter, the present invention will be described with reference to the following specific examples, but the present invention is not limited to the following examples.

Example

Example  One

According to the manufacturing method described in a paper published by WA Freeman et al . ( J. Am. Chem . Soc. , 1981 , 103 , 7367-7368), using HCl instead of H ₂ SO ₄ Thus, a crystalline polymorph consisting of a cucurbituril [6] compound was synthesized. The crystalline polymorph synthesized in this way was vacuum dried at 100 ° C. for 2 days, and activated by removing water present as guest molecules in the pores in the cavity and the cucurbituryl [6] compound molecule. An experiment was conducted to adsorb nitrogen and argon gas to the activated crystalline polymorph. Quantachrome's Autosorp-1-MP was used as the adsorption equipment for the gas. The saturated vapor pressure was fixed at 763 torr and the pressure of each gas was increased from 10 ⁻⁵ atm to 1.1 atm. As the measured adsorption and desorption point, the volume when no pressure change was greater than 0.0008 atm within 3 minutes of equilibration time was recorded. Liquid nitrogen was used to maintain the temperature at 77 K, and liquid argon was used to maintain the temperature at 87 K. The purity of nitrogen used in the experiment is 99.9999% and the argon purity is 99.9995%.

9A and 9B are graphs showing adsorption isotherms for nitrogen and argon of crystalline polymorphs prepared and activated in Example 1 measured at temperatures of 77K and 87K, respectively. The porosity and surface area of this crystalline polymorph were obtained from the results of adsorption isotherms for nitrogen measured at a temperature of 77 K shown in FIG. 9A. This adsorption isotherm is a Type I isotherm that is typically reversible at low pressures and saturates adsorption and desorption, which is typical of fine porous materials. By BET method, the surface area of this porous material was measured to be 210 m ² g ^{- 1} by BET method. Further, according to the pupil size distribution (Fig. 9B) obtained by the Horvath-Kawazoe method from the argon adsorption isotherm obtained at 87K, this crystalline polymorph has a uniform cavity (channel form) having a diameter of 6 mm 3. The amount of adsorption to nitrogen and argon at 77K and 87K of this crystalline polymorph is summarized in Table 1 below.

matter Nitrogen adsorption amount (cm ³ g ^-1 ) Argon adsorption amount (cm ³ g ^-1 ) 77 K 87 K Crystalline Polymorph Prepared and Activated from Example 1 84 77

From the results of Table 1, it can be seen that the crystalline polymorph prepared and activated from Example 1 can store nitrogen and argon or gases of similar size or similar properties.

Example  1-1

A crystalline polymorph was synthesized in the same manner as in Example 1 for the crystalline polymorph of the cucurbituril compound ((methyl) ₁₂ CB [6]) when R is a methyl group and n is 6 in the compound of Formula 3 . X-ray diffraction experiments were performed on the crystalline polymorphs of the cucurbituril compound thus synthesized, and the results are shown in FIGS. 12A and 12B. 12A is a top view and FIG. 12B is a side-view. The part indicated in yellow represents the accessible internal cavity and the part indicated in gray represents the surface of the cucurbituril compound of the accessible cavity. The X-ray crystal structure of the crystalline polymorph is as follows (water and acid are removed):

Monoclinic, P 2 ₁ / c , a = 25.672 (5) Å, a = 11.958 (2) c , c = 45.3845 (9) Å, V = 13646 (3) Å ³ , R ₁ = 0.0910, GOF = 1.106.

Example  1-2

A crystalline polymorph was synthesized in the same manner as in Example 1 for the cucurbituril compound ((hydroxy) ₁₂ CB [6]) where n is 6 in the compound of Formula 4. X-ray diffraction experiments were performed on the crystalline polymorphs of the cucurbituril compound thus synthesized, and the results are shown in FIGS. 13A and 13B. FIG. 13A is a top view and FIG. 13B is a side-view. The part indicated in yellow represents the accessible internal cavity and the part indicated in gray represents the surface of the cucurbituril compound of the accessible cavity. The X-ray crystal structure of the crystalline polymorph is as follows (water and acid are removed):

Trigonal, R- 3, a = 16.758 (2) Å, c = 21.786 (4) Å, V = 5299 (1) Å ³ , R ₁ = 0.0792, GOF = 1.057.

Example  1-3

A crystalline polymorph was synthesized in the same manner as in Example 1 for the cucurbituril compound ((cyclohexyl) ₁₂ CB [6]) when n is 6 in the compound of Formula 5. X-ray diffraction experiments were performed on the crystalline polymorphs of the cucurbituril compound thus synthesized, and the results are shown in FIGS. 14A and 14B. FIG. 14A is a top view and FIG. 14B is a side-view. The part indicated in yellow represents the accessible internal cavity and the part indicated in gray represents the surface of the cucurbituril compound of the accessible cavity. The X-ray crystal structure of the crystalline polymorph is as follows (water and acid are removed):

Trigonal, R -3, a = 19.345 (1) Å, c = 34.235 (4) Å, V = 10320 (1) Å ³ , R ₁ = 0.0492, GOF = 1.006.

According to the X-ray diffraction experiments of the above examples, it was confirmed that the crystalline polymorphs of the cucurbituril compound may have different sizes of cavities inside, depending on the kind of the cucurbituril compound, thereby allowing the selective adsorption of various gases. .

Example  2

A crystalline polymorph was prepared in the same manner as in Example 1, and the crystalline polymorph was vacuum dried at 100 ° C. for 2 days to remove water present as guest molecules in the pores in the cavity and cucurbituryl [6] compound molecules. After removing and activating, experiments were performed to adsorb the gas by varying the combination of temperature and gas. A dry ice / acetone mixture was used to maintain the temperature at 196 K, ice water was used to maintain the temperature of 273 K, and a water bath was used to maintain the temperature of 298 K. The gases used in the experiment were hydrogen, nitrogen, carbon dioxide, methane, acetylene and xenon, and the purity of hydrogen, nitrogen and carbon dioxide was 99.9999%, the purity of methane was 99.9995%, the purity of acetylene was 99.95%, and the purity of xenon was 99.998. It was%.

9C, 9D and 9E are adsorption isotherms for hydrogen, nitrogen, methane, acetylene, carbon dioxide and xenon, of the same crystalline polymorph prepared and activated as in Example 1, measured at temperatures of 196K, 273K and 298K A graph representing. The adsorption amount was measured in the same manner with other porous materials. In Table 2, the adsorption amounts of crystalline polymorph consisting of cucurbituril [6] to acetylene and carbon dioxide, measured at temperatures of 196K, 273K and 298K, are summarized in comparison with the results of adsorption of other porous materials.

matter Acetylene adsorption amount (cm ³ g ^-1 ) Carbon dioxide adsorption amount (cm ³ g ^-1 ) 196 K 273 K 298 K 196 K 273 K 298 K Crystalline Polymorph of Example 2 91 60 52 97 61 48 porous material consisting of p - tert -butylcalix [4] arene 18 porous material consisting of tris- o- phenylene-dioxycyclotriphosphazene 60.5 Porous material consisting of [Cu ₂ (pzdc) ₂ (pyz)] 42 Porous material consisting of Mg (HCOO) ₂ 72.5 69.4 65.7 62.1 45.3 Porous material consisting of Mn (HCOO) ₂ 68.2 57.7 51.2 54.7 38.3

Referring to Table 2, the crystalline polymorph of Example 2 adsorbs 91 cm ³ g ^-1 acetylene and 97 cm ³ g ^-1 carbon dioxide at 196 K, respectively, Mg (HCOO) ₂ or Mn (HCOO). _{It is} known to adsorb acetylene and carbon dioxide, such as ₂ , but higher amounts of acetylene or nearly similar at other temperatures than metal-organic porous materials synthesized with metals that can be harmful to humans and the environment and are relatively expensive to manufacture. It was confirmed to adsorb levels of acetylene and carbon dioxide. And, it shows the result of adsorbing more carbon dioxide than organic molecular porous material such as tris- o- phenylenedioxycyclotriphosphazene (TPP). In addition, the crystalline polymorph of the cucurbituril [6] compound of Example 2 showed the ability to adsorb a significant amount of acetylene and carbon dioxide even at room temperature (298 K). Also, at 298K, organic molecular porous materials such as p - tert -butylcalix [4] arene (TBC [4]) or metal-organic porous materials such as [Cu ₂ (pzdc) ₂ (pyz)] More acetylene was adsorbed.

In addition, the adsorption amounts of the crystalline polymorph prepared and activated in Example 2, measured at temperatures of 196K, 273K and 298K, to methane and xenon are summarized in Table 3 above.

matter Methane Adsorption (cm ³ g ^-1 ) Xenon adsorption amount (cm ³ g ^-1 ) 196 K 273 K 298 K 196 K 273 K 298 K Crystalline Polymorph of Example 2 48 17 11 51 33 26 tris- o -phenylene-dioxycyclotriphosphazene 33.2 8.4

Referring to Table 3, the cucurbituril compound 6 crystalline polymorph of Example 2 showed better methane adsorption results than tris- o- phenylenedioxycyclotriphosphazene (TPP), an organic molecular porous material. . On the other hand, the cucurbituril [6] compound crystalline polymorph of Example 2 was confirmed to adsorb a similar amount of methane to xenon having a kinetic diameter similar to that of methane.

Example 3 :

The crystalline polymorph prepared in the same manner as in Example 2 was vacuum dried at 100 ° C. for 2 days to remove water present as guest molecules in the cavities in the cavity and the cucurbituryl [6] compound molecule, thereby activating. Then, experiments were carried out to adsorb hydrogen gas to the crystalline polymorph in the activated state. Quantachrome's Autosorp-1-MP was used as the adsorption equipment for the gas. The saturated vapor pressure was fixed at 763 torr and the pressure of hydrogen gas increased from 10 ⁻⁵ atm to 1.1 atm. As the measured adsorption and desorption point, the volume when no pressure change was greater than 0.0008 atm within 3 minutes of equilibration time was recorded. Liquid nitrogen was used to maintain the temperature at 77K. The purity of hydrogen used in the experiment is 99.9999%.

10 is a graph showing the adsorption isotherm for hydrogen of the crystalline polymorph in Example 3 at a temperature of 77 K. FIG. The crystalline polymorph in Example 3 was confirmed to adsorb 0.62% by weight of hydrogen at a pressure of 1 atm and a temperature of 77K, which means that it can be used for storage and separation of hydrogen.

Example  4

In the same manner as in Example 2, except that the crystalline polymorph of the cucurbituryl [7] compound instead of the cucurbituryl [6] compound was vacuum-dried at 130 ° C. for 2 days, so that the pores in the cavity and the molecule of the cucurbituryl [7] compound were Water present in the guest molecules was removed and activated. Then, experiments were carried out to adsorb hydrogen gas to the crystalline polymorph in the activated state. Quantachrome's Autosorp-1-MP was used as the adsorption equipment for the gas. The saturated vapor pressure was fixed at 763 torr and the pressure of hydrogen gas increased from 10 ⁻⁵ atm to 1.1 atm. As the measured adsorption and desorption point, the volume when no pressure change was greater than 0.0008 atm within 3 minutes of equilibration time was recorded. Liquid nitrogen was used to maintain the temperature at 77K. The purity of hydrogen used in the experiment is 99.9999%.

11 is a graph showing the adsorption isotherm for hydrogen of the crystalline polymorph in Example 4 at a temperature of 77 K. FIG. The crystalline polymorph in Example 4 adsorbs 1.55% by weight of hydrogen at a pressure of 1 atm and a temperature of 77K, and the amount of adsorption is MOF-5 (Metal Organic Framework-5), which is a representative metal-organic porous material. Adsorption results better than the hydrogen adsorption amount (1.32% by weight, 77K, 1 atm). In addition, the crystalline polymorph in Example 4 shows hysteresis at low pressure, which means that a large amount of hydrogen can be stored at low temperature and low pressure.

From the above examples, the crystalline polymorph of the cucurbituril [6] or cucurbituril [7] compound can be adsorbed and stored at a low temperature or at room temperature, and thus it is useful for preparing and storing high purity gas. .

9D and 9E which are the results of the adsorption isotherm obtained in Example 2, the adsorption amount of hydrogen, nitrogen, methane and xenon at 1 atm, 0 ° C. or room temperature is insignificant, but in the case of acetylene or carbon dioxide, Since the gas of adsorbed to the cucurbituril [6] crystalline polymorph, it was found that these gases can be separated from the mixed gas by selectively adsorbing acetylene or carbon dioxide from the gas mixture.

Conversely to the method of selectively separating acetylene or carbon dioxide from the mixed gas, it is also possible to remove acetylene and carbon dioxide from the gas mixture by using a cucurbituryl [6] compound crystalline polymorph as a filter material.

Figures 1a, 1b and 1c shows the crystal structure obtained by X-ray crystal structure analysis for the crystalline polymorph of the cucurbituril compound prepared according to one embodiment of the present invention.

FIG. 1D illustrates a crystal structure obtained by X-ray crystal structure analysis after adsorption of acetylene to a crystalline polymorph of a cucurbituril compound prepared according to another embodiment of the present invention.

Figure 2 illustrates the crystal structure obtained by X-ray crystal structure analysis for the crystalline polymorph of the cucurbituril compound prepared according to another embodiment of the present invention.

3a and 3b show the crystal structure obtained by X-ray crystal structure analysis for the crystalline polymorph of the cucurbituril compound prepared according to another embodiment of the present invention.

Figures 4a and 4b shows the crystal structure obtained by X-ray crystal structure analysis for the crystalline polymorph of the cucurbituril compound prepared according to another embodiment of the present invention.

Figures 5a and 5b, respectively, TGA analysis (ThermoGravimetric Analysis thermogram) for the crystalline polymorph of the cucurbituril compound prepared according to another embodiment of the present invention, Powder XRD patterns (Temperature- dependent Powder X-Ray Diffraction patterns).

FIG. 6 illustrates Powder X-Ray Diffraction patterns of the crystalline polymorph of the cucurbituril compound prepared according to another embodiment of the present invention.

7A and 7B illustrate crystal structures obtained by X-ray crystal structure analysis after acetylene is adsorbed onto the crystalline polymorph of a cucurbituril compound prepared according to another embodiment of the present invention.

FIG. 8 illustrates the heat of adsorption of crystalline polymorphs of the cucurbituril compound prepared according to another embodiment of the present invention against acetylene compared with the heat of adsorption of acetylene of metal formate.

9A and 9B are graphs showing adsorption isotherms for nitrogen at 77K and argon at 87K, respectively, of the crystalline polymorph of the cucurbituril compound prepared according to another embodiment of the present invention.

9C, 9D and 9E are for the hydrogen, nitrogen, methane, acetylene, carbon dioxide and xenon of the crystalline polymorph of the cucurbituril compound prepared according to another embodiment of the present invention at temperatures of 196K, 273K and 298K, respectively. A graph showing adsorption isotherms.

10 is a graph showing the adsorption isotherm for hydrogen at 77 K of the crystalline polymorph of the cucurbituril compound prepared according to another embodiment of the present invention.

11 is a graph showing the adsorption isotherm for hydrogen at 77 K of the crystalline polymorph of the cucurbituril compound prepared according to another embodiment of the present invention.

12a and 12b show the crystal structure obtained by X-ray crystal structure analysis for the crystalline polymorph of the cucurbituril compound prepared according to another embodiment of the present invention.

13A and 13B illustrate crystal structures obtained by X-ray crystal structure analysis for crystalline polymorphs of a cucurbituril compound prepared according to another embodiment of the present invention.

14A and 14B illustrate crystal structures obtained by X-ray crystal structure analysis for crystalline polymorphs of a cucurbituril compound prepared according to another embodiment of the present invention.

Claims (33)

A crystalline polymorph of a cucurbituril compound represented by Formula 1, comprising a cavity, wherein the cavity is surrounded by a plurality of adjacent cucurbituryl compounds: <Formula 1>

Wherein n A ₁ and n A ₂ are each independently hydrogen, a hydroxy group, a substituted or unsubstituted C 1 -C 30 alkyloxy group, a substituted or unsubstituted C 1 -C 30 alkene. Nyloxy group, substituted or unsubstituted C1-C30 alkynyloxy group, substituted or unsubstituted C2-C30 carbonylalkyloxy group, substituted or unsubstituted C1-C30 thioalkyloxy group, substituted Or an unsubstituted C1-C30 alkylthioloxy group, a substituted or unsubstituted C1-C30 hydroxyalkyloxy group, a substituted or unsubstituted C1-C30 alkylsilyloxy group, a substituted or unsubstituted C1-C30 aminoalkyloxy group, substituted or unsubstituted C1-C30 aminoalkylthioalkyloxy group, substituted or unsubstituted C5-C30 cycloalkyloxy group, substituted or unsubstituted C5-C30 A heterocycloalkyloxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C6-C20 a A arylalkyloxy group, a substituted or unsubstituted C4-C30 heteroaryloxy group, a substituted or unsubstituted C4-C20 heteroarylalkyloxy group, a substituted or unsubstituted C1-C30 alkylthio group, Substituted or unsubstituted C1-C30 alkenylthio group, substituted or unsubstituted C1-C30 alkynylthio group, substituted or unsubstituted C2-C30 carbonylalkylthio group, substituted or unsubstituted C1-C30 thioalkylthio group, substituted or unsubstituted C1-C30 hydroxyalkylthio group, substituted or unsubstituted C1-C30 alkylsilylthio group, substituted or unsubstituted C1-C30 Aminoalkylthio group, substituted or unsubstituted C1-C30 aminoalkylthioalkylthio group, substituted or unsubstituted C5-C30 cycloalkylthio group, substituted or unsubstituted C5-C30 heterocycloalkyl Thiothio, substituted or unsubstituted C6-C30 arylthio group, substituted or unsubstituted C6-C20 arylal Thio group, substituted or unsubstituted C4-C30 heteroarylthio group, substituted or unsubstituted C4-C20 heteroarylalkylthio group, substituted or unsubstituted C1-C30 alkylamine group, substituted Or unsubstituted C1-C30 alkenylamine group, substituted or unsubstituted C1-C30 alkynylamine group, substituted or unsubstituted C2-C30 carbonylalkylamine group, substituted or unsubstituted C1-C30 thioalkylamine group, substituted or unsubstituted C1-C30 hydroxyalkylamine group, substituted or unsubstituted C1-C30 alkylsilylamine group, substituted or unsubstituted C1-C30 Aminoalkylamine groups, substituted or unsubstituted C1-C30 aminoalkylthioalkylamine groups, substituted or unsubstituted C5-C30 cycloalkylamine groups, substituted or unsubstituted C5-C30 heterocycloalkyl Amine group, substituted or unsubstituted C6-C30 arylamine group, substituted or unsubstituted C6-C20 arylalkylah Group, is selected from the group consisting of a substituted or unsubstituted heteroaryl amine groups and substituted or unsubstituted heteroaryl alkyl amine of the unsubstituted C4-C20 of C4- C30, wherein n number of A ₁ and A ₂ of the at least one n One is not hydrogen and n is an integer from 4 to 12. The crystalline polymorph of the cucurbituryl compound according to claim 1, wherein the cavity is regularly distributed in the crystalline polymorph of the cucurbituryl compound. The crystalline polymorph of the cucurbituril compound according to claim 1, wherein the cavity is in the form of a channel. The method of claim 1, wherein the crystalline polymorph of the cucurbituryl compound is hydrochloric acid (HCl), hydrobromic acid (HBr), hydroiodic acid (HI), phosphoric acid (H ₃ PO ₃ ), p-toluenesulfonic acid (p-toluenesulfonic acid) , Methanesulfonic acid, sulfuric acid (H ₂ SO ₄ ), nitric acid (HNO ₃ ), acetic acid (CH ₃ COOH), carbonic acid (H ₂ CO ₃ ), formic acid (CH ₂ O ₂ ), trifluoro A crystalline polymorph of a cucurbituril compound, which is formed by preparing a cucurbituril compound using trifluoromethanesulfonic acid (CF ₃ SO ₃ H) or a mixture of two or more of these acids. The crystalline polymorph of the cucurbituryl compound according to claim 3, wherein the crystalline polymorph of the cucurbituryl compound is prepared under hydrochloric acid, and the interval between the channels is 0.2 nm to 4.0 nm. The crystalline polymorph of the cucurbituril compound according to claim 5, wherein the channel has a diameter of 0.3 nm to 1.0 nm. The crystalline polymorph of the cucurbituryl compound according to claim 3, wherein the crystalline polymorph of the cucurbituryl compound is prepared under sulfuric acid conditions, and the interval between channels is 0.2 nm to 4.0 nm. 8. The crystalline polymorph of the cucurbituril compound according to claim 7, wherein the channel has a diameter of 0.6 nm to 1.0 nm. The crystalline polymorph of any one of claims 1 to 8, wherein the general formula (1) is represented by the following general formula (2): <Formula 2>

In said formula, n is an integer of 4-12. The crystalline polymorph of any one of claims 1 to 8, wherein Chemical Formula 1 is represented by the following Chemical Formula 3: <Formula 3>

In said formula, R is a methyl group (Me) and n is an integer of 4-12. The crystalline polymorph of any one of claims 1 to 8, wherein the general formula (1) is represented by the following general formula (4): <Formula 4>

In said formula, n is an integer of 4-12. The crystalline polymorph of any one of claims 1 to 8, wherein the general formula (1) is represented by the following general formula (5): <Formula 5>

In said formula, n is an integer of 4-12. A crystalline polymorph of a cucurbituril compound represented by the following formula (1) comprising a cavity and a structure carrying a gas into the cavity, wherein the cavity is surrounded by a plurality of adjacent cucurbituryl compounds: <Formula 1>

Wherein n A ₁ and n A ₂ are each independently hydrogen, a hydroxy group, a substituted or unsubstituted C 1 -C 30 alkyloxy group, a substituted or unsubstituted C 1 -C 30 alkene. Nyloxy group, substituted or unsubstituted C1-C30 alkynyloxy group, substituted or unsubstituted C2-C30 carbonylalkyloxy group, substituted or unsubstituted C1-C30 thioalkyloxy group, substituted Or an unsubstituted C1-C30 alkylthioloxy group, a substituted or unsubstituted C1-C30 hydroxyalkyloxy group, a substituted or unsubstituted C1-C30 alkylsilyloxy group, a substituted or unsubstituted C1-C30 aminoalkyloxy group, substituted or unsubstituted C1-C30 aminoalkylthioalkyloxy group, substituted or unsubstituted C5-C30 cycloalkyloxy group, substituted or unsubstituted C5-C30 Heterocycloalkyloxy groups, substituted or unsubstituted C6-C30 aryloxy groups, substituted or unsubstituted C6-C20 Alkyloxy group, substituted or unsubstituted C4-C30 heteroaryloxy group, substituted or unsubstituted C4-C20 heteroarylalkyloxy group, substituted or unsubstituted C1-C30 alkylthio group, substitution Or unsubstituted C1-C30 alkenylthio group, substituted or unsubstituted C1-C30 alkynylthio group, substituted or unsubstituted C2-C30 carbonylalkylthio group, substituted or unsubstituted C1 -C30 thioalkylthio group, substituted or unsubstituted C1-C30 hydroxyalkylthio group, substituted or unsubstituted C1-C30 alkylsilylthio group, substituted or unsubstituted C1-C30 amino Alkylthio group, substituted or unsubstituted C1-C30 aminoalkylthioalkylthio group, substituted or unsubstituted C5-C30 cycloalkylthio group, substituted or unsubstituted C5-C30 heterocycloalkyl tee Or substituted or unsubstituted C6-C30 arylthio groups, substituted or unsubstituted C6-C20 arylal Thio group, substituted or unsubstituted C4-C30 heteroarylthio group, substituted or unsubstituted C4-C20 heteroarylalkylthio group, substituted or unsubstituted C1-C30 alkylamine group, substituted Or unsubstituted C1-C30 alkenylamine group, substituted or unsubstituted C1-C30 alkynylamine group, substituted or unsubstituted C2-C30 carbonylalkylamine group, substituted or unsubstituted C1-C30 thioalkylamine group, substituted or unsubstituted C1-C30 hydroxyalkylamine group, substituted or unsubstituted C1-C30 alkylsilylamine group, substituted or unsubstituted C1-C30 Aminoalkylamine groups, substituted or unsubstituted C1-C30 aminoalkylthioalkylamine groups, substituted or unsubstituted C5-C30 cycloalkylamine groups, substituted or unsubstituted C5-C30 heterocycloalkyl Amine group, substituted or unsubstituted C6-C30 arylamine group, substituted or unsubstituted C6-C20 arylalkylah Group, is selected from the group consisting of a substituted or unsubstituted hetero aryl amine group of the unsubstituted C4-C30, and substituted or unsubstituted heteroaryl alkyl amine of unsubstituted C4-C20, wherein n number of A ₁ and n A ₂ of at least One is not hydrogen and n is an integer from 4 to 12. The structure according to claim 13, further comprising a cavity inside the cooker kituril compound, and further comprising a gas supported in the pupil. 15. The process of claim 13 or 14, wherein the gas is propene, isobutylene, butadiene, isoprene, terpenes, hydrogen, nitrogen, oxygen, argon, methane , Ethane, propane, butane, isobutane, acetylene, carbon dioxide, xenon, carbon monoxide, SF ₆ , NO, N ₂ O, NO ₂ , H ₂ S, SO ₂ , Cl ₂ or krypton or selected from the group consisting of these gases A structure, characterized in that it is two or more mixed gases. The structure according to claim 13 or 14, wherein the molar ratio of the cucurbituryl compound to gas is 1: 0.02 to 6. The structure according to claim 13 or 14, wherein the crystalline polymorph of the cucurbituryl compound is prepared under hydrochloric acid, and the gas is hydrogen, nitrogen, oxygen, argon, methane, acetylene, carbon dioxide, or xenon. . 18. The structure of claim 17, wherein the ratio of the cucurbituryl compound to the gas is 1: 0.03-6. The structure according to claim 13 or 14, wherein the crystalline polymorph of the cucurbituryl compound is prepared under sulfuric acid conditions, and the gas is hydrogen, nitrogen, oxygen, argon, methane, acetylene, carbon dioxide or xenon. . 20. The structure of claim 19, wherein the content ratio of the cucurbituril compound to gas is 1: 0.03 to 6. Forming the crystalline polymorph of the cucurbituril compound by preparing the cucurbituril compound under acidic conditions and activating the crystalline polymorph of the formed cucurbituril compound by vacuum drying at 50 ° C to 300 ° C for 30 minutes to 96 hours. A method for preparing a crystalline polymorph of a cucurbituril compound comprising: the cucurbituryl compound is represented by the following Formula 1, wherein the crystalline polymorph of the cucurbituryl compound includes a cavity, and the cavity is surrounded by a plurality of adjacent cucurbituryl compounds Method for producing a crystalline polymorph of a cucurbituril compound <Formula 1>

Wherein n A ₁ and n A ₂ are each independently hydrogen, a hydroxy group, a substituted or unsubstituted C 1 -C 30 alkyloxy group, a substituted or unsubstituted C 1 -C 30 alkene. Nyloxy group, substituted or unsubstituted C1-C30 alkynyloxy group, substituted or unsubstituted C2-C30 carbonylalkyloxy group, substituted or unsubstituted C1-C30 thioalkyloxy group, substituted Or an unsubstituted C1-C30 alkylthioloxy group, a substituted or unsubstituted C1-C30 hydroxyalkyloxy group, a substituted or unsubstituted C1-C30 alkylsilyloxy group, a substituted or unsubstituted C1-C30 aminoalkyloxy group, substituted or unsubstituted C1-C30 aminoalkylthioalkyloxy group, substituted or unsubstituted C5-C30 cycloalkyloxy group, substituted or unsubstituted C5-C30 Heterocycloalkyloxy groups, substituted or unsubstituted C6-C30 aryloxy groups, substituted or unsubstituted C6-C20 Alkyloxy group, substituted or unsubstituted C4-C30 heteroaryloxy group, substituted or unsubstituted C4-C20 heteroarylalkyloxy group, substituted or unsubstituted C1-C30 alkylthio group, substitution Or unsubstituted C1-C30 alkenylthio group, substituted or unsubstituted C1-C30 alkynylthio group, substituted or unsubstituted C2-C30 carbonylalkylthio group, substituted or unsubstituted C1 -C30 thioalkylthio group, substituted or unsubstituted C1-C30 hydroxyalkylthio group, substituted or unsubstituted C1-C30 alkylsilylthio group, substituted or unsubstituted C1-C30 amino Alkylthio group, substituted or unsubstituted C1-C30 aminoalkylthioalkylthio group, substituted or unsubstituted C5-C30 cycloalkylthio group, substituted or unsubstituted C5-C30 heterocycloalkyl tee Or substituted or unsubstituted C6-C30 arylthio groups, substituted or unsubstituted C6-C20 arylal Thio group, substituted or unsubstituted C4-C30 heteroarylthio group, substituted or unsubstituted C4-C20 heteroarylalkylthio group, substituted or unsubstituted C1-C30 alkylamine group, substituted Or unsubstituted C1-C30 alkenylamine group, substituted or unsubstituted C1-C30 alkynylamine group, substituted or unsubstituted C2-C30 carbonylalkylamine group, substituted or unsubstituted C1-C30 thioalkylamine group, substituted or unsubstituted C1-C30 hydroxyalkylamine group, substituted or unsubstituted C1-C30 alkylsilylamine group, substituted or unsubstituted C1-C30 Aminoalkylamine groups, substituted or unsubstituted C1-C30 aminoalkylthioalkylamine groups, substituted or unsubstituted C5-C30 cycloalkylamine groups, substituted or unsubstituted C5-C30 heterocycloalkyl Amine group, substituted or unsubstituted C6-C30 arylamine group, substituted or unsubstituted C6-C20 arylalkylamine Group, a substituted or unsubstituted C4-C30 heteroarylamine group and a substituted or unsubstituted C4-C20 heteroarylalkylamine group, wherein at least n A ₁ and n A ₂ One is not hydrogen and n is an integer from 4 to 12. The method of claim 21, wherein the acid is hydrochloric acid (HCl), hydrobromic acid (HBr), hydroiodic acid (HI), phosphoric acid (H ₃ PO ₃ ), p-toluenesulfonic acid, methanesulfonic acid , Sulfuric acid (H ₂ SO ₄ ), nitric acid (HNO ₃ ), acetic acid (CH ₃ COOH), carbonic acid (H ₂ CO ₃ ), formic acid (CH ₂ O ₂ ), trifluoromethanesulfonic acid , CF ₃ SO ₃ H) or a mixture of two or more of these acids, the method for producing a crystalline polymorph of a cucurbituril compound. A gas storage method for supporting a gas into a cavity included in a crystalline polymorph of a cucurbituril compound represented by Formula 1, wherein the cavity is surrounded by a plurality of adjacent cucurbituryl compounds: <Formula 1>

Wherein n A ₁ and n A ₂ are each independently hydrogen, a hydroxy group, a substituted or unsubstituted C 1 -C 30 alkyloxy group, a substituted or unsubstituted C 1 -C 30 alkene. Nyloxy group, substituted or unsubstituted C1-C30 alkynyloxy group, substituted or unsubstituted C2-C30 carbonylalkyloxy group, substituted or unsubstituted C1-C30 thioalkyloxy group, substituted Or an unsubstituted C1-C30 alkylthioloxy group, a substituted or unsubstituted C1-C30 hydroxyalkyloxy group, a substituted or unsubstituted C1-C30 alkylsilyloxy group, a substituted or unsubstituted C1-C30 aminoalkyloxy group, substituted or unsubstituted C1-C30 aminoalkylthioalkyloxy group, substituted or unsubstituted C5-C30 cycloalkyloxy group, substituted or unsubstituted C5-C30 Heterocycloalkyloxy groups, substituted or unsubstituted C6-C30 aryloxy groups, substituted or unsubstituted C6-C20 Alkyloxy group, substituted or unsubstituted C4-C30 heteroaryloxy group, substituted or unsubstituted C4-C20 heteroarylalkyloxy group, substituted or unsubstituted C1-C30 alkylthio group, substitution Or unsubstituted C1-C30 alkenylthio group, substituted or unsubstituted C1-C30 alkynylthio group, substituted or unsubstituted C2-C30 carbonylalkylthio group, substituted or unsubstituted C1 -C30 thioalkylthio group, substituted or unsubstituted C1-C30 hydroxyalkylthio group, substituted or unsubstituted C1-C30 alkylsilylthio group, substituted or unsubstituted C1-C30 amino Alkylthio group, substituted or unsubstituted C1-C30 aminoalkylthioalkylthio group, substituted or unsubstituted C5-C30 cycloalkylthio group, substituted or unsubstituted C5-C30 heterocycloalkyl tee Or substituted or unsubstituted C6-C30 arylthio groups, substituted or unsubstituted C6-C20 arylal Thio group, substituted or unsubstituted C4-C30 heteroarylthio group, substituted or unsubstituted C4-C20 heteroarylalkylthio group, substituted or unsubstituted C1-C30 alkylamine group, substituted Or unsubstituted C1-C30 alkenylamine group, substituted or unsubstituted C1-C30 alkynylamine group, substituted or unsubstituted C2-C30 carbonylalkylamine group, substituted or unsubstituted C1-C30 thioalkylamine group, substituted or unsubstituted C1-C30 hydroxyalkylamine group, substituted or unsubstituted C1-C30 alkylsilylamine group, substituted or unsubstituted C1-C30 Aminoalkylamine groups, substituted or unsubstituted C1-C30 aminoalkylthioalkylamine groups, substituted or unsubstituted C5-C30 cycloalkylamine groups, substituted or unsubstituted C5-C30 heterocyclo Alkylamine group, substituted or unsubstituted C6-C30 arylamine group, substituted or unsubstituted C6-C20 arylalkylah Group, is selected from the group consisting of a substituted or unsubstituted hetero aryl amine group of the unsubstituted C4-C30, and substituted or unsubstituted heteroaryl alkyl amine of unsubstituted C4-C20, wherein n number of A ₁ and n A ₂ of at least One is not hydrogen and n is an integer from 4 to 12. 24. The method of claim 23, wherein the gas is hydrogen, nitrogen, oxygen or argon, or a gas mixture of two or more selected from the group consisting of these gases. The method of claim 24, wherein the gas is contacted with the crystalline polymorph of the cucurbituril compound at a temperature of 77K-150K. The method of claim 23, wherein the gas is propene, isobutylene, butadiene, isoprene, terpenes, hydrogen, nitrogen, oxygen, argon, methane, ethane, propane _Two or more mixed gases selected from the group consisting of butane, isobutane, acetylene, carbon dioxide, xenon, carbon monoxide, SF ₆ , NO, N ₂ O, NO ₂ , H ₂ S, SO ₂ , Cl ₂ or krypton Gas storage method characterized in that. 27. The method of claim 26, wherein the gas is contacted with the crystalline polymorph of the cucurbituril compound at a temperature of 196K-325K. A selective separation method of a gas for selectively supporting only a specific gas in a gas mixture into a cavity included in a crystalline polymorph of a cucurbituril compound represented by Formula 1, wherein the cavity is surrounded by a plurality of adjacent cucurbituryl compounds Selective separation of certain gases: <Formula 1>

Wherein n A ₁ and n A ₂ are each independently hydrogen, a hydroxy group, a substituted or unsubstituted C 1 -C 30 alkyloxy group, a substituted or unsubstituted C 1 -C 30 alkene. Nyloxy group, substituted or unsubstituted C1-C30 alkynyloxy group, substituted or unsubstituted C2-C30 carbonylalkyloxy group, substituted or unsubstituted C1-C30 thioalkyloxy group, substituted Or an unsubstituted C1-C30 alkylthioloxy group, a substituted or unsubstituted C1-C30 hydroxyalkyloxy group, a substituted or unsubstituted C1-C30 alkylsilyloxy group, a substituted or unsubstituted C1-C30 aminoalkyloxy group, substituted or unsubstituted C1-C30 aminoalkylthioalkyloxy group, substituted or unsubstituted C5-C30 cycloalkyloxy group, substituted or unsubstituted C5-C30 Heterocycloalkyloxy groups, substituted or unsubstituted C6-C30 aryloxy groups, substituted or unsubstituted C6-C20 Alkyloxy group, substituted or unsubstituted C4-C30 heteroaryloxy group, substituted or unsubstituted C4-C20 heteroarylalkyloxy group, substituted or unsubstituted C1-C30 alkylthio group, substitution Or unsubstituted C1-C30 alkenylthio group, substituted or unsubstituted C1-C30 alkynylthio group, substituted or unsubstituted C2-C30 carbonylalkylthio group, substituted or unsubstituted C1 -C30 thioalkylthio group, substituted or unsubstituted C1-C30 hydroxyalkylthio group, substituted or unsubstituted C1-C30 alkylsilylthio group, substituted or unsubstituted C1-C30 amino Alkylthio group, substituted or unsubstituted C1-C30 aminoalkylthioalkylthio group, substituted or unsubstituted C5-C30 cycloalkylthio group, substituted or unsubstituted C5-C30 heterocycloalkyl tee Or substituted or unsubstituted C6-C30 arylthio groups, substituted or unsubstituted C6-C20 arylal Thio group, substituted or unsubstituted C4-C30 heteroarylthio group, substituted or unsubstituted C4-C20 heteroarylalkylthio group, substituted or unsubstituted C1-C30 alkylamine group, substituted Or unsubstituted C1-C30 alkenylamine group, substituted or unsubstituted C1-C30 alkynylamine group, substituted or unsubstituted C2-C30 carbonylalkylamine group, substituted or unsubstituted C1-C30 thioalkylamine group, substituted or unsubstituted C1-C30 hydroxyalkylamine group, substituted or unsubstituted C1-C30 alkylsilylamine group, substituted or unsubstituted C1-C30 Aminoalkylamine groups, substituted or unsubstituted C1-C30 aminoalkylthioalkylamine groups, substituted or unsubstituted C5-C30 cycloalkylamine groups, substituted or unsubstituted C5-C30 heterocycloalkyl Amine group, substituted or unsubstituted C6-C30 arylamine group, substituted or unsubstituted C6-C20 arylalkylah Group, is selected from the group consisting of a substituted or unsubstituted hetero aryl amine group of the unsubstituted C4-C30, and substituted or unsubstituted heteroaryl alkyl amine of unsubstituted C4-C20, wherein n number of A ₁ and n A ₂ of at least One is not hydrogen and n is an integer from 4 to 12. The method of claim 28, wherein the gas mixture comprises acetylene, carbon dioxide or a mixture of acetylene and carbon dioxide, comprising: propene, isobutylene, butadiene, isoprene, terpenes, From the group consisting of hydrogen, nitrogen, oxygen, argon, methane, ethane, propane, butane, isobutane, xenon, carbon monoxide, SF ₆ , NO, N ₂ O, NO ₂ , H ₂ S, SO ₂ , Cl ₂ or krypton A method of selective separation of a particular gas, wherein the gas mixture further comprising at least one selected is contacted with the crystalline polymorph of the cucurbituril compound to selectively support only acetylene or carbon dioxide from the gas mixture. 30. The method of claim 28 or 29, wherein the gas mixture is contacted with the crystalline polymorph of the cucurbituril compound at a temperature of 196K-325K. A method for selectively removing a specific gas to selectively remove a specific gas into a cavity included in a crystalline polymorph of the cucurbituryl compound represented by Formula 1, wherein the cavity is surrounded by a plurality of adjacent cucurbituryl compound molecules. Selective removal of certain gases characterized by: <Formula 1>

Wherein n A ₁ and n A ₂ are each independently hydrogen, a hydroxy group, a substituted or unsubstituted C 1 -C 30 alkyloxy group, a substituted or unsubstituted C 1 -C 30 alkene. Nyloxy group, substituted or unsubstituted C1-C30 alkynyloxy group, substituted or unsubstituted C2-C30 carbonylalkyloxy group, substituted or unsubstituted C1-C30 thioalkyloxy group, substituted Or an unsubstituted C1-C30 alkylthioloxy group, a substituted or unsubstituted C1-C30 hydroxyalkyloxy group, a substituted or unsubstituted C1-C30 alkylsilyloxy group, a substituted or unsubstituted C1-C30 aminoalkyloxy group, substituted or unsubstituted C1-C30 aminoalkylthioalkyloxy group, substituted or unsubstituted C5-C30 cycloalkyloxy group, substituted or unsubstituted C5-C30 Heterocycloalkyloxy groups, substituted or unsubstituted C6-C30 aryloxy groups, substituted or unsubstituted C6-C20 A arylalkyloxy group, a substituted or unsubstituted C4-C30 heteroaryloxy group, a substituted or unsubstituted C4-C20 heteroarylalkyloxy group, a substituted or unsubstituted C1-C30 alkylthio group, Substituted or unsubstituted C1-C30 alkenylthio group, substituted or unsubstituted C1-C30 alkynylthio group, substituted or unsubstituted C2-C30 carbonylalkylthio group, substituted or unsubstituted C1-C30 thioalkylthio group, substituted or unsubstituted C1-C30 hydroxyalkylthio group, substituted or unsubstituted C1-C30 alkylsilylthio group, substituted or unsubstituted C1-C30 Aminoalkylthio group, substituted or unsubstituted C1-C30 aminoalkylthioalkylthio group, substituted or unsubstituted C5-C30 cycloalkylthio group, substituted or unsubstituted C5-C30 heterocycloalkyl Thiothio, substituted or unsubstituted C6-C30 arylthio group, substituted or unsubstituted C6-C20 arylal Thio group, substituted or unsubstituted C4-C30 heteroarylthio group, substituted or unsubstituted C4-C20 heteroarylalkylthio group, substituted or unsubstituted C1-C30 alkylamine group, substituted Or unsubstituted C1-C30 alkenylamine group, substituted or unsubstituted C1-C30 alkynylamine group, substituted or unsubstituted C2-C30 carbonylalkylamine group, substituted or unsubstituted C1-C30 thioalkylamine group, substituted or unsubstituted C1-C30 hydroxy alkylamine group, substituted or unsubstituted C1-C30 alkylsilylamine group, substituted or unsubstituted C1-C30 Aminoalkylamine groups, substituted or unsubstituted C1-C30 aminoalkylthioalkylamine groups, substituted or unsubstituted C5-C30 cycloalkylamine groups, substituted or unsubstituted C5-C30 heterocycloalkyl Amine group, substituted or unsubstituted C6-C30 arylamine group, substituted or unsubstituted C6-C20 arylalkylah Group, is selected from the group consisting of a substituted or unsubstituted hetero aryl amine group of the unsubstituted C4-C30, and substituted or unsubstituted heteroaryl alkyl amine of unsubstituted C4-C20, wherein n number of A ₁ and n A ₂ of at least One is not hydrogen and n is an integer from 4 to 12. 32. A gas mixture comprising acetylene, carbon dioxide or a mixture of acetylene and carbon dioxide, comprising: propene, isobutylene, butadiene, isoprene, terpenes, From the group consisting of hydrogen, nitrogen, oxygen, argon, methane, ethane, propane, butane, isobutane, xenon, carbon monoxide, SF ₆ , NO, N ₂ O, NO ₂ , H ₂ S, SO ₂ , Cl ₂ or krypton A method of selective removal of a particular gas, wherein the gas mixture further comprising at least one selected is contacted with the crystalline polymorph of the cucurbituril compound to selectively support only acetylene or carbon dioxide from the gas mixture. 33. The method of claim 32, wherein the gas mixture is contacted with the crystalline polymorph of the cucurbi turil compound at a temperature of 196K-325K.

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