JP7161657B2 - Novel polymer compound - Google Patents

Description

The present invention relates to novel polymeric compounds.

An amphipathic polymer is a polymer compound that has both a “hydrophilic group” that is compatible with water (aqueous phase) and a “lipophilic group” (hydrophobic group) that is compatible with oil (organic phase) in one molecule. , are widely used in environments where compatibility between hydrophilicity and hydrophobicity is required (eg Patent Documents 1 to 4).

On the other hand, a cyclic compound having inclusion ability is a compound having the function of including another molecule as a guest. According to such a cyclic compound, even for a compound that is usually difficult to disperse stably under a certain environment, by selectively incorporating it as a guest, the compound can be dispersed more efficiently than when the compound is used alone. It is known that stability can be improved (for example, Patent Document 5).

New polymer compounds that combine amphiphilic polymers with such special functions and cyclic compounds by chemical bonding can further improve their functions and exhibit new functions by exhibiting their unique functions. It is expected that new applications will be developed.
However, it has not been easy to newly synthesize such a polymer compound or to modify an existing polymer compound to prepare a new polymer compound.

Japanese Patent Application Laid-Open No. 2000-356088 JP-A-2002-308946 JP 2006-096933 A JP 2015-224223 A JP 2017-014431 A

Accordingly, an object of the present invention is to provide a novel polymer compound in which an amphipathic polymer and a cyclic compound having encapsulating ability are integrated by chemical bonding.

As a result of intensive studies, the present inventors have found that by utilizing the hydrophilic group of a cyclic compound, a high molecular weight compound having a cyclic unit having inclusion ability and an amphiphilic polymer unit chemically bonded to the cyclic unit can be obtained. The inventors have found that it is possible to obtain a novel polymer compound in which the cyclic unit has a hydrophobic site on the inside and a hydrophilic group on the outside, and have completed the present invention. .

That is, the gist and configuration of the present invention are as follows.
[1] A polymer compound having a cyclic unit having inclusion ability and an amphiphilic polymer unit chemically bonded to the cyclic unit,
the cyclic unit has a hydrophobic site on the inside and a hydrophilic group on the outside;
polymer compound.
[2] The polymer compound according to [1] above, wherein the cyclic unit is derived from at least one cyclic compound selected from cyclodextrin, calixarene, cucurbituril, and derivatives thereof.
[3] The above [1] or [2], wherein the amphiphilic polymer unit is derived from a polymer obtained by polymerizing at least one monomer selected from N-vinyl-ε-caprolactam and N-vinylpyrrolidone. The polymer compound according to .
[4] The polymer compound according to any one of [1] to [3] above, wherein the amphiphilic polymer unit is bonded to 1 unit of the cyclic unit and 1 unit or more and 8 units or less. .

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a novel polymer compound in which an amphiphilic polymer and an encapsulating cyclic compound are integrated by chemical bonding.

Embodiments of polymeric compounds according to the present invention are described in detail below.

The polymer compound of the present invention has a cyclic unit having encapsulating ability and an amphipathic polymer unit chemically bonded to the cyclic unit, and the cyclic unit has a hydrophobic field inside. , and has a hydrophilic group on the outside.
Hereinafter, the structure of the polymer compound will be described in detail for each unit.

(Annular unit)
The polymer compound of the present invention has a cyclic unit having inclusion ability. Such cyclic units have hydrophobic sites on the inside and hydrophilic groups on the outside. The term "inclusion ability" as used herein refers to the ability to take in a hydrophobic molecule into the hydrophobic field inside the cyclic unit and include it in the interior of the cyclic unit.

The cyclic unit is not particularly limited as long as it is derived from a cyclic compound having a hydrophobic site on the inside and a hydrophilic group on the outside. Examples thereof include the following cyclic compounds.
Cyclic compounds include cyclodextrin, calixarene, resorcinarene, pillararene, cucurbituril, derivatives thereof, and the like. Among them, at least one selected from cyclodextrin, calixarene, cucurbituril and derivatives thereof is preferable.

Cyclodextrins (cyclic oligosaccharides) have a structure in which both ends of oligosaccharides made of D-glucose are connected to form a ring (ring), and the number of D-glucose connections (ring members) is 5 or more. are known, α-cyclodextrin (6 ring members) with 6 D-glucose bonds, β-cyclodextrin (7 ring members) with 7 D-glucose bonds, and 8 glucose bonds γ-cyclodextrin (having 8 ring members) is generally used. Among them, β-cyclodextrin is preferred.

Calixarene is an oligomer having a structure in which several phenolic 2 and 6-positions are cyclically linked via methylene groups. Calixarene is generally written as calix[n]arene, where [n] represents the number of phenolic units (number of ring members). The phenol unit [n] is known to be about 3-20, preferably 3-10.

Resorcinarene is a cyclic molecule in which the phenol of calixarene is replaced with resorcinol (1,3-dihydroxybenzene). Resorcinarene is generally referred to as resorcin[n]arene, where [n] represents the number of resorcinol units (number of ring members). As for the resorcinol unit [n], 4 and 6 are known.

A pillar arene is generally written as pillar [n] arene, where [n] represents the number of arene units (the number of ring members). The arene units [n] of 5 and 6 are known, and higher-order pillar arenes can be synthesized, but 5 to 6 are preferred in the present invention. For example, a dialkoxy pillar arene is a cyclic condensate in which 1,4-dialkoxybenzenes are bridged with methylene at their 2 and 5 positions. Here, the number of carbon atoms in the alkoxy group is preferably 1-8.

Cucurbiturils are macrocyclic molecules consisting of glycoluril (=C ₄ H ₂ N ₄ O ₂ ) monomers linked by methylene groups (-CH ₂ -). Cucurbiturils are generally written as cucurbit[n]urils, where [n] represents the number of glycoluril units (number of ring members). The number of glycoluril units [n] is known to be 5, 6, 7, 8, 10 or 14, preferably 6-8.

The number of ring members of the cyclic compound is not particularly limited, but since the spatial size of the hydrophobic field varies depending on the number of ring members, a cyclic compound with a predetermined number of ring members is selected according to the size of the guest to be included. preferably.

(Amphiphilic polymer unit)
The polymer compound of the present invention has an amphipathic polymer unit. Such an amphipathic polymer unit may be derived from an amphipathic polymer.

The amphipathic polymer as described above is preferably a polymer obtained by polymerizing the following monomers.
Monomers constituting amphiphilic polymers include, for example, N-vinylamide derivatives (N-vinyllactam, N-vinyl-ε-caprolactam, N-vinylpyrrolidone, N-vinylpiperidone, N-vinylacetamide, N-vinylformamide , N-alkyl-N-vinylalkylamide, etc.), acrylamide and its derivatives (N-alkylacrylamide, etc.), and the like.

上記式（１）中、Ｒ^１及びＲ^２はそれぞれ独立して、水素原子又は炭素数１～８の炭化水素基を表す。ただし、Ｒ^１とＲ^２とは互いに連結して炭素数２～６のアルキレン基を構成してもよい。また、具体例としては、Ｒ^１が水素原子でＲ^２がイソプロピル基、Ｒ^１が水素原子でＲ^２がプロピル基、Ｒ^１が水素原子でＲ^２が２－ブテニル基、Ｒ^１がイソプロピル基でＲ^２が水素原子、Ｒ^１及びＲ^２が共に水素原子、Ｒ^１がメチル基でＲ^２がプロピル基、Ｒ^１がメチル基でＲ^２がイソブチル基、Ｒ^１がメチル基でＲ^２がイソペンチル基、Ｒ^１がメチル基でＲ^２がメチル基、Ｒ^１がメチル基でＲ^２がエチル基、Ｒ^１が水素原子でＲ^２がシクロヘキシルメチル基、Ｒ^１が水素原子でＲ^２が２－シクロペンチルエチル基であるものが挙げられる。 Examples of N-vinylamide derivatives include those represented by the following formula (1).

In formula (1) above, R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. However, R ¹ and R ² may be linked together to form an alkylene group having 2 to 6 carbon atoms. Further, as specific examples, R ¹ is a hydrogen atom, R ² is an isopropyl group, R ¹ is a hydrogen atom, R ² is a propyl group, R ¹ is a hydrogen atom, R ² is a 2-butenyl group, and R ¹ is an isopropyl group. R ² is a hydrogen atom, both R ¹ and R ² are hydrogen atoms, R ¹ is a methyl group and R ² is a propyl group, R ¹ is a methyl group and R ² is an isobutyl group, R ¹ is a methyl group and R ² is isopentyl group, ^R1 is a methyl group and ^R2 is a methyl group, ^R1 is a methyl group and ^R2 is an ethyl group, ^R1 is a hydrogen atom and ^R2 is a cyclohexylmethyl group, ^R1 is a hydrogen atom and ^R2 is 2 -Cyclopentylethyl group.

In particular, at least one selected from N-vinyl-ε-caprolactam and N-vinylpyrrolidone is preferable as the monomer constituting the amphiphilic polymer.

The amphipathic polymer as described above preferably has a weight average molecular weight of 500 to 30,000, more preferably 1,000 to 10,000.

Such amphiphilic macromolecular units are chemically bonded to cyclic units. A chemical bond with the cyclic unit is not particularly limited, and includes a covalent bond or an ionic bond, preferably a covalent bond from the viewpoint of stability as a polymer compound.

In the polymer compound of the present invention, the amphiphilic polymer unit preferably has 1 unit or more and 8 units or less, and preferably 1 unit or more and 5 units or less, per unit of the cyclic unit. is more preferred. Here, each number of units is counted for each part corresponding to each structural unit. For example, when the polymer compound of the present invention contains one portion corresponding to the cyclic unit and two portions corresponding to the amphipathic polymer unit in one molecule, the polymer compound has cyclic unit 1 It is considered that two amphiphilic polymer units are bound to each unit. Incidentally, the number of units of such a structural unit can be determined, for example, by a known method, by cleaving the bond between each structural unit of the polymer compound of the present invention to form a compound derived from a cyclic unit and an amphipathic polymer unit. The molecular weight of each derived polymer compound is determined, the number of moles of each structural unit is calculated therefrom, and the ratio can be estimated.

The weight average molecular weight of the polymer compound of the present invention is preferably 1,000 to 30,000, more preferably 1,500 to 10,000. By setting the length within the above range, deactivation due to entanglement of the polymer units is unlikely to occur, and a polymer chain having a length sufficient to enclose the target substance can be secured.

(effect/use)
The polymer compound of the present invention exhibits a function of encapsulating a hydrophobic molecule as a guest while maintaining an amphipathic function. Such a polymer compound can be suitably used, for example, in fields where amphipathic polymers and cyclic compounds have been conventionally used.
Specifically, amphipathic polymers have been used, for example, as gas hydrate formation inhibitors, poorly water-soluble drug carriers, thickeners, water retention agents, DDS, cell sheets, and the like.
Cyclic compounds have also been used for drug carriers, adsorbents, molecular group recognition materials, template polymerization, rotaxane polymers, and the like.
Among them, the polymer compound of the present invention can be suitably used as a gas hydrate formation inhibitor.

<Gas hydrate formation inhibitor>
Conventionally, amphiphilic polymers have been widely used as gas hydrate formation inhibitors (see JP-A-2001-139966).
Gas hydrates are produced by placing dissolved gas molecules such as hydrocarbons such as methane and ethane, and various gas molecules such as carbon dioxide in an aqueous medium under a specific temperature and pressure, whereby water molecules surround the dissolved gas molecules. It is known to form as ice-like crystals. Generation of such gas hydrates causes problems such as clogging of transportation pipes for natural gas, for example, and suppression of the generation is desired.

In order to suppress the formation of such gas hydrates, it is important to control interactions between hydrophobic gas molecules and water molecules. It is known that amphipathic polymers can more appropriately control interactions between gas molecules and water molecules by making use of both hydrophilic and hydrophobic properties. However, amphipathic polymers have the problem that they tend to leave even if they approach the crystal growth site of gas hydrate, and the effect of inhibiting the formation of gas hydrate has not yet been sufficient. Therefore, in recent years, there has been a demand for the development of polymer compounds that are more effective in inhibiting production.

On the other hand, the polymer compound of the present invention exhibits an even better effect of inhibiting gas hydrate formation due to the encapsulating ability of the cyclic unit while making use of the amphipathic properties derived from conventional amphiphilic polymers. obtain. Although the detailed mechanism by which such an effect is exhibited is not clear, the present inventors consider as follows.

First, the cyclic unit that constitutes the polymer compound of the present invention has a hydrophobic field on the inside and a hydrophilic group on the outside. , and the hydrophobic field inside it allows easy access to hydrophobic gas molecules (eg, methane, ethane, etc.) that act as nuclei for gas hydrate formation. Furthermore, it is thought that by enclosing gas molecules that approach closely in the hydrophobic field of the cyclic unit, the polymer compound of the present invention can be fixed to the crystal growth site of the gas hydrate, making it difficult to separate. As a result, it is considered that the amphipathic polymer unit chemically bonded to such a cyclic unit can sufficiently exhibit the effect of inhibiting gas hydrate formation at the crystal growth site of the gas hydrate.

Such a polymer compound of the present invention can exhibit a production inhibitory effect equal to or greater than that of a conventional amphipathic polymer when used in a small amount.

In particular, in the polymer compound of the present invention used as a gas hydrate formation inhibitor, the cyclic unit is derived from at least one cyclic compound selected from cyclodextrin, calixarene, cucurbituril and derivatives thereof. is preferred, and among them, it is more preferred that it is derived from cyclodextrin. In such a polymer compound, the amphiphilic polymer unit is preferably derived from a polymer obtained by polymerizing at least one monomer selected from N-vinyl-ε-caprolactam and N-vinylpyrrolidone. Among them, it is more preferably derived from a polymer obtained by polymerizing N-vinyl-ε-caprolactam.

(Method for synthesizing polymer compound)
Although the method for synthesizing the polymer compound of the present invention is not particularly limited, it can be synthesized, for example, by the following method.
In the following description, cyclodextrin (CD) is used as the cyclic compound, and polyvinylcaprolactam (PVCcap) is used as the amphipathic polymer. Even if a cyclic compound and an amphiphilic polymer are used, basically the same procedure can be performed.

<Method 1: Method of forming an ester bond with CD>
First, as shown by the following formula (I), azobisisobutyronitrile (AIBN) as an azo radical polymerization initiator, dimethylformamide (DMF) as a polymerization solvent, and mercaptoacetic acid as a chain transfer agent. Vinylcaprolactam (VCap) is polymerized in the presence of VCap to synthesize PVCcap [polymer (A)] having a terminal carboxyl group.
Next, as shown by the following formula (II), thionyl chloride (SOCl ₂ ) is used to chlorinate the carboxyl groups of the polymer (A) to obtain PVCcap [polymer (B) ].
Furthermore, as shown by the following formula (III), in the presence of triethanolamine (TEA) and DMF, the polymer (B) and CD are reacted to form an ester bond to form a novel polymer compound. (X) is obtained. When multiple (2 to 5) hydroxyl groups at the 6-position of CD are modified, the modification may be performed randomly or in blocks (also in the following modification of CD same.).

<Method 2: Method of forming an amide bond with CD>
First, as represented by the following formulas (IV) to (V), a compound (E) is obtained in which the hydroxyl group at the 6-position of CD is substituted with an amino group.
Furthermore, as shown in the following formula (VI), in the presence of 1-hydroxybenzotriazole (HOBt) and water-soluble carbodiimide (WSC), the compound (E) and the terminal carboxyl obtained in the above formula (I) A group-containing PVC Cap [polymer (A)] is reacted to form an amide bond to obtain a novel polymer compound (Y).

<Method 3: Method of converting CD into a chain transfer agent and using it>
For example, it can be carried out by any of the following methods.
<Method 3-1>
As shown by the following formula (VII), the compound (E) obtained by the above formula (V) is reacted with dithioglycolic acid to prepare a compound (F), and as shown by the following formula (VIII) , the compound (F) is reduced to give CD [compound (G)] with —SH.
Then, as represented by the following formula (IX), in the presence of AIBN, which is an azo radical polymerization initiator, VCap is polymerized using compound (G) as a chain transfer agent to obtain a novel polymer compound. (Y) is obtained.

<Method 3-2>
As shown by the following formula (X), the compound (C) of the above formula (IV) is reacted with thiourea to prepare the compound (H), and as shown by the following formula (XI), the compound ( H) is reduced to give CD [compound (I)] with —SH.
Then, as represented by the following formula (XII), in the presence of AIBN, which is an azo radical polymerization initiator, VCap is polymerized using compound (I) as a chain transfer agent to obtain a novel polymer compound. (Z) is obtained.

The compound of the present invention can be synthesized, for example, by the methods described above, but may be synthesized by methods other than those described above.

Although the embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, and includes various aspects within the scope of the present invention including the concept of the present invention and the scope of claims. can be modified to

EXAMPLES The present invention will be described in more detail below with reference to examples. However, the present invention is by no means limited to the following examples.

(Production example 1)
12 g of β-cyclodextrin (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was placed in a reaction vessel and dissolved in 172 mL of deionized water to obtain a reaction solution. At 0° C., 12 mL of a 4.5 mol/L aqueous solution of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was slowly added over 2 minutes to the reaction solution. Subsequently, a solution obtained by dissolving 2.89 g of p-toluenesulfonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 6.6 mL of acetonitrile (manufactured by Nacalai Tesque Co., Ltd.) was slowly added dropwise to the reaction solution. . After reacting this reaction solution at room temperature for 4 hours, the pH of the reaction solution was adjusted to 6 using a 3 mol/L solution of hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.). Thereafter, the precipitate was collected to obtain tosylated CD (compound (C) above).

3.01 g of the synthesized tosylated CD and 1.78 g of thiourea (manufactured by Nacalai Tesque Co., Ltd.) were dissolved in 120 mL of DMF (manufactured by Kanto Chemical Co., Ltd., anhydrous), and the mixture was dissolved in a nitrogen gas atmosphere at 75° C. for 48 hours. allowed to stir. After cooling the reaction solution with air, the product was reprecipitated in diethyl ether (manufactured by Nacalai Tesque, Inc.) to collect the precipitate, which was then recrystallized using acetone to collect the precipitate. The resulting precipitate is reduced using sodium pyrosulfite (Na ₂ S ₂ O ₅ , manufactured by Nacalai Tesque Co., Ltd.), purified by a freeze-drying method, and a CD derivative chain transfer agent (the above compound (I) ).

103 mg of the synthesized chain transfer agent, N-vinylcaprolactam (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.106 g, DMF 1.11 mL, and AIBN (manufactured by Wako Pure Chemical Industries, Ltd.) 3.68 mg were placed in a flask, After bubbling nitrogen gas for 2 minutes, the reaction was started at 80°C. After 16 hours, the reaction solution was air-cooled, reprecipitated in diethyl ether, and centrifuged to separate and purify the target polymer compound.

The obtained compound was identified by ¹ H-NMR measurement using a nuclear magnetic resonance apparatus (JNM-ECX400, manufactured by JEOL RESONANCE Co., Ltd.) and mass spectrometry using a MALDI-TOF/MS apparatus (AutoflexII, manufactured by BRUKER). and molecular weight measurement using a GPC measurement device (Shimadzu Corporation, Prominence GPC system, detector: RI, UV). As a result of the identification, synthesis of the polymer compound of the present invention (compound (Z) above) in which PVCap having a molecular weight of about 1300 to 4000 was directly bound to CD was confirmed.

[Evaluation] Method for evaluating gas hydrate formation inhibition performance The gas hydrate formation inhibition performance of the inhibitor was evaluated by the following method.
(1) First, 26.28 g of common salt (NaCl) and 170 g of tetrahydrofuran (THF, 99.9%, manufactured by Kanto Kagaku Co., Ltd.) are mixed, water is added, and THF is added so that the final volume becomes 900 mL. / NaCl aqueous solution is prepared. 80 mL of this THF/NaCl aqueous solution is placed in a 100 mL glass beaker.
(2) Next, 0.16 g of the inhibitor is added to the THF/NaCl aqueous solution in the beaker to prepare a solution having an inhibitor concentration of 0.2% by mass. In addition, inhibitors are as described in Example 1 and Comparative Examples 1 and 2 below.
(3) Place the beaker of the inhibitor/THF/NaCl aqueous solution prepared in (2) above in a cooling bath set at -0.5°C (±0.05°C).
(4) Stir the solution every 5 minutes and cool for 20 minutes.

(5) Next, a glass tube (diameter 7 mm) is filled with ice kept at -10°C.
(6) Immerse the tip of the glass tube at least halfway in the chilled inhibitor/THF/NaCl aqueous solution and cool for 30 minutes. A high-low temperature circulator (F12-ED, manufactured by JULABO) was used as the cooling bath.

(7) Then, THF hydrate is allowed to crystallize at the end of the tube for 30 minutes. After that, the tube is taken out, the form of THF hydrate is confirmed, the amount of THF hydrate produced is measured, and the production rate (g/min) is calculated. A smaller production rate means a greater inhibitory effect of the inhibitor.

(Example 1)
As the inhibitor for evaluation 1, the polymer compound produced in Production Example 1 was used. At this time, the form of the product was sherbet-like, and the production rate was 0.89 g/min.

Here, the term "sherbet-like" refers to a fluid state in which fine crystals are aggregated rather than completely solidified crystals (the same applies hereinafter). Normally, when no inhibitor is used, the crystal growth of the product proceeds, and the product solidifies in lumps, causing clogging of gas pipes and the like. However, if the product is sherbet-like, it is possible to ensure adequate fluidity, so clogging of gas pipes and the like can be suppressed.

In the sherbet-like product, unlike solid crystals, the crystals and water cannot be completely separated. Therefore, when calculating the production rate, the amount of production is the value measured when the sherbet-like product is collected, drained moderately at the edge of the beaker using a medicine spoon, and contains water as it is. (same below).

(Comparative example 1)
As an inhibitor for evaluation 1, PVCap synthesized by the following method was used. At this time, the product was sherbet-like and the production rate was 1.40 g/min.

The PVCcap used in Comparative Example 1 was synthesized by the following method.
First, 1.26 mL of mercaptoacetic acid (manufactured by Wako Pure Chemical Industries, Ltd.), 21.0 g of N-vinylcaprolactam, 102 mL of DMF, and 0.342 g of AIBN were placed in a flask, and nitrogen gas was bubbled for 2 minutes. °C, the reaction was initiated. After 8 hours, the reaction solution was air-cooled, reprecipitated in diethyl ether, and separated and purified by centrifugation to PVCcap.
As a result of identification of the compound by the same method as above, the synthesis of PVCap (compound (A) above) having a molecular weight of about 2000 was confirmed.

(Comparative example 2)
As an inhibitor for evaluation 1, the mixture of PVCcap and β-cyclodextrin used in Comparative Example 1 (mixing ratio: 1:1 by weight) was used. At this time, the product was sherbet-like and the production rate was 1.61 g/min.

It was confirmed that the polymer compound of the present invention is effective as an inhibitor for suppressing the production of THF hydrate (Example 1). On the other hand, it was confirmed that PVCap, which has been conventionally used as an inhibitor, is inferior to the polymer compound of the present invention in the effect of suppressing the formation of THF hydrate (Comparative Examples 1 and 2).

In particular, as can be seen from the comparison between Example 1 and Comparative Example 2, the THF hydrate formation inhibitory effect is higher when PVCCap and β-cyclodextrin are chemically bonded together. It was confirmed that the size increased compared to the case where PVCCap and β-cyclodextrin were simply mixed.

Claims (4)

A polymer compound having a cyclic unit having encapsulating ability and an amphipathic polymer unit chemically bonded to the cyclic unit,
the cyclic unit has a hydrophobic site on the inside and a hydrophilic group on the outside;
A polymer compound, wherein the amphipathic polymer unit is derived from a polymer obtained by polymerizing only at least one monomer selected from N-vinyl-ε-caprolactam and N-vinylpyrrolidone. A polymer compound having a cyclic unit having encapsulating ability and an amphipathic polymer unit chemically bonded to the cyclic unit,
the cyclic unit has a hydrophobic site on the inside and a hydrophilic group on the outside;
A polymer compound, wherein the amphipathic polymer unit is derived from a polymer obtained by polymerizing N-vinyl-ε-caprolactam. 3. The polymer compound according to claim 1, wherein the cyclic unit is derived from at least one cyclic compound selected from cyclodextrin, calixarene, cucurbituril and derivatives thereof. 4. The polymer compound according to any one of claims 1 to 3, wherein the amphipathic polymer unit is bonded to 1 unit or more and 8 units or less with respect to 1 unit of the cyclic unit.