JP7653148B2 - Polymeric material and its manufacturing method - Google Patents

Description

The present invention relates to a polymeric material having a polysiloxane skeleton and a method for producing the same.

Synthetic polymer compounds (polysiloxanes) with siloxane bonds (Si-O bonds) in the main skeleton are known to have unique properties not found in organic polymers, and are used in a variety of fields. Siloxane bonds have stronger bonding strength than the carbon-carbon or carbon-oxygen bonds present in general organic polymers, and are chemically stable, so polysiloxanes formed with repeated siloxane bonds have, for example, excellent heat resistance and weather resistance. In addition, polysiloxanes can form a helical structure in which inorganic siloxane bonds are located on the inside and organic side chain substituents are located on the outside, making them flexible, water repellent, and less biotoxic. Therefore, polysiloxanes are highly valuable materials in a variety of applications, such as medical devices, rubber, paints, and protective films.

On the other hand, in recent years, there has been a demand for providing further functionality to polysiloxane-based materials, such as further improvements in mechanical properties and self-repairing properties. From this perspective, for example, Non-Patent Document 1 proposes a technology in which functional groups capable of hydrogen bonding are introduced into the polysiloxane skeleton, and self-repairing properties are exerted through the hydrogen bonds of such functional groups.

Adv. Mater. 2018,30,1706846

However, recently, there has been a strong demand for adding further functions to polysiloxanes so that they can be used in a variety of applications. For example, one of the features of polysiloxanes is their excellent water repellency, but since it has been difficult to improve their hygroscopicity, the applications of polysiloxanes are often limited. For this reason, there is a demand for polysiloxanes with high hygroscopicity. From this perspective, if it were possible to produce polysiloxanes with excellent mechanical properties and further improved hygroscopicity, it would be possible to apply polysiloxanes to applications that were not possible with conventional polysiloxanes, and it could be said that such polysiloxanes would have very high utility value.

The present invention has been made in consideration of the above, and aims to provide a polymeric material having a polysiloxane skeleton with excellent mechanical properties and high moisture absorption, and a method for producing the same.

As a result of extensive research into achieving the above-mentioned objective, the inventors discovered that the above-mentioned objective can be achieved by introducing specific functional groups capable of host-guest interaction into the polysiloxane skeleton, thus completing the present invention.

That is, the present invention includes, for example, the subject matter described in the following sections.
Item 1
A polymer material having a polysiloxane skeleton,
The polysiloxane skeleton has a side chain represented by the following general formula (1):
-R ¹ -R ^H (1)
(In formula (1), R ¹ represents NH or O, and R ^H represents a host group.)
The structural unit represented by
the host group is a monovalent group obtained by removing one hydrogen atom or one hydroxyl group from a cyclodextrin or a cyclodextrin derivative,
The cyclodextrin derivative is a polymeric material having a structure in which a hydrogen atom of at least one hydroxyl group of cyclodextrin is substituted with at least one group selected from the group consisting of a hydrocarbon group, an acyl group, and -CONHR (R is a methyl group or an ethyl group).
Item 2
Item 2. The polymer material according to item 1, wherein the host group includes the guest group to form an inclusion complex, and the included guest group is chemically bonded to a side chain of the polysiloxane skeleton.
Item 3
Item 2. The polymer material according to item 1, having a structure in which polysiloxane penetrates into the ring of the host group.
Item 4
Item 3. A method for producing a polymeric material according to item 1 or 2,
The following general formula (1a)
R ² -R ^H (1a)
(In formula (1a), ^R2 represents _NH2 or OH, and ^RH has the same meaning as ^RH in formula (1).)
and a guest molecule is included in the compound represented by the formula:
A polysiloxane having a reactive functional group in a side chain;
A method for producing a polymer material, comprising the step of reacting
Item 5
Item 5. The method according to item 4, wherein the reactive functional group is an epoxy group.

The polymeric material of the present invention has excellent mechanical properties and high moisture absorption.

FIG. 1 is a diagram for illustrating a schematic example of a polymer material of the present invention. FIG. 2 is a diagram for explaining a schematic diagram of another example of the polymer material of the present invention. 6(a) and 6(b) show the results of mass spectrum and NMR spectrum of NH ₂ -PMβCD, respectively. 1 is a reaction scheme of the reaction carried out in Example 1. 1 is a ¹ H-NMR spectrum (CDCl ₃ , 500 MHz, 25° C.) of the polymer material obtained in Example 1.

Hereinafter, an embodiment of the present invention will be described in detail. In this specification, the expressions "containing" and "comprise" include the concepts of "containing," "comprises," "consists essentially of," and "consists only of."

1. Polymer Material The polymer material of the present invention has a polysiloxane skeleton, and the polysiloxane skeleton has a side chain represented by the following general formula (1):
-R ¹ -R ^H (1)
(In formula (1), R ¹ represents NH or O, and R ^H represents a host group.)
Here, the host group is a monovalent group obtained by removing one hydrogen atom or hydroxyl group from cyclodextrin or a cyclodextrin derivative, and the cyclodextrin derivative has a structure in which the hydrogen atom of at least one hydroxyl group in the cyclodextrin is substituted with at least one group selected from the group consisting of a hydrocarbon group, an acyl group, and -CONHR (R is a methyl group or an ethyl group).

In this specification, "at least one group selected from the group consisting of hydrocarbon groups, acyl groups, and -CONHR (R is a methyl group or an ethyl group)" may be referred to as "hydrocarbon groups, etc." for convenience.

The polymer material of the present invention is a material formed of a molecular chain having a polysiloxane skeleton. The polysiloxane skeleton is a chain polymer having a siloxane bond and has a "-Si-O-Si-" structure as the smallest structural unit. The polysiloxane skeleton may be linear. In addition, in the polysiloxane skeleton, when the Si atom in the "-Si-O-Si-" structure further has a siloxane bond (-O-Si), the polysiloxane skeleton may be a branched structure or a crosslinked structure. From the viewpoint that the polymer material has appropriate mechanical properties and is easy to exhibit the self-repairing property described below, it is preferable that the polysiloxane skeleton is linear.

When the polysiloxane skeleton is linear, the polysiloxane skeleton may contain, for example, a structural unit represented by the following formula (2):

In formula (2), ^R3 and ^R4 are the same or different and each represents a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted with a substituent, or an aryl group having 6 to 20 carbon atoms which may be substituted with a substituent.

In formula (2), the linear or branched alkyl group having 1 to 10 carbon atoms preferably has 1 to 4 carbon atoms, and particularly preferably has 1 or 2 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group.

In formula (2), when the linear or branched alkyl group having 1 to 10 carbon atoms is substituted with a substituent, the number of the substituents can be 1 or 2 or more. In this case, examples of the substituent include a hydroxy group, an alkoxy group, an ester group, a cyano group, a nitro group, a sulfo group, a carboxy group, an aryl group, and a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom).

In formula (2), examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, and a tetrahydronaphthyl group. When the aryl group is substituted with a substituent, the number of the substituents can be 1 or 2 or more. In this case, examples of the substituent include a hydroxy group, an alkoxy group, an ester group, a cyano group, a nitro group, a sulfo group, a carboxy group, an aryl group, and a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom).

In formula (2), ^R3 and ^R4 may be the same or different. In formula (2), ^R3 and ^R4 are preferably both a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and a methyl group is particularly preferred. When ^R3 and ^R4 are both a methyl group, the polysiloxane skeleton contains polydimethylsiloxane.

As described above, the polysiloxane skeleton has a structural unit "-R ¹ -R ^H " represented by the above formula (1) in a side chain. R ¹ in such a structural unit can be directly bonded to Si in the polysiloxane skeleton, or can be indirectly bonded (i.e., another group is interposed between R ¹ and Si). In yet another embodiment, R ¹ can be directly bonded to a side chain of a vinyl polymer.

When ^R1 is directly bonded to Si in the polysiloxane skeleton or indirectly bonded (i.e., another group is present between ^R1 and Si), for example, the polysiloxane skeleton can further include a constitutional unit represented by the following formula (3).

In formula (3), ^R5 has the same meaning as ^R3 and ^R4 in formula (2). In formula (3), ^R6 represents a divalent group containing an alkylene having 1 to 10 carbon atoms, and n is the number of 0 or 1. When n is 0, this means that ^R6 is absent, that is, ^R1 is directly bonded to a silicon atom.

In formula (3), R ⁵ is preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and particularly preferably a methyl group.

In formula (3), R ⁶ is not particularly limited as long as it is a divalent group containing an alkylene having 1 to 10 carbon atoms. In R ⁶ , the number of carbon atoms of the alkylene is preferably 1 to 8, more preferably 2 to 6. R ⁶ can also contain, for example, a heteroatom. Examples of the heteroatom include oxygen and nitrogen. When R ⁶ contains a heteroatom, R ⁶ can also have an ether bond, an amide bond, an amino group, etc., and among them, it is preferable to have an ether bond (for example, -(CH ₂ ) ₃ -O-(CH ₂ ) ₃ - bond is exemplified). The monovalent group containing an alkylene having 1 to 10 carbon atoms can further have a substituent. The type of the substituent is not particularly limited, and examples thereof include a hydroxy group, an alkoxy group, an ester group, a cyano group, a nitro group, a sulfo group, a carboxy group, an aryl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), etc., and a hydroxy group is particularly preferable.

On the other hand, when R ¹ is directly bonded to the side chain of the vinyl polymer as described above, the vinyl polymer can be, for example, a known vinyl polymer, for example, various acrylic polymers can be exemplified. Among them, (meth)acrylic acid ester, N-substituted (meth)acrylamide, etc. can be exemplified. In these cases, R ¹ can be bonded to the ester moiety of the (meth)acrylic acid ester or the amide moiety of the N-substituted (meth)acrylamide. As an example of the case where R ¹ is directly bonded to the side chain of the vinyl polymer, for example, a polymer of a host group-containing polymerizable monomer described in International Publication No. 2018/159791 can be exemplified.

In formula (1), R ¹ is NH or O, and is particularly preferably NH.

R ^H , that is, the host group, is a monovalent group obtained by removing one hydrogen atom or hydroxyl group from cyclodextrin or a cyclodextrin derivative. In particular, the host group is preferably a monovalent group obtained by removing one hydrogen atom or hydroxyl group from a cyclodextrin derivative. The cyclodextrin derivative has a structure in which the hydrogen atom of at least one hydroxyl group in cyclodextrin is substituted with a hydrocarbon group or the like (that is, at least one group selected from the group consisting of hydrocarbon groups, acyl groups, and -CONHR (R is a methyl group or an ethyl group)). In other words, a cyclodextrin derivative refers to a molecule having a structure in which a cyclodextrin molecule is substituted with another organic group. However, the cyclodextrin derivative has at least one hydrogen atom or one hydroxyl group, and preferably has at least one hydroxyl group.

As a precautionary note, the term "cyclodextrin" used in this specification means at least one selected from the group consisting of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin. Therefore, the cyclodextrin derivative is at least one selected from the group consisting of α-cyclodextrin derivatives, β-cyclodextrin derivatives, and γ-cyclodextrin derivatives.

The host group is preferably a monovalent group in which one hydroxyl group has been removed from a cyclodextrin or cyclodextrin derivative.

A host group is a monovalent group in which one hydrogen atom or hydroxyl group has been removed from a cyclodextrin or cyclodextrin derivative, but the hydrogen atom or hydroxyl group removed in the cyclodextrin or cyclodextrin derivative may be at any position on the cyclodextrin or cyclodextrin derivative.

Here, if the total number of hydroxyl groups in one cyclodextrin molecule is N, then for α-cyclodextrin, N is 18, for β-cyclodextrin, N is 21, and for γ-cyclodextrin, N is 24.

If the host group is a monovalent group obtained by removing one "hydroxyl group" from a cyclodextrin derivative, the cyclodextrin derivative is formed by replacing the hydrogen atoms of up to N-1 hydroxyl groups per cyclodextrin molecule with hydrocarbon groups, etc. On the other hand, if the host group is a monovalent group obtained by removing one "hydrogen atom" from a cyclodextrin derivative, the cyclodextrin derivative can have the hydrogen atoms of up to N hydroxyl groups per cyclodextrin molecule replaced with hydrocarbon groups, etc.

The host group preferably has a structure in which the hydrogen atoms of 70% or more of the total number of hydroxyl groups present in one molecule of the cyclodextrin are substituted with the hydrocarbon group or the like. In this case, the structural unit represented by formula (1) can exhibit a higher affinity for hydrophobic monomer units. The host group more preferably has the hydrogen atoms of 80% or more of the total number of hydroxyl groups present in one molecule of the cyclodextrin substituted with the hydrocarbon group or the like, and particularly preferably has the hydrogen atoms of 90% or more of the total number of hydroxyl groups substituted with the hydrocarbon group or the like.

The host group preferably has a structure in which the hydrogen atoms of 13 or more of the total hydroxyl groups present in one molecule of α-cyclodextrin are substituted with the hydrocarbon group, etc. It is more preferable that the hydrogen atoms of 15 or more of the total hydroxyl groups present in one molecule of α-cyclodextrin are substituted with the hydrocarbon group, etc., and it is particularly preferable that the hydrogen atoms of 17 of the total hydroxyl groups are substituted with the hydrocarbon group, etc.

The host group preferably has a structure in which the hydrogen atoms of 15 or more of the total hydroxyl groups present in one β-cyclodextrin molecule are substituted with the hydrocarbon group, etc. It is more preferable that the hydrogen atoms of 17 or more of the total hydroxyl groups present in one β-cyclodextrin molecule are substituted with the hydrocarbon group, etc., and it is particularly preferable that the hydrogen atoms of 19 or more of the total hydroxyl groups are substituted with the hydrocarbon group, etc.

The host group preferably has a structure in which the hydrogen atoms of 17 or more of the total hydroxyl groups present in one molecule of γ-cyclodextrin are substituted with the hydrocarbon group, etc. It is more preferable that the hydrogen atoms of 19 or more of the total hydroxyl groups present in one molecule of γ-cyclodextrin are substituted with the hydrocarbon group, etc., and it is particularly preferable that the hydrogen atoms of 21 or more of the total hydroxyl groups are substituted with the hydrocarbon group, etc.

When the host group has two or more hydrocarbon groups, they may all be the same or some may be different.

In the cyclodextrin derivative, the type of the hydrocarbon group is not particularly limited. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group.

The number of carbon atoms in the hydrocarbon group is not particularly limited, and for example, it is preferable that the number of carbon atoms in the hydrocarbon group is 1 to 4.

Specific examples of hydrocarbon groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, and butyl groups. When the hydrocarbon group is a butyl group, it may be either linear or branched.

The hydrocarbon group may have a substituent as long as the effect of the present invention is not impaired.

In the cyclodextrin derivative, examples of the acyl group include an acetyl group, a propionyl group, and a formyl group. The acyl group may further have a substituent. From the viewpoint of facilitating the formation of host-guest interactions and facilitating the production of a polymer material having excellent toughness and strength, it is preferable that the acyl group is an acetyl group.

In the cyclodextrin derivative, -CONHR (R is a methyl group or an ethyl group) is a methyl carbamate group or an ethyl carbamate group. From the viewpoint of facilitating the formation of host-guest interactions, -CONHR is preferably an ethyl carbamate group.

In cyclodextrin derivatives, the hydrocarbon groups etc. are preferably methyl groups and acyl groups, more preferably methyl groups, acetyl groups and propionyl groups, and particularly preferably methyl groups and acetyl groups.

The polysiloxane skeleton may have other structural units. Examples of the other structural units include siloxane units in which a reactive functional group is directly or indirectly bonded to a silicon atom. Specifically, the polysiloxane skeleton may further include a structural unit represented by the following formula (4):

In formula (4), ^R7 has the same meaning as ^R3 and ^R4 in formula (2) above. In formula (4), ^R8 represents a monovalent group containing an alkylene having 1 to 8 carbon atoms, and A represents a reactive functional group.

In formula (4), R ⁷ is preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and particularly preferably a methyl group.

In formula (4), R ⁸ is not particularly limited as long as it is a divalent group containing an alkylene having 1 to 8 carbon atoms. In R ⁸ , the number of carbon atoms of the alkylene is preferably 1 to 8, more preferably 2 to 7, even more preferably 2 to 6, and particularly preferably 2 to 5. R ⁸ can also contain, for example, a heteroatom. Examples of heteroatoms include oxygen and nitrogen. When R ⁸ contains a heteroatom, R ⁸ can also have, for example, an ether bond, an amide bond, an amino group, and the like, and among these, it is preferable to have an ether bond (for example, -(CH ₂ ) ₃ -O-(CH ₂ )- bond is exemplified). The monovalent group containing an alkylene having 1 to 8 carbon atoms can further have a substituent. The type of the substituent is not particularly limited, and examples thereof include a hydroxy group, an alkoxy group, an ester group, a cyano group, a nitro group, a sulfo group, a carboxy group, an aryl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), and the like, and a hydroxy group is particularly preferable.

In formula (4), the reactive functional group A can be, for example, an epoxy group, a carboxy group, an amino group, a hydroxyl group, an ester group, etc., and is preferably an epoxy group because of its high reactivity with the guest molecule described below.

In the polysiloxane skeleton, the content ratio of the structural unit represented by the formula (2) can be, for example, 5 to 95 mol% based on the total amount of the structural units represented by the formulas (2), (3), and (4). From the viewpoint of easily controlling the hygroscopicity of the polymer material and easily exhibiting the self-repairing performance described below, the content ratio of the structural unit represented by the formula (2) is, for example, preferably 20 mol% or more, more preferably 30 mol% or more, particularly preferably 40 mol% or more, and preferably 90 mol% or less, more preferably 80 mol% or less, and particularly preferably 75 mol% or less based on the total amount of the structural units represented by the formulas (2), (3), and (4).

In the polysiloxane skeleton, the content ratio of the structural unit represented by the formula (3) can be, for example, 0.01 to 30 mol% based on the total amount of the structural units represented by the formulas (3) and (4). From the viewpoint of easily controlling the hygroscopicity of the polymer material and easily exhibiting the self-repairing performance described below, the content ratio of the structural unit represented by the formula (3) is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, particularly preferably 1 mol% or more, and preferably 20 mol% or less, more preferably 15 mol% or less, particularly preferably 10 mol% or less, based on the total amount of the structural units represented by the formulas (3) and (4).

In the polymer material of the present invention, the polysiloxane skeleton may have other structural units in addition to the structural units represented by the formulas (2), (3), and (4) as necessary. In other words, the polymer material of the present invention may be formed of a molecular chain having structural units represented by the formulas (2), (3), and (4) and other structural units. The other structural units may be, for example, 5% by mass or less, preferably 1% by mass or less, more preferably 0.1% by mass or less, and particularly preferably 0.05% by mass or less, based on the total amount of the structural units represented by the formulas (2), (3), and (4). The polysiloxane skeleton may also be formed only from the structural units represented by the formulas (2), (3), and (4). In other words, the polymer material of the present invention may also be formed of a molecular chain having only the structural units represented by the formulas (2), (3), and (4).

In the polymeric material of the present invention, the polysiloxane skeleton may have any structure, such as a random polymer or a block polymer, and it is preferable that the structure is a random polymer, for example, because of ease of production.

The polymeric material has improved hydrophilicity due to the inclusion of the structural unit represented by formula (1) in the side chain of the polysiloxane skeleton, and therefore has moisture absorption properties equal to or superior to those of conventional silicon materials. Therefore, the polymeric material has excellent moisture absorption properties despite having a polysiloxane skeleton, and furthermore, since it has the flexibility and toughness that are characteristic of the polysiloxane skeleton, it also has excellent mechanical properties.

In the polymer material of the present invention, the host group encapsulates the guest group to form an inclusion complex, and the encapsulated guest group may be chemically bonded (e.g., covalently bonded) to a side chain of the polysiloxane skeleton.

A guest group is a group derived from a guest molecule, specifically, a group formed by removing one or two hydrogen atoms from a guest molecule. Examples of guest molecules include compounds capable of forming an inclusion complex with the host group.

The guest molecule is not particularly limited as long as it can form an inclusion complex with the host group, and examples thereof include a compound having one or two (preferably one) amino groups, a compound having one or two (preferably one) hydroxyl groups, a compound having one or two (preferably one) carboxy groups, a compound having one or two (preferably one) epoxy groups, a compound having one or two (preferably one) isocyanate groups, a compound having one or two (preferably one) thiol groups, and a compound having one or two carboxylic acid chlorides.

Examples of compounds having one or two amino groups include 1-adamantanamine, benzylamine, tert-butylamine, butylamine, 1-aminopyrene, aminoferrocene, 4-aminoazobenzene, 4-aminostilbene, cyclohexylamine, hexylamine, 4,4'-diaminodiphenylmethane, p-xylylenediamine, diaminoferrocene, 4,4'-diaminoazobenzene, 4,4'-diaminostilbene, 1,4-diaminocyclohexane, 1,6-diaminocyclohexane, α,ω-diaminopolyethylene glycol, α,ω-diaminopolypropylene glycol, 2,2-bis(4-aminophenyl)propane, 1,1-bis(4-aminophenyl)-1-phenylethane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2 bis(4-aminophenyl)butane, bis(4-aminophenyl)diphenylmethane, 2,2-bis(3-methyl-4-aminophenyl)propane, bis(4-aminophenyl)-2,2-dichloroethylene, 1,1-bis(4-aminophenyl)ethane, 2,2-bis(4-amino-3-isopropylphenyl)propane, 1,3-bis(2-(4-aminophenyl)-2-propyl)benzene, bis(4-aminophenyl)sulfone, 1,4-bis(2-(4-aminophenyl)-2-propyl)benzene, 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-amine]propane, 1,1-bis(4-aminophenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-aminophenyl)cyclohexane, and the like.

Examples of compounds having one or two hydroxyl groups include 1-hydroxyadamantane, benzyl alcohol, tert-butyl alcohol, butyl alcohol, 1-hydroxypyrene, 1-hydroxymethylferrocene, 4-hydroxyazobenzene, 4-hydroxystilbene, cyclohexanol, hexanol, 4,4'-dihydroxydiphenylmethane, 2,2-bis(4-hydroxyphenyl)propane, 1,4-benzenedimethanol, 1,1'-dihydroxymethylferrocene, 4,4'-dihydroxyazobenzene, 4,4'-dihydroxystilbene, 1,4-cyclohexenol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, bis(4-hydroxyphenyl)sulfone, 1,4-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-hydroxy]propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bisphenol A, and the like can be mentioned.

Examples of compounds having one or two carboxy groups include 1-carboxyadamantane, benzoic acid, pivalic acid, butanoic acid, 1-carboxypyrene, 1-carboxyferrocene, 4-carboxyazobenzene, 4-carboxystilbene, cyclohexanoic acid, hexanoic acid, 4,4'-dicarboxydiphenylmethane, 1,4-benzenedicarboxylic acid, 1,4-phenylenediacetic acid, 1,1'-dicarboxyferrocene, 4,4'-dicarboxyazobenzene, 4,4'-dicarboxystilbene, 1,4-cyclohexanedicarboxylic acid, 1,6-hexanedicarboxylic acid, α,ω-dicarboxypolyethylene glycol, α,ω-dicarboxypolypropylene glycol, 2,2-bis(4-carboxyphenyl)propane, 1,1-bis(4-carboxyphenyl)-1-phenylethane, and 2,2-bis(4-carboxyphenyl)hexafluoro. Examples of the bis(4-carboxyphenyl)propane include propane, 2,2-bis(4-carboxyphenyl)butane, bis(4-carboxyphenyl)diphenylmethane, 2,2-bis(3-methyl-4-carboxyphenyl)propane, bis(4-carboxyphenyl)-2,2-dichloroethylene, 1,1-bis(4-carboxyphenyl)ethane, 2,2-bis(4-carboxy-3-isopropylphenyl)propane, 1,3-bis(2-(4-carboxyphenyl)-2-propyl)benzene, bis(4-carboxyphenyl)sulfone, 1,4-bis(2-(4-carboxyphenyl)-2-propyl)benzene, 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-carboxy]propane, 1,1-bis(4-carboxyphenyl)-3,3,5-trimethylcyclohexane, and 1,1-bis(4-carboxyphenyl)cyclohexane.

Examples of compounds having one or two carboxylic acid chlorides include 1-adamantanecarbonyl chloride, terephthaloyl chloride, trimethylacetyl chloride, butyryl chloride, 1-pyrenecarbonyl chloride, 1-ferrocenecarbonyl chloride, 4-azobenzenecarbonyl chloride, 4-stilbenecarbonyl chloride, cyclohexanecarbonyl chloride, hexyl chloride, 4,4'-diphenylmethanedicarbonyl chloride, 1,4-benzenedicarbonyl chloride, 1,4-phenylene dicarbonyl chloride, 1,1'-ferrocenedicarbonyl chloride, 4,4'-azobenzenedicarbonyl chloride, 4,4'-stilbenecarbonyl chloride, 1,4-cyclohexanedicarbonyl chloride, 1,6-hexanedicarbonyl chloride, α,ω-polyethylene glycol dicarbonyl chloride, α,ω-polypropylene glycol dicarbonyl chloride, 2,2-bis(4-phenylcarbonyl chloride)propane, 1,1-bis(4-phenylcarbonyl chloride)-1-phenylethane, 2,2-bis(4-phenylcarbonyl chloride)hexafluoropropane, 2,2-bis(4-phenylcarbonyl chloride)butane, bis(4-phenylcarbonyl chloride)diphenylmethane, 2,2-bis(3-methyl-4-phenylcarbonyl chloride)propane, bis(4-phenylcarbonyl chloride)-2,2-dichloroethylene, 1,1-bis(4-phenylcarbonyl chloride)ethane, 2,2-bis(3-isopropylphenyl-4-carbonyl chloride)propane, 1,3-bis(2- (4-phenylcarbonyl chloride)-2-propyl)benzene, bis(4-phenylcarbonyl chloride)sulfone, 1,4-bis(2-(4-phenylcarbonyl chloride)-2-propyl)benzene, 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-carbonyl chloride]propane, 1,1-bis(4-phenylcarbonyl chloride)-3,3,5-trimethylcyclohexane, 1,1-bis(4-phenylcarbonyl chloride)cyclohexane, and the like can be mentioned.

Examples of compounds having one or two epoxy groups include adamantane oxide, styrene oxide, 1,2-epoxybutane, 1-epoxypyrene, epoxyferrocene, 4-epoxyazobenzene, 4-epoxystilbene, cyclohexyl oxide, 1,2-epoxyhexane, 2,2'-bis(4-glycidyloxyphenyl)propane, p-diglycidyloxybenzene, diglycidyloxyferrocene, 4,4'-diglycidyloxyazobenzene, 4,4'-diglycidyloxyferrocene, 1,4-diglycidyloxycyclohexane, 1,6-diglycidyloxycyclohexane, α,ω-diglycidyloxypolyethylene glycol, α,ω-diglycidyloxypolypropylene glycol, 1,1-bis(4-glycidyloxyphenyl)-1-phenylethane, 2,2-bis(4-glycidyloxyphenyl)hexafluoropropane, 2,2-bis(4-glycidyloxyphenyl)hexafluoropropane, bis(4-glycidyloxyphenyl)butane, bis(4-glycidyloxyphenyl)diphenylmethane, 2,2-bis(3-methyl-4-glycidyloxyphenyl)propane, bis(4-glycidyloxyphenyl)-2,2-dichloroethylene, 1,1-bis(4-glycidyloxyphenyl)ethane, 2,2-bis(4-glycidyloxy-3-isopropylphenyl)propane, 1,3-bis(2-(4-glycidyloxyphenyl)-2-propyl )benzene, bis(4-glycidyloxyphenyl)sulfone, 1,4-bis(2-(4-glycidyloxyphenyl)-2-propyl)benzene, 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-glycidyloxy]propane, 1,1-bis(4-glycidyloxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-glycidyloxyphenyl)cyclohexane, and the like.

Examples of compounds having one or two isocyanate groups include 1-adamantane isocyanate, benzyl isocyanate, phenyl isocyanate, tert-butyl isocyanate, butyl isocyanate, 1-pyrene isocyanate, ferrocene isocyanate, azobenzene-4-isocyanate, stilbene-4-isocyanate, cyclohexane isocyanate, hexane isocyanate, 4,4'-diisocyanate phenylmethane, p-benzene diisocyanate, cyanate, ferrocene-1,1'-diisocyanate, azobenzene-4,4'-diisocyanate, stilbene-4,4'-diisocyanate, cyclohexane-1,4-diisocyanate, cyclohexane-1,6-diisocyanate, polyethylene glycol diisocyanate, polypropylene glycol diisocyanate, 2,2-bis(4-phenylisocyanate)propane, 1,1-bis(4-phenylisocyanate)-1-phenylethane, 2,2-bis (4-phenylisocyanate)hexafluoropropane, 2,2-bis(4-phenylisocyanate)butane, bis(4-phenylisocyanate)diphenylmethane, 2,2-bis(3-methyl-4-phenylisocyanate)propane, bis(4-phenylisocyanate)-2,2-dichloroethylene, 1,1-bis(4-phenylisocyanate)ethane, 2,2-bis(3-isopropyl-4-phenylisocyanate)propane, 1,3-bis(2-(4-fu Examples of the bis(4-phenylisocyanate)-2-propyl)benzene, bis(4-phenylisocyanate)sulfone, 1,4-bis(2-(4-phenylisocyanate)-2-propyl)benzene, 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-isocyanate]propane, 1,1-bis(4-phenylisocyanate)-3,3,5-trimethylcyclohexane, 1,1-bis(4-phenylisocyanate)cyclohexane, and the like can be mentioned.

Examples of compounds having one or two thiol groups include 1-adamantanethiol, benzylthiol, tert-mercaptan, butanethiol, 1-thiolpyrene, ferrocenethiol, 4-thioazobenzene, 4-thiostilbene, cyclohexylthiol, hexanethiol, 4,4'-dithiophenylmethane, p-benzenedithiol, 1,1'-dithioferrocene, 4,4'-dithioazobenzene, 4,4'-dithiostilbene, 1,4-dithiocyclohexane, 1,6-dithiocyclohexane, α,ω-dithiopolyethylene glycol, α,ω-dithiopolypropylene glycol, 1,1-bis(4-thiophenyl)-1-phenylethane, 2,2-bis(4-thiophenyl)hexafluoropropane, 2,2-bis(4 bis(4-thiophenyl)butane, bis(4-thiophenyl)diphenylmethane, 2,2-bis(3-methyl-4-thiophenyl)propane, bis(4-thiophenyl)-2,2-dichloroethylene, 1,1-bis(4-thiophenyl)ethane, 2,2-bis(4-thio-3-isopropylphenyl)propane, 1,3-bis(2-(4-thiophenyl)-2-propyl)benzene, bis(4-thiophenyl)sulfone, 1,4-bis(2-(4-thiophenyl)-2-propyl)benzene, 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-thiol]propane, 1,1-bis(4-thiophenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-thiophenyl)cyclohexane, and the like.

The guest molecule is preferably at least one of a compound having one amino group and a compound having one hydroxyl group, and more preferably a compound having one amino group. Specific examples of the guest molecule include 1-adamantanamine, benzylamine, tert-butylamine, butylamine, 1-aminopyrene, aminoferrocene, 4-aminoazobenzene, 4-aminostilbene, cyclohexylamine, hexylamine, 1-hydroxyadamantane, benzyl alcohol, tert-butyl alcohol, butyl alcohol, 1-hydroxypyrene, 1-hydroxymethylferrocene, 4-hydroxyazobenzene, and 4-hydroxystilbene, and more preferably 1-adamantanamine and 1-hydroxyadamantane, and particularly preferably 1-adamantanamine. In this case, the guest group is more likely to bond to the side chain of the polysiloxane skeleton, and the self-repairing property is more likely to be exhibited.

The guest molecule can be appropriately selected depending on the size of the ring of the host group, cyclodextrin or cyclodextrin derivative. For example, when the guest molecule is 1-adamantanamine, 1-hydroxyadamantane, etc., the host group is preferably β-cyclodextrin or a β-cyclodextrin derivative. In this case, the guest group is easily included in the host group.

In the polymer material of the present invention, the guest group included in the host group can be chemically bonded to the side chain of the polysiloxane skeleton. In this case, another functional group is usually present between the guest group and the Si of the polysiloxane skeleton. An example of the other functional group is ^R6 in the formula (3).

Furthermore, when the polysiloxane skeleton has a structural unit represented by formula (4), the guest molecule encapsulated in the host group can react with the reactive functional group in the structural unit represented by formula (4) to form a structure in which the guest group is bonded to the polysiloxane skeleton.

In the polymer material of the present invention, the polysiloxane molecular chain to which the guest group is bonded (a molecular chain having a polyrotaxane skeleton) may be a polysiloxane molecular chain to which a host group that encapsulates the guest group is bonded, or may be a polysiloxane molecular chain different from the polysiloxane molecular chain to which a host group that encapsulates the guest group is bonded.

When the host group in the side chain of the polysiloxane skeleton encapsulates the guest group, the inclusion ratio is not particularly limited, and for example, the inclusion ratio can be 10 mol% or more of the total amount of host groups in the polysiloxane skeleton, preferably 20 mol% or more, more preferably 30 mol% or more, even more preferably 40 mol% or more, and particularly preferably 50 mol% or more.

By having a structural unit represented by formula (1) in the side chain of the polysiloxane skeleton (specifically, by having a structural unit represented by the above formula (3)), the polymer material can form various polymer structures, one of which is the structure formed by the introduction of the guest group described above. In the polysiloxane skeleton, as described above, the guest group is included in the host group and the guest group is bonded to the polysiloxane skeleton, so that the polymer material can have reversible host-guest interactions within or between molecules (see Figure 1 described later). As a result, the polymer material containing such a polysiloxane skeleton has improved toughness and strength, and can also exhibit self-repairing properties. For example, even if the polymer material is cut, by re-adhering the cut surfaces, the host-guest interaction between the polymer materials occurs again between the cut surfaces, and the polymer material is repaired. In other words, when the polymer material is controlled to a specific structure, the cut polymer material can also have self-repairing properties.

Figure 1 is a diagram illustrating the structure of the polymer material of the present invention when the host group of the side chain of the polysiloxane skeleton is formed by inclusion of the guest group. In this structure, the polymer material has a cross-linked structure, i.e., a three-dimensional network structure.

In the polymer material in the form shown in Fig. 1, the guest group 20 is bonded to a side chain of the polysiloxane skeleton 30. More specifically, the guest group 20 is included in the host group 10 to form an inclusion complex, and one end of the guest group 20 is bonded to the polysiloxane skeleton 30. Furthermore, a group 40 including ^R1 bonded to the host group 10 is bonded to a side chain of the polysiloxane skeleton 30. That is, in the polymer material in the form shown in Fig. 1, R ^H -R ¹ - represented by the above formula (1) is bonded to the polysiloxane skeleton 30. The polymer material in the form shown in Fig. 1 has, for example, properties as an elastomer.

In the polymer material of Fig. 1, when a force such as shear is applied to the polymer material, the guest group 20 in the polymer chain may separate from the host group R 1 ^H , causing the material to break. However, by re-adhering the cut surface, the guest group 20 may bond again with the host group R 1 ^H to form an inclusion complex. This allows the cut surface to re-bond, and the polymer material may be repaired.

Figure 2 shows a schematic diagram of another embodiment of the polymer material of the present invention. The polymer material of the form of Figure 2 has a structure in which a polysiloxane penetrates the ring of the host group. The polysiloxane penetrating the ring of the host group may be a polysiloxane having a host group, or may be a polysiloxane not having a host group (e.g., polydimethylsiloxane, etc.).

The polymer material in the form shown in Figure 2 has a cross-linked structure, i.e., a three-dimensional mesh structure, and has a structure in which the polysiloxane skeleton 30 penetrates into the rings of the host group 10.

In the polymer material of the embodiment shown in Fig. 2, similarly to the polymer material of the embodiment shown in Fig. 1, ^R1 bonded to the host group 10 is bonded to the polysiloxane skeleton 30. In this polymer material, the host group 10 can slide while including the polysiloxane skeleton 30, and therefore, for example, the material has an excellent stress relaxation effect and can have high toughness and strength, and therefore has excellent mechanical properties.

Whether or not a polymeric material has the form shown in Figure 2 can be determined, for example, from the results of a swelling test of the polymeric material. For example, when a polymeric material is prepared without using a chemical crosslinking agent and the resulting polymeric material is added to a solvent, if a swelling phenomenon is observed without dissolving, it can be determined that the form shown in Figure 2 (so-called mobile crosslinked polymer) has been formed, and if it dissolves, it can be determined that a mobile crosslinked polymer has not been formed.

In the present invention, the shape of the polymeric material is not particularly limited. For example, the polymeric material may be in various forms such as a membrane, film, sheet, particle, plate, block, pellet, powder, foam material, liquid, etc.

Polymeric materials can be used for a variety of applications. For example, polymeric materials can be suitably used for a variety of components, such as automobiles, adhesives, electronic components, building materials, food containers, and transport containers. In particular, polymeric materials are highly hygroscopic, so they can also be used for clothing, medical equipment, and medical instruments (specifically, contact lenses, etc.).

2. Method for Producing Polymeric Material The method for producing the polymeric material described above is not particularly limited. For example, the polymeric material of the present invention described above can be produced by a method represented by the following general formula (1a):
R ² -R ^H (1a)
and a guest molecule is included in the compound represented by the formula:
A polysiloxane having a reactive functional group in a side chain;
The method may include a step of reacting

Here, in formula (1a), ^R2 represents _NH2 or OH, and ^R2H has the same meaning as ^R2H in formula (1). That is, ^R2H is the host group. The step in the above-mentioned production method is referred to as "step 1".

A specific example of the compound represented by formula (1a) is the compound represented by formula (21) below.

In formula (21), ^R2 is equal to ^R2 in formula (1a), i.e., represents _NH2 or OH; ^R5 in formula (21) represents the aforementioned hydrocarbon group or the like; and n is 5, 6, or 7.

In addition, in formula (21), all of ^R5 (hydrocarbon groups, etc.) may be one selected from the group consisting of methyl groups, acetyl groups, methyl carbamate groups, and ethyl carbamate groups. In formula (21), it is preferable that all of ^R5 are methyl groups or acetyl groups, and it is particularly preferable that all of ^R5 are methyl groups.

Examples of compounds represented by formula (21) include 6-monodeoxy-6-monoamino-trimethyl-cyclodextrin, 6-monohydroxy-trimethyl-cyclodextrin, 6-monodeoxy-6-monoamino-triacetyl-cyclodextrin, 6-monohydroxy-triacetyl-cyclodextrin, 6-monodeoxy-6-monoamino-triethylcarbamate-cyclodextrin, and 6-monohydroxy-triethylcarbamate-cyclodextrin.

The type of guest molecule in the inclusion compound is the same as the guest molecule for forming the guest group described above in section "1. Polymeric Materials."

The method for producing the inclusion compound used in step 1 is not particularly limited, and any known method for producing an inclusion compound can be widely adopted. For example, the compound can be produced by a method including a step of mixing a compound represented by formula (1a) with a guest molecule to obtain the inclusion compound.

In the process of obtaining the inclusion compound, the mixing ratio of the compound represented by formula (1a) to the guest molecule can be, for example, in molar ratio, compound represented by formula (1a):guest molecule=10:1 to 1:10, preferably 3:1 to 1:3, and more preferably 2:1 to 1:2. The compound represented by formula (1a):guest molecule can also be 1:1 (molar ratio).

There is no particular limitation on the type of polysiloxane having a reactive functional group in the side chain used in step 1. Hereinafter, the polysiloxane having a reactive functional group in the side chain used in step 1 will be referred to as "polysiloxane P."

The type of polysiloxane P is not particularly limited as long as it has a reactive functional group in the side chain, and for example, a wide variety of known polysiloxanes can be used. The reactive functional group is the same as the reactive functional group A in the above formula (4). In other words, examples of the reactive functional group include an epoxy group, a carboxy group, an amino group, a hydroxyl group, and an ester group, and an epoxy group is preferable because of the high reactivity of the inclusion compound.

It is preferable that the polysiloxane P has a structural unit represented by the formula (2) and a structural unit represented by the formula (4). In this case, the polysiloxane P may have any structure such as a random polymer or a block polymer, and is preferably a random polymer in terms of ease of production.

When polysiloxane P has a structural unit represented by formula (2) and a structural unit represented by formula (4), the content ratio of the structural unit represented by formula (2) can be, for example, 5 to 95 mol% based on the total amount of the structural units represented by formulas (2) and (4). From the viewpoint of easily controlling the hygroscopicity of the polymer material and easily exhibiting self-repairing performance, the content ratio of the structural unit represented by formula (2) is, for example, preferably 20 mol% or more, more preferably 30 mol% or more, particularly preferably 40 mol% or more, and preferably 90 mol% or less, more preferably 80 mol% or less, and particularly preferably 75 mol% or less based on the total amount of the structural units represented by formulas (2) and (4).

The number average molecular weight Mn of polysiloxane P is not particularly limited and can be, for example, 500 to 100,000, and preferably 1,000 to 50,000.

The method for producing polysiloxane P is not particularly limited, and it can be obtained, for example, by a known production method, or it can be obtained as a commercially available product.

In step 1, the method of reacting the inclusion compound with the polysiloxane having a reactive functional group in the side chain is not particularly limited. For example, a method of mixing the compound represented by the general formula (1a), the guest molecule, and the polysiloxane P in a predetermined mixing ratio can be mentioned. This mixing can be carried out, for example, in an appropriate solvent. The type of solvent is not particularly limited, and examples thereof include aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; chlorine-based hydrocarbons such as chloroform and 1,2-dichloroethane; and alcohols such as methanol, ethanol, isopropyl alcohol, and t-butanol. The solvent can be used alone or as a mixture of two or more kinds. The reaction temperature in step 1 is also not particularly limited, and can be, for example, 10 to 200°C, preferably 50 to 150°C, and more preferably 80 to 120°C.

After the reaction in step 1, the desired polymeric material having a polysiloxane skeleton can be obtained by drying or other treatments as necessary. The polymeric material obtained by this method has, for example, the structure shown in Figure 1 above, and has the properties of an elastomer.

In addition, when producing a polymer material in the form of FIG. 2 described above, a production method including a step of mixing the compound represented by formula (1a) with the polysiloxane P (hereinafter referred to as "step 2") can be adopted. In step 2 of this production method, the conditions can be the same as those of step 1 described above, except that no guest molecule is used. In the mixing of step 2, a polysiloxane other than the polysiloxane P (i.e., a polysiloxane that does not have a reactive functional group A in the side chain) can be used as necessary, and it is preferable to use a polysiloxane other than polysiloxane P (e.g., dimethylpolysiloxane).

Here, the method for producing the compound represented by the formula (1a) is not particularly limited, and a wide variety of known production methods can be adopted. For example, the compound represented by the formula (1a) can be produced by a method similar to the method for producing a host group-containing polymerizable monomer described in International Publication No. 2018/159791 (specifically, the method for producing a host group-containing vinyl monomer or the method for producing a host group-containing non-vinyl monomer).

The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to the aspects of these examples.

(Production Example 1)
First, NH ₂ -PMβCD was produced according to the scheme of formula (21-1) below.

6.9 mmol of 6-deoxy-6-monoazido-β-cyclodextrin was added to a recovery flask as the raw material for the host molecule, and 500 mL of dehydrated N,N-dimethylformamide was added. The mixture was stirred under ice cooling, and then 150 mmol of sodium hydride and 150 mmol of methyl iodide were added and stirred for 12 hours. 20 mL of methanol was then added to the recovery flask, followed by 20 mL of water to quench the mixture. The resulting solution was dried under reduced pressure using an evaporator, after which 100 mL of dichloromethane was added and the mixture was washed with 50 mL of saturated aqueous sodium bicarbonate solution, 50 mL of aqueous solution containing 2.5 g of sodium thiosulfate pentahydrate, and 50 mL of saturated saline.

10 g of magnesium sulfate was added to the washed dichloromethane layer, stirred at room temperature, filtered, and the filtrate was dried in an evaporator. The resulting solid was dissolved in 100 mL of tetrahydrofuran, and 15 mmol of triphenylphosphine and 30 mL of 28% aqueous ammonia were added and stirred at room temperature for 12 hours. Next, after drying under reduced pressure in an evaporator, the resulting dried product was dissolved in 100 mL of dichloromethane and washed with 100 mL of water and 100 mL of saturated saline.

10 g of magnesium sulfate was added to the washed dichloromethane layer, stirred at room temperature, filtered, and the filtrate was dried in an evaporator. The solid matter obtained was purified by silica column chromatography (eluent composition: dichloromethane:methanol=9:1). This host group-containing polymerizable monomer was designated as NH ₂ -PMβCD.

3(a) and (b) show the mass spectrum and NMR spectrum of NH ₂ -PMβCD, respectively. From these results, it was confirmed that the target NH ₂ -PMβCD was produced. It was found that in NH ₂ -PMβCD, 100% (i.e., N-1 = 20) of the total number of hydroxyl groups present in one molecule of the raw host molecule had been substituted with methyl groups.

Example 1
A polymeric material was synthesized according to the reaction scheme shown in FIG. 4. First, "Epoxy-modified silicone KF-101" (molecular weight about 1600, epoxy introduction rate about 33 mol%) manufactured by Shin-Etsu Silicone Co., Ltd. was prepared as polysiloxane P having reactive functional groups in the side chain. 360 mg of this polysiloxane P, 72 mg of NH ₂ -PMβCD obtained in Production Example 1, and 7.7 mg of 1-adamantanamine (guest molecule) were placed in a sample bottle, and 400 μL of toluene was added and mixed. In this mixing, the amount of each was adjusted so that the number of moles of NH ₂ -PMβCD and 1-adamantanamine were both 5 mol% relative to the total number of moles of epoxy groups in polysiloxane P. A uniform solution was obtained by the above mixing, and then, when heated in an oil bath at 100°C for 6 hours, a yellow transparent oil with increased viscosity was obtained. This was dried under reduced pressure at 60°C for two nights to obtain a polymeric material.

5 is a ¹ H-NMR spectrum (CDCl ₃ , 500 MHz, 25° C.) of the polymer material obtained in Example 1. From this ¹ H-NMR spectrum, it was confirmed that the target polymer material had been synthesized.

Example 2
A polymer material was obtained in the same manner as in Example 1, except that the amount of each was adjusted so that the number of moles of NH ₂ -PMβCD and 1-adamantanamine were each 3 mol % relative to the total number of moles of epoxy groups in polysiloxane P.

(Comparative Example 1)
As polysiloxane P, 1.8 g (5.1 mmol, 1 eq.) of Shin-Etsu Silicone's "Epoxy Modified Silicone KF-101" (molecular weight approximately 1600, epoxy introduction rate approximately 33 mol%) and 17 μL (0.25 mmol, 0.05 eq.) of ethylenediamine (EDA) were placed in a sample bottle, and 2.0 mL of toluene was added and mixed. In this mixing, the amount of each compound was adjusted so that the number of moles of EDA was 5 mol% relative to the total number of moles of epoxy groups in polysiloxane P. After obtaining a homogeneous solution by the above mixing, the solution was heated in an oil bath at 100°C for 17 hours and then dried under reduced pressure at 60°C for two nights to obtain a polymer material.

(Tensile test)
A "stroke-test force curve" test ("AUTOGRAPH" (model: AGX-plus) manufactured by Shimadzu Corporation) was performed on the polymer materials (thickness 1 mm) obtained in the examples and comparative examples, and the breaking point (breaking strain) of the polymer material was observed from the resulting breaking stress curve (stress-strain curve). This breaking point was set as the end point, and the maximum stress up to the end point was taken as the breaking stress of the polymer material. The fracture energy of the polymer material was calculated from the stress-strain curve. This tensile test was performed using the up method, in which the lower end of the polymer material was fixed and the upper end was moved at a tensile speed of 0.1 to 1 mm/min.

In addition, in the "stroke-test force curve" test, a material that exhibits high values for either or both of the breaking stress and breaking strain (also simply called strain) can be judged to have excellent toughness and strength as a polymer material. In particular, a material that exhibits high values for both the breaking stress and breaking strain (also simply called strain) can be judged to have excellent fracture energy.

As a result of the tensile test, the polymer material obtained in Example 1 had a breaking stress of 30 kPa, a breaking strain of 28%, a Young's modulus of 120 kPa, and a breaking energy of 5.5 ^Jm2 , which was a material superior in toughness and strength compared to conventional polymer materials. The polymer material obtained in Example 2 had a breaking stress of 19 kPa, a breaking strain of 77%, a Young's modulus of 36 kPa, and a breaking energy of 8.7 ^Jm2 , which was a material superior in toughness and strength compared to conventional polymer materials. In contrast, the polymer material (chemically cross-linked structure) obtained in Comparative Example 1 was a material that was so brittle that it was impossible to prepare a sample for a tensile test, and was a material that clearly did not have toughness and strength. The polymer material obtained in Comparative Example 1 did not have a cross-linked structure due to host-guest interactions as in Example 1, but had a conventional chemically cross-linked structure, so it can be said that it is not suitable as a means for improving the mechanical properties of a polymer material having a polysiloxane skeleton.

(Self-repairability evaluation)
The polymeric materials (thickness 1 mm) obtained in Examples 1 and 2 were cut in the center and divided into two pieces, and the two pieces were kept in contact at room temperature (25°C) for 24 hours, and it was confirmed that both pieces re-adhered. In addition, the breaking stress after re-adhesion was about 30% of that before cutting, and it was found that about 30% had recovered by self-repair.

(Evaluation of moisture absorption)
The polymeric materials obtained in Example 1 and Comparative Example 1 were each placed in a sample bottle and immersed in 6 mL of water for 20 hours. After that, each elastomer was taken out, the water on the surface was lightly wiped off, and the mass was measured, and the moisture content was calculated from the change in mass before and after immersion in water. As a result, the moisture content of the polymeric material obtained in Example 1 was 8.7%, and the moisture content of the polymeric material obtained in Comparative Example 1 was 0.4%. From this result, it was also found that the polymeric material obtained in Example 1 has high hygroscopicity.

Claims (6)

A polymer material having a polysiloxane skeleton,
The polysiloxane skeleton has a side chain represented by the following general formula (1):
-R ¹ -R ^H (1)
(In formula (1), R ¹ represents NH, and R ^H represents a host group.)
The structural unit represented by
the host group is a monovalent group obtained by removing one hydrogen atom or one hydroxyl group from a cyclodextrin or a cyclodextrin derivative,
The cyclodextrin derivative is a polymeric material having a structure in which a hydrogen atom of at least one hydroxyl group of cyclodextrin is substituted with at least one group selected from the group consisting of a hydrocarbon group, an acyl group, and -CONHR (R is a methyl group or an ethyl group). A polymer material having a polysiloxane skeleton,
The polysiloxane skeleton has a structural unit represented by -O-R ^H (R ^H represents a host group) in a side chain, and the polysiloxane skeleton is represented by the following general formula (3):

(In formula (3), ^R1 represents O, ^R2 represents a host group, ^R5 represents a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted with a substituent, or an aryl group having 6 to 20 carbon atoms which may be substituted with a substituent. In formula (3), ^R6 represents an unsubstituted alkylene group having 1 to 10 carbon atoms, or an unsubstituted alkylene group having 1 to 10 carbon atoms and an ether bond , and n is the number of 0 or 1. When n is 0, this means that ^R6 is absent, that is, ^R1 is directly bonded to a silicon atom.)
The structural unit represented by
the host group is a monovalent group obtained by removing one hydrogen atom or one hydroxyl group from a cyclodextrin or a cyclodextrin derivative,
The cyclodextrin derivative is a polymeric material having a structure in which a hydrogen atom of at least one hydroxyl group of cyclodextrin is substituted with at least one group selected from the group consisting of a hydrocarbon group, an acyl group, and -CONHR (R is a methyl group or an ethyl group). The polymer material according to claim 1 or 2, wherein the host group includes the guest group to form an inclusion complex, and the included guest group is chemically bonded to a side chain of the polysiloxane skeleton. The polymer material according to claim 1 or 2, having a structure in which polysiloxane penetrates the ring of the host group. A method for producing a polymeric material having a polysiloxane skeleton, comprising the steps of:
The polysiloxane skeleton has a side chain represented by the following general formula (1):
-R ¹ -R ^H (1)
(In formula (1), R ¹ represents NH or O, and R ^H represents a host group.)
The structural unit represented by
the host group is a monovalent group obtained by removing one hydrogen atom or one hydroxyl group from a cyclodextrin or a cyclodextrin derivative,
The cyclodextrin derivative has a structure in which a hydrogen atom of at least one hydroxyl group of cyclodextrin is substituted with at least one group selected from the group consisting of a hydrocarbon group, an acyl group, and -CONHR (R is a methyl group or an ethyl group),
The following general formula (1a)
R ² -R ^H (1a)
(In formula (1a), ^R2 represents _NH2 or OH, and ^RH has the same meaning as ^RH in formula (1).)
and a guest molecule is included in the compound represented by the formula:
A polysiloxane having a reactive functional group in a side chain;
A method for producing a polymer material, comprising the step of reacting The method of claim 5, wherein the reactive functional group is an epoxy group.

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