Polymeric material and its manufacturing method

Abstract

Provided are: a polymer material that has a polysiloxane backbone and that has excellent mechanical properties and high hygroscopicity; and a production method for the polymer material.　The present invention is a polymer material having a polysiloxane backbone, wherein the polysiloxane backbone has, at a side chain thereof, a constituent unit represented by general formula (1): -R1-RH (in formula (1), R1 represents NH or O, and RH represents a host group). The host group is a monovalent group in which a hydrogen atom or a hydroxy group is removed from a cyclodextrin or a cyclodextrin derivative. The cyclodextrin derivative has a structure obtained by substituting the hydrogen atom of at least one hydroxy group possessed by a cyclodextrin, with at least one group selected from the group consisting of hydrocarbon groups, acyl groups, and -CONHR (R represents a methyl group or an ethyl group).

Description

[Technical field]

[0001] The present invention relates to a polymeric material having a polysiloxane skeleton and a method for producing the same. [Background technology]

[0002] Synthetic polymer compounds (polysiloxanes) having siloxane bonds (Si-O bonds) in the main skeleton are known to have unique properties not found in organic polymers, and are used in various fields. Siloxane bonds have stronger bonding strength than carbon-carbon or carbon-oxygen bonds present in general organic polymers, and have chemically stable properties, so polysiloxanes formed by repeating 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 arranged on the inside and organic side chain substituents are arranged on the outside, so they are flexible, water repellent, and have low biotoxicity. Therefore, polysiloxanes are highly useful materials in various applications such as medical instruments, rubber, paints, and protective films.

[0003] On the other hand, in recent years, there has been a demand for imparting further functionality to polysiloxane-based materials, such as further improvement of mechanical properties, imparting self-repairing properties, etc. From this perspective, for example, Non-Patent Document 1 proposes a technology in which a functional group capable of forming a hydrogen bond is introduced into a polysiloxane skeleton, and the self-repairing properties are exerted through the hydrogen bonds of the functional group. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] Adv. Mater.2018,30,1706846 Summary of the Invention [Problem to be solved by the invention]

[0005] However, in recent years, there has been a strong demand for adding further functions to polysiloxanes so that they can be used in various applications. For example, one of the features of polysiloxanes is their excellent water repellency, but it has been difficult to improve their hygroscopicity, so the applications of polysiloxanes are often limited. For this reason, there is a demand for polysiloxanes with high hygroscopicity. From this perspective, if polysiloxanes with excellent mechanical properties and improved hygroscopicity can be produced, they can be used in applications that could not be used with conventional polysiloxanes, so the utility value of such polysiloxanes can be said to be very high.

[0006] The present invention has been made in view of the above, and an object of the present invention is to provide a polymeric material having a polysiloxane skeleton that is excellent in mechanical properties and has high hygroscopicity, and a method for producing the same. [Means for solving the problem]

[0007] As a result of intensive research into achieving the above object, the inventors have discovered that the above object can be achieved by introducing a specific functional group capable of host-guest interaction into a polysiloxane skeleton, thereby completing the present invention.

[0008] 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, R H indicates 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 the 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). Section 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. Section 3 Item 2. The polymer material according to item 1, having a structure in which polysiloxane penetrates into the ring of the host group. Section 4 Item 1 or 2, a method for producing a polymeric material, The following general formula (1a) R 2 -R H (1a) (In formula (1a), R 2 NH 2 or OH, R H is R in the above formula (1). H (Synonymous with 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 Section 5 Item 5. The method according to item 4, wherein the reactive functional group is an epoxy group. Effect of the Invention

[0009] The polymer material of the present invention has excellent mechanical properties and high moisture absorption. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 is a diagram for illustrating a schematic example of a polymer material of the present invention. [Diagram 2] FIG. 2 is a diagram for explaining a schematic diagram of another example of the polymer material of the present invention. [Diagram 3](a) and (b) show the mass spectrum and NMR spectrum of NH2-PMβCD, respectively. [Figure 4] 1 is a reaction scheme of the reaction carried out in Example 1. [Diagram 5] 1 is a 1H-NMR spectrum (CDCl3, 500 MHz, 25° C.) of the polymer material obtained in Example 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Hereinafter, embodiments 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".

[0012] 1.Polymer materials 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, R H indicates 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).

[0013] In this specification, "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)" may be expressed as "hydrocarbon group, etc." for convenience.

[0014] 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 later, it is preferable that the polysiloxane skeleton is linear.

[0015] When the polysiloxane skeleton is linear, the polysiloxane skeleton can contain, for example, a constitutional unit represented by the following formula (2).

[0016] [ka]

[0017] In formula (2), R 3 and R 4 are the same or different and represent a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, or an aryl group having 6 to 20 carbon atoms which may be substituted.

[0018] 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 1 or 2. 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.

[0019] 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 may be 1 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).

[0020] 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 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).

[0021] In formula (2), R 3 and R 4 can be the same or different. In formula (2), R 3 and R 4 Each of R is preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and particularly preferably a methyl group. 3 and R 4 are all methyl groups, the polysiloxane backbone comprises polydimethylsiloxane.

[0022] As described above, the polysiloxane skeleton has a side chain having a structural unit "-R 1 -R H In such a constitutional unit, R 1 can be directly bonded to the Si in the polysiloxane backbone or indirectly bonded (i.e., R 1 In still another embodiment, R 1 can be directly bonded to the side chain of the vinyl polymer.

[0023] R1 is directly or indirectly bonded to the Si in the polysiloxane skeleton (i.e., R 1 and Si) the polysiloxane skeleton may further include a constitutional unit represented by the following formula (3):

[0024] [ka]

[0025] In formula (3), R 5 is R in the above formula (2). 3 and R 4 In formula (3), R 6 represents a divalent group containing an alkylene having 1 to 10 carbon atoms, and n is the number 0 or 1. When n is 0, R 6 This means that there is no R 1 is directly bonded to the silicon atom.

[0026] 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.

[0027] 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. 6 In the formula, the alkylene preferably has 1 to 8 carbon atoms, and more preferably has 2 to 6 carbon atoms. 6 R may contain, for example, a heteroatom. Examples of the heteroatom include oxygen and nitrogen. 6 When R contains a heteroatom, 6 The alkyl group may have an ether bond, an amide bond, an amino group, or the like, and among these, an ether bond is preferred (for example, -(CH 2 ) 3 -O-(CH 2 ) 3-bond is an example. The monovalent group containing 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, and a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), and a hydroxy group is particularly preferred.

[0028] On the other hand, as mentioned above, R 1 When R is directly bonded to the side chain of the vinyl polymer, the vinyl polymer may be, for example, a known vinyl polymer, such as various acrylic polymers. Among them, (meth)acrylic acid esters, N-substituted (meth)acrylamides, etc. may be mentioned. In these cases, R 1 can be bonded to the ester moiety of a (meth)acrylic acid ester or the amide moiety of an N-substituted (meth)acrylamide. 1 An example of a case in which the vinyl polymer is directly bonded to a side chain of the vinyl polymer is, for example, a polymer of a host group-containing polymerizable monomer described in WO 2018 / 159791.

[0029] In formula (1), R 1 is NH or O, and is particularly preferably NH.

[0030] R HThat is, the host group is a monovalent group obtained by removing one hydrogen atom or hydroxyl group from cyclodextrin or a cyclodextrin derivative. Among them, 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 of cyclodextrin is substituted with a hydrocarbon group or the like (that is, 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)). That is, the 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.

[0031] 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. Thus, the cyclodextrin derivative is at least one selected from the group consisting of α-cyclodextrin derivatives, β-cyclodextrin derivatives, and γ-cyclodextrin derivatives.

[0032] The host group is preferably a monovalent group obtained by removing one hydroxyl group from cyclodextrin or a cyclodextrin derivative.

[0033] A host group is a monovalent group obtained by removing one hydrogen atom or hydroxyl group from a cyclodextrin or a cyclodextrin derivative, and the hydrogen atom or hydroxyl group removed in the cyclodextrin or cyclodextrin derivative may be at any position on the cyclodextrin or cyclodextrin derivative.

[0034] Here, if the total number of hydroxyl groups in one cyclodextrin molecule is N, then for α-cyclodextrin, N=18, for β-cyclodextrin, N=21, and for γ-cyclodextrin, N=24.

[0035] If the host group is a monovalent group obtained by removing one "hydroxyl group" from a cyclodextrin derivative, the cyclodextrin derivative is formed by substituting 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 substituted with hydrocarbon groups, etc.

[0036] The host group preferably has a structure in which 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 constitutional unit represented by formula (1) can exhibit a higher affinity for hydrophobic monomer units. The host group more preferably has 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 hydrogen atoms of 90% or more of the total number of hydroxyl groups substituted with the hydrocarbon group or the like.

[0037] 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. The host group more preferably has the hydrogen atoms of 15 or more of the total hydroxyl groups present in one molecule of α-cyclodextrin substituted with the hydrocarbon group, etc., and particularly preferably has the hydrogen atoms of 17 of the total hydroxyl groups substituted with the hydrocarbon group, etc.

[0038] The host group preferably has a structure in which the hydrogen atoms of 15 or more of the hydroxyl groups among all the hydroxyl groups present in one molecule of β-cyclodextrin are substituted with the hydrocarbon group, etc. The host group more preferably has the hydrogen atoms of 17 or more of the hydroxyl groups among all the hydroxyl groups present in one molecule of β-cyclodextrin substituted with the hydrocarbon group, etc., and particularly preferably has the hydrogen atoms of 19 or more of the hydroxyl groups among all the hydroxyl groups substituted with the hydrocarbon group, etc.

[0039] The host group preferably has a structure in which the hydrogen atoms of 17 or more of the hydroxyl groups among all the hydroxyl groups present in one molecule of γ-cyclodextrin are substituted with the hydrocarbon group, etc. The host group more preferably has the hydrogen atoms of 19 or more of the hydroxyl groups among all the hydroxyl groups present in one molecule of γ-cyclodextrin substituted with the hydrocarbon group, etc., and particularly preferably has the hydrogen atoms of 21 or more of the hydroxyl groups among all the hydroxyl groups substituted with the hydrocarbon group, etc.

[0040] When the host group has two or more hydrocarbon groups, they may all be the same or some may be different.

[0041] In the cyclodextrin derivative, the type of the hydrocarbon group is not particularly limited, and examples of the hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group.

[0042] The number of carbon atoms in the hydrocarbon group is not particularly limited, and the hydrocarbon group preferably has 1 to 4 carbon atoms, for example.

[0043] Specific examples of the hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a butyl group. When the hydrocarbon group is a butyl group, it may be either a straight chain or a branched chain.

[0044] The hydrocarbon group may have a substituent as long as the effect of the present invention is not impaired.

[0045] In the cyclodextrin derivative, the acyl group may be exemplified by an acetyl group, a propionyl group, a formyl group, etc. The acyl group may further have a substituent. From the viewpoint of easily forming a host-guest interaction and easily obtaining a polymer material having excellent toughness and strength, the acyl group is preferably an acetyl group.

[0046] 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.

[0047] In the cyclodextrin derivative, the hydrocarbon group etc. is preferably a methyl group or an acyl group, more preferably a methyl group, an acetyl group or a propionyl group, and particularly preferably a methyl group or an acetyl group.

[0048] The polysiloxane skeleton may have other structural units. For example, the other structural units may be 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).

[0049] [ka]

[0050] In formula (4), R 7 is R in the above formula (2). 3 and R 4 In formula (4), R 8 represents a monovalent group containing an alkylene having 1 to 8 carbon atoms, and A represents a reactive functional group.

[0051] 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.

[0052] In formula (4), R 8 is not particularly limited as long as it is a divalent group containing an alkylene group having 1 to 8 carbon atoms. 8 In the above formula, the alkylene preferably has 1 to 8 carbon atoms, more preferably 2 to 7 carbon atoms, further preferably 2 to 6 carbon atoms, and particularly preferably 2 to 5 carbon atoms. 8 R may contain, for example, a heteroatom. Examples of the heteroatom include oxygen and nitrogen. 8 When R contains a heteroatom, 8 The alkyl group may have, for example, an ether bond, an amide bond, an amino group, or the like, and among these, an ether bond is preferred (for example, -(CH 2 ) 3 -O-(CH 2 )-bond is an example. The monovalent group containing 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, and a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), and a hydroxy group is particularly preferred.

[0053] In formula (4), the reactive functional group A may be, for example, an epoxy group, a carboxy group, an amino group, a hydroxyl group, an ester group, or the like, and is preferably an epoxy group because of its high reactivity with guest molecules described below.

[0054] In the polysiloxane skeleton, the content ratio of the constitutional unit represented by the formula (2) can be, for example, 5 to 95 mol% based on the total amount of the constitutional 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 later, the content ratio of the constitutional 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, particularly preferably 75 mol% or less based on the total amount of the constitutional units represented by the formulas (2), (3), and (4).

[0055] In the polysiloxane skeleton, the content ratio of the constitutional unit represented by the formula (3) can be, for example, 0.01 to 30 mol% based on the total amount of the constitutional 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 later, the content ratio of the constitutional 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 constitutional units represented by the formulas (3) and (4).

[0056] In the polymeric 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. That is, the polymeric 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). That is, the polymeric 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).

[0057] In the polymer material of the present invention, the polysiloxane skeleton 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, for example.

[0058] 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.

[0059] In the polymer material of the present invention, the host group may include the guest group to form an inclusion complex, and the included guest group may be chemically bonded (e.g., covalently bonded) to a side chain of the polysiloxane skeleton.

[0060] The guest group is a group derived from a guest molecule, specifically, a group formed by removing one or two hydrogen atoms from the guest molecule. Examples of the guest molecule include compounds capable of forming an inclusion complex with the host group.

[0061] 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.

[0062] Examples of the compound 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.

[0063] Examples of the compound 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 -hydroxyphenyl)butane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)-2,2-dichloroethylene, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, 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.

[0064] 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, 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-carboxy3-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.

[0065] Examples of the compound 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, and 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- Examples of such compounds include (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, and 1,1-bis(4-phenylcarbonyl chloride)cyclohexane.

[0066] Examples of the compound 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 ... 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.

[0067] 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, and the like. 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 suitable 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.

[0068] Examples of the compound 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 -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.

[0069] 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.Specifically, the guest molecule is preferably 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 easily bonded to the side chain of the polysiloxane skeleton, and self-repairing property is more easily exhibited.

[0070] 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 and 1-hydroxyadamantane, 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.

[0071] 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. Examples of the other functional group include R 6 Examples include:

[0072] Furthermore, when the polysiloxane skeleton has a structural unit represented by formula (4), the guest molecule included 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.

[0073] In the polymer material of the present invention, the polysiloxane molecular chain to which a 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 the host group that encapsulates the guest group is bonded.

[0074] When the host group in the side chain of the polysiloxane skeleton includes 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.

[0075] 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 a reversible host-guest interaction within or between molecules (see FIG. 1 described later). As a result, the polymer material containing such a polysiloxane skeleton can have 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 rebonded, thereby repairing the polymer material. In other words, when the polymer material is controlled to a specific structure, the cut polymer material can also have self-repairing properties.

[0076] 1 is a schematic diagram illustrating a configuration of the polymer material of the present invention in which a host group in a side chain of a polysiloxane skeleton is formed by inclusion of a guest group, in which the polymer material has a crosslinked structure, i.e., a three-dimensional network structure.

[0077] In the polymer material in the form of 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, R 1 In other words, the polymer material in the form of FIG. 1 is a polymer material having a structure in which a group 40 containing H -R 1 - is bonded to the polysiloxane skeleton 30. The polymer material having the form of Fig. 1 has, for example, properties as an elastomer.

[0078] In the polymer material of FIG. 1, when a shear force or the like is applied to the polymer material, the guest group 20 in the polymer chain and the host group R H However, by reattaching the cut surfaces, the guest group 20 and the host group R can be reunited. H and can combine to form an inclusion complex, which can recombine the cut surfaces and repair the polymeric material.

[0079] Fig. 2 is a schematic diagram showing another embodiment of the polymer material of the present invention. The polymer material in the form of Fig. 2 has a structure in which a polysiloxane penetrates into the ring of the host group. The polysiloxane penetrating into 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.).

[0080] The polymer material in the form of FIG. 2 has a crosslinked structure, that is, a three-dimensional network structure, and also has a structure in which the polysiloxane skeleton 30 penetrates into the rings of the host group 10.

[0081] In the polymer material in the form of FIG. 2, similarly to the polymer material in the form of FIG. 1, R 1is bonded to the polysiloxane skeleton 30. In this polymer material, the host group 10 can slide while being enclosed within the polysiloxane skeleton 30, and therefore, for example, the polymer material has excellent stress relaxation properties and can have high toughness and strength, resulting in excellent mechanical properties.

[0082] Whether or not a polymer material has the form shown in Fig. 2 can be determined, for example, from the results of a swelling test of the polymer material. For example, when a polymer material is prepared without using a chemical crosslinking agent and the obtained polymer material is added to a solvent, if a swelling phenomenon is observed without dissolving, it can be determined that the form shown in Fig. 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.

[0083] In the present invention, the shape of the polymer material is not particularly limited. For example, the polymer material may be in various forms such as a membrane, a film, a sheet, a particle, a plate, a block, a pellet, a powder, a foam material, or a liquid.

[0084] Polymer materials can be used in various applications. For example, polymer materials can be suitably used for various members such as automobiles, adhesives, electronic parts, building materials, food containers, and transport containers. In particular, polymer materials have high hygroscopicity, and therefore can be used for clothing, medical equipment, and medical instruments (specifically, contact lenses, etc.).

[0085] 2. Manufacturing methods for polymer materials The method for producing the polymer material is not particularly limited. For example, the polymer material of the present invention may be prepared by reacting a compound 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

[0086] In the formula (1a), R 2NH 2 or OH, R H is R in the above formula (1). H That is, R H is the host group. The step in the above production method is referred to as "Step 1."

[0087] A specific example of the compound represented by the formula (1a) is a compound represented by the following formula (21).

[0088] [ka]

[0089] In formula (21), R 2 is R in the formula (1a) 2 That is, NH 2 or OH, and R in formula (21) 5 represents the above-mentioned hydrocarbon group, etc., and n is 5, 6, or 7.

[0090] In addition, in formula (21), R 5 In some cases, all of R (hydrocarbon groups, etc.) may be one selected from the group consisting of methyl groups, acetyl groups, methyl carbamate groups, and ethyl carbamate groups. 5 is preferably a methyl group or an acetyl group, and all R 5 is particularly preferably a methyl group.

[0091] Examples of the compound 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.

[0092] The type of guest molecule in the inclusion compound is the same as the guest molecule for forming the guest group described in the above section "1. Polymer material."

[0093] The method for producing the inclusion compound used in step 1 is not particularly limited, and a wide variety of known methods for producing inclusion compounds can be used. For example, the compound can be produced by a method including a step of mixing the compound represented by formula (1a) with a guest molecule to obtain the inclusion compound.

[0094] In the step 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).

[0095] There is no particular limitation on the type of polysiloxane having a reactive functional group on the side chain used in step 1. Hereinafter, the polysiloxane having a reactive functional group on the side chain used in step 1 will be referred to as "polysiloxane P."

[0096] 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, known polysiloxanes can be widely used. The reactive functional group is the same as the reactive functional group A in the above formula (4). That is, the reactive functional group can be, for example, an epoxy group, a carboxy group, an amino group, a hydroxyl group, an ester group, etc., and the epoxy group is preferable in terms of high reactivity of the inclusion compound.

[0097] The polysiloxane P preferably has a constitutional unit represented by the formula (2) and a constitutional 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, for example.

[0098] When the polysiloxane P has a constitutional unit represented by the formula (2) and a constitutional unit represented by the formula (4), the content ratio of the constitutional unit represented by the formula (2) can be, for example, 5 to 95 mol% based on the total amount of the constitutional units represented by the 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 constitutional 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, particularly preferably 75 mol% or less based on the total amount of the constitutional units represented by the formulas (2) and (4).

[0099] The number average molecular weight Mn of the polysiloxane P is not particularly limited and can be, for example, 500 to 100,000, and preferably 1,000 to 50,000.

[0100] The method for producing the polysiloxane P is not particularly limited, and for example, it can be obtained by a known production method, or it can be obtained as a commercially available product.

[0101] 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 at a predetermined mixing ratio can be mentioned. This mixing can be carried out, for example, in a suitable solvent. The type of the 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.

[0102] After the reaction in step 1, the target polymer material having a polysiloxane skeleton can be obtained by performing a treatment such as drying as necessary. The polymer material obtained by such a method has, for example, the structure shown in Figure 1 above, and has the properties of an elastomer.

[0103] Furthermore, when producing a polymer material having 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. Step 2 in this production method can be carried out under the same conditions as step 1 described above, except that no guest molecule is used. In the mixing in step 2, a polysiloxane other than the polysiloxane P (i.e., a polysiloxane not having 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).

[0104] Here, the method for producing the compound represented by the formula (1a) is not particularly limited, and known production methods can be widely 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). EXAMPLES

[0105] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the embodiments of these examples.

[0106] (Production Example 1) First, NH 2 -PMβCD was produced.

[0107] [ka]

[0108] As the raw material for the host molecule, 6.9 mmol of 6-deoxy-6-monoazido-β-cyclodextrin was added to a recovery flask, 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. Then, 20 mL of methanol was added to the recovery flask, and 20 mL of water was added to quench the mixture. The resulting solution was dried under reduced pressure using an evaporator, and then 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.

[0109] 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 obtained 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 obtained dried product was dissolved in 100 mL of dichloromethane and washed with 100 mL of water and 100 mL of saturated saline.

[0110] 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 NH 2 -PMβCD

[0111] Figure 3(a) and (b) show the NH 2 The mass spectrum and NMR spectrum of -PMβCD are shown below. From these results, the target NH 2 It was confirmed that -PMβCD was produced. 2 It was found that in -PMβCD, 100% (i.e., N-1 = 20) of the total hydroxyl groups present in one molecule of the raw host molecule were replaced with methyl groups.

[0112] Example 1 A polymeric material was synthesized according to the reaction scheme shown in Figure 4. First, "Epoxy-modified silicone KF-101" (molecular weight approximately 1600, epoxy introduction rate approximately 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 and the NH 2 72 mg of -PMβCD 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 mixture, NH 2 The amount of each compound was adjusted so that the moles of -PMβCD and 1-adamantanamine were both 5 mol%. The above mixing resulted in a homogeneous solution, which was then heated in a 100°C oil bath for 6 hours to obtain a yellow transparent oil with increased viscosity. This was then dried under reduced pressure at 60°C for two nights to obtain a polymer material.

[0113] FIG. 5 shows the polymer material obtained in Example 1. 1 H-NMR spectrum (CDCl 3 , 500MHz, 25℃). 1 H-NMR spectrum confirmed that the desired polymer material had been synthesized.

[0114] Example 2 NH 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 -PMβCD and the amount of 1-adamantanamine were both 3 mol %.

[0115] Comparative Example 1 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, it was heated in a 100°C oil bath for 17 hours and then dried under reduced pressure at 60°C for two nights to obtain a polymer material.

[0116] (Tensile test) A "stroke-test force curve" test (Shimadzu Corporation's "AUTOGRAPH" (model number: AGX-plus)) was conducted 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 obtained 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 also calculated from the stress-strain curve. This tensile test was conducted 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.

[0117] 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. 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.

[0118] 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 Jm 2 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 and was a material superior in toughness and strength to conventional polymer materials. In contrast, the polymer material (chemically cross-linked structure) obtained in Comparative Example 1 was a material so brittle that it was impossible to prepare a sample for a tensile test, and was clearly a material lacking 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, and therefore 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.

[0119] (Self-repair evaluation) The polymeric materials (1 mm thick) obtained in Examples 1 and 2 were cut in the center and divided into two pieces, and then the two pieces were left 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 due to self-repair.

[0120] (Moisture absorption evaluation) 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. Then, 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

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, 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).

2. 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), R １ indicates O, R Ｈ represents a host group. ５ 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. ６ 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 0 or 1. When n is 0, R ６ This means that there is no R １ 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).

3. 3. The polymer material according to claim 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.

4. The polymer material according to claim 1 or 2, which has a structure in which a polysiloxane penetrates into the ring of the host group.

5. 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, 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), R ２ NH ２ or OH, R Ｈ is R in the formula (1). Ｈ (Synonymous with 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

6. The method according to claim 5 , wherein the reactive functional group is an epoxy group.

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