WO2021045203A1 - 高分子材料及びその製造方法 - Google Patents

高分子材料及びその製造方法 Download PDF

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WO2021045203A1
WO2021045203A1 PCT/JP2020/033642 JP2020033642W WO2021045203A1 WO 2021045203 A1 WO2021045203 A1 WO 2021045203A1 JP 2020033642 W JP2020033642 W JP 2020033642W WO 2021045203 A1 WO2021045203 A1 WO 2021045203A1
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polymer material
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polysiloxane
formula
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French (fr)
Japanese (ja)
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義徳 ▲高▼島
原田　明
浩靖 山口
基史 大▲崎▼
大地 吉田
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University of Osaka NUC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/16—Cyclodextrin; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes

Definitions

  • the present invention relates to a polymer material having a polysiloxane skeleton and a method for producing the same.
  • Synthetic polymer compounds having a siloxane bond (Si—O bond) as the main skeleton are known to have unique properties not found in organic polymers, and are used in various fields.
  • a siloxane bond has a stronger bonding force than a carbon-carbon or carbon-oxygen bond existing in a general organic polymer and has chemically stable properties. Therefore, a poly formed by repeatedly having a siloxane bond.
  • Siloxane has, for example, excellent heat resistance and weather resistance.
  • polysiloxane can form a spiral structure in which an inorganic siloxane bond is arranged on the inside and an organic side chain substituent is arranged on the outside, so that it is flexible, has water repellency, and has low biotoxicity. Therefore, polysiloxane is a material having high utility value in various applications such as medical instruments, rubber, paints, and protective films.
  • Non-Patent Document 1 proposes a technique of introducing a hydrogen-bondable functional group into a polysiloxane skeleton and exerting self-repairing property through hydrogen bonding of the functional group.
  • polysiloxane in order to apply polysiloxane to various uses, it is strongly desired to add a further function to polysiloxane.
  • one of the features of polysiloxane is excellent water repellency, but it is difficult to improve hygroscopicity, so that the use of polysiloxane is often limited. Therefore, a polysiloxane having high hygroscopicity is required. From this point of view, if a polysiloxane having excellent mechanical properties and further improved hygroscopicity can be produced, it can be applied to applications that could not be applied with conventional polysiloxanes. Therefore, it can be said that the utility value of such polysiloxane is very high.
  • the present invention has been made in view of the above, and an object of the present invention is to provide a polymer material having a polysiloxane skeleton having excellent mechanical properties and high hygroscopicity, and a method for producing the same.
  • the present inventors have found that the above object can be achieved by introducing a specific functional group capable of host-guest interaction into the polysiloxane skeleton. Has been completed.
  • the present invention includes, for example, the subjects described in the following sections.
  • Item 1 A polymer material with a polysiloxane skeleton
  • the polysiloxane skeleton has the following general formula (1) in the side chain.
  • -R 1- RH (1) (In formula (1), R 1 represents NH or O, and RH represents a host group.)
  • R 1 represents NH or O
  • RH represents a host group.
  • Has a structural unit represented by The host group is a monovalent group obtained by removing one hydrogen atom or a hydroxyl group from a cyclodextrin or a cyclodextrin derivative.
  • the hydrogen atom of at least one hydroxyl group of cyclodextrin is replaced 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.
  • Item 3 Item 2.
  • the polymer material according to Item 1 which has a structure in which polysiloxane penetrates the ring of the host group.
  • Item 4 Item 2.
  • the following general formula (1a) R 2 -R H (1a) (In the formula (1a), R 2 represents a NH 2 or OH, R H is as defined R H in the formula (1))
  • Item 5 Item 4.
  • the polymer material of the present invention has excellent mechanical properties and high hygroscopicity.
  • the polymer material of the present invention has a polysiloxane skeleton, and the polysiloxane skeleton has the following general formula (1) in the side chain.
  • -R 1- RH (1) (In formula (1), R 1 represents NH or O, and RH represents a host group.) It has a structural unit represented by.
  • the host group is a monovalent group obtained by removing one hydrogen atom or a hydroxyl group from a cyclodextrin or a cyclodextrin derivative
  • the cyclodextrin derivative is a hydrogen having at least one hydroxyl group of the cyclodextrin. It has a structure in which an atom 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).
  • hydrocarbon group or the like 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)
  • R is a methyl group or an ethyl group
  • 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.
  • the polysiloxane skeleton when the Si atom in the "-Si-O-Si-" structure further has a siloxane bond (-O-Si), the polysiloxane skeleton may have a branched structure. It may have a crosslinked structure.
  • the polysiloxane skeleton is preferably linear from the viewpoint that the polymer material has appropriate mechanical properties and easily exhibits the self-repairing property described later.
  • the polysiloxane skeleton can contain, for example, a structural unit represented by the following formula (2).
  • R 3 and R 4 may be the same or different and may be substituted with a substituent or a linear or branched alkyl group having 1 to 10 carbon atoms, or may be substituted with a substituent. It shows an aryl group having 6 to 20 carbon atoms.
  • the linear or branched alkyl group having 1 to 10 carbon atoms is preferably 1 to 4 carbon atoms, and particularly preferably 1 or 2 carbon atoms.
  • the alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group and n-. Examples thereof include a heptyl group, an n-octyl group, an n-nonyl group and an n-decyl group.
  • the number of substituents can be 1 or 2 or more.
  • substituents in this case 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 (for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom). And so on.
  • examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, a tetrahydronaphthyl group and the like.
  • the number of substituents can be 1 or 2 or more.
  • the substituent in this case 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 (for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom). And so on.
  • R 3 and R 4 can be the same or different.
  • all of R 3 and R 4 are preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and a methyl group is particularly preferable.
  • the polysiloxane skeleton contains polydimethylsiloxane.
  • the polysiloxane skeleton has a structural unit "-R 1- RH " represented by the above formula (1) in the side chain.
  • R 1 can be directly bonded to Si in the polysiloxane skeleton, or can be indirectly bonded (that is, another group is interposed between R 1 and Si). it can.
  • R 1 can be directly attached to the side chain of the vinyl polymer.
  • the polysiloxane skeleton has the following formula.
  • the structural unit represented by (3) can be further included.
  • R 5 is synonymous with R 3 and R 4 in formula (2).
  • R 6 represents a divalent group containing an alkylene having 1 to 10 carbon atoms, and n is a number of 0 or 1. When n is 0, it means that there is no R 6 , that is, R 1 is directly bonded to the silicon atom.
  • R 5 is a methyl group, an ethyl group, n- propyl group, preferably an isopropyl group, a methyl group is particularly preferred.
  • R 6 is not particularly limited as long as it is a divalent group containing an alkylene having 1 to 10 carbon atoms.
  • the number of carbon atoms of the alkylene is preferably 1 to 8, and more preferably 2 to 6.
  • R 6 can also contain, for example, a heteroatom. Examples of the hetero atom include oxygen, nitrogen and the like.
  • R 6 may have an ether bond, an amide bond, an amino group, or the like, and among them, it is preferable to have an ether bond (for example,-(CH 2 ) 3- O- (for example). CH 2 ) 3 -Binding is exemplified).
  • a 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 for example, 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 (for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine). Atomic) and the like, and a hydroxy group is particularly preferable.
  • examples of the vinyl polymer include known vinyl polymers, and for example, various acrylics.
  • a system polymer can be exemplified. Among them, (meth) acrylic acid ester, N-substituted (meth) acrylamide and the like can be mentioned.
  • R 1 can be attached to the ester moiety of the (meth) acrylic acid ester or the amide moiety of the N-substituted (meth) acrylamide.
  • the polymer of the host group-containing polymerizable monomer described in International Publication No. 2018/159791 can be mentioned. ..
  • R 1 is NH or O, and it is particularly preferable that it is NH.
  • RH is a monovalent group obtained by removing one hydrogen atom or hydroxyl group from a cyclodextrin or cyclodextrin derivative.
  • the host group is preferably a monovalent group obtained by removing one hydrogen atom or a hydroxyl group from the cyclodextrin derivative.
  • the cyclodextrin derivative is selected from the group in which the hydrogen atom of at least one hydroxyl group of cyclodextrin is a hydrocarbon group or the like (that is, a hydrocarbon group, an acyl group and -CONHR (R is a methyl group or an ethyl group). It has a structure substituted with at least one group).
  • the cyclodextrin derivative refers to a molecule having a structure in which a cyclodextrin molecule is substituted with another organic group.
  • the cyclodextrin derivative has at least one hydrogen atom or one hydroxyl group, and preferably has at least one hydroxyl group.
  • the notation cyclodextrin in this specification means at least one selected from the group consisting of ⁇ -cyclodextrin, ⁇ -cyclodextrin and ⁇ -cyclodextrin. Therefore, the cyclodextrin derivative is at least one selected from the group consisting of ⁇ -cyclodextrin derivative, ⁇ -cyclodextrin derivative and ⁇ -cyclodextrin derivative.
  • the host group is preferably a monovalent group obtained by removing one hydroxyl group from a cyclodextrin or a cyclodextrin derivative.
  • the host group is a monovalent group obtained by removing one hydrogen atom or hydroxyl group from a cyclodextrin or cyclodextrin derivative, whereas the hydrogen atom or hydroxyl group removed from the cyclodextrin or cyclodextrin derivative is cyclodextrin or cyclo. It may be any site of the dextrin derivative.
  • ⁇ -cyclodextrin 18
  • ⁇ -cyclodextrin 21
  • ⁇ -cyclodextrin 24.
  • the cyclodextrin derivative is carbonized with a maximum of N-1 hydroxyl group hydrogen atoms per cyclodextrin molecule. It is formed by being substituted with a hydrogen group or the like.
  • the cyclodextrin derivative has a maximum of N hydroxyl group hydrogen atoms per cyclodextrin molecule as a hydrocarbon. It can be replaced with a group or the like.
  • 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 cyclodextrin are substituted with the hydrocarbon group or the like.
  • the structural unit represented by the formula (1) can exhibit a higher affinity for the hydrophobic monomer unit.
  • the hydrogen atom of 80% or more of the total number of hydroxyl groups present in one molecule of the cyclodextrin is substituted with the hydrocarbon group or the like, and the total number of hydroxyl groups is the same. It is particularly preferable that the hydrogen atom of 90% or more of the hydroxyl groups is substituted with the hydrocarbon group or the like.
  • the host group preferably has a structure in which the hydrogen atoms of 13 or more hydroxyl groups among all the hydroxyl groups existing in one molecule of ⁇ -cyclodextrin are substituted with the hydrocarbon group or the like.
  • the hydrogen atoms of 15 or more hydroxyl groups among all the hydroxyl groups existing in one molecule of ⁇ -cyclodextrin are substituted with the hydrocarbon group or the like, and 17 of all the hydroxyl groups It is particularly preferable that the hydrogen atoms of the hydroxyl groups are substituted with the hydrocarbon group or the like.
  • the host group preferably has a structure in which hydrogen atoms of 15 or more hydroxyl groups among all the hydroxyl groups existing in one molecule of ⁇ -cyclodextrin are substituted with the hydrocarbon group or the like.
  • the hydrogen atoms of 17 or more hydroxyl groups among all the hydroxyl groups existing in one molecule of ⁇ -cyclodextrin are substituted with the hydrocarbon group or the like, and 19 of all the hydroxyl groups It is particularly preferable that the hydrogen atoms of one or more hydroxyl groups are substituted with the hydrocarbon group or the like.
  • the host group preferably has a structure in which hydrogen atoms of 17 or more hydroxyl groups among all the hydroxyl groups existing in one molecule of ⁇ -cyclodextrin are substituted with the hydrocarbon group or the like.
  • the hydrogen atoms of 19 or more hydroxyl groups among all the hydroxyl groups existing in one molecule of ⁇ -cyclodextrin are substituted with the hydrocarbon group or the like, and 21 of all the hydroxyl groups. It is particularly preferable that the hydrogen atoms of one or more hydroxyl groups are substituted with the hydrocarbon group or the like.
  • the host group has two or more hydrocarbon groups, they may all be the same or some may be different.
  • the type of the hydrocarbon group is not particularly limited.
  • the hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group.
  • the number of carbon atoms of the hydrocarbon group is not particularly limited, and for example, the number of carbon atoms of the hydrocarbon group is preferably 1 to 4.
  • 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.
  • hydrocarbon group When the hydrocarbon group is a butyl group, it may be either a linear chain or a branched chain.
  • the hydrocarbon group may have a substituent as long as the effect of the present invention is not impaired.
  • the acyl group may be an acetyl group, a propionyl group, a formyl group or the like.
  • the acyl group can also have a substituent.
  • the acyl group is preferably an acetyl group from the viewpoint of easily forming a host-guest interaction and easily obtaining a polymer material having excellent toughness and strength and excellent toughness and strength.
  • -CONHR (R is a methyl group or an ethyl group) is a methyl carbamate group or an ethyl carbamate group.
  • -CONHR is preferably an ethyl carbamate group from the viewpoint that a host-guest interaction is easily formed.
  • the hydrocarbon group and the like are preferably a methyl group and an acyl group, more preferably a methyl group, an acetyl group and a propionyl group, and particularly preferably a methyl group and an acetyl group.
  • the polysiloxane skeleton can have other building blocks.
  • Other building blocks include, for example, a siloxane unit in which a reactive functional group is directly or indirectly bonded to a silicon atom.
  • the structural unit represented by the following formula (4) can be further included.
  • R 7 is synonymous with R 3 and R 4 in formula (2).
  • R 8 represents a monovalent group containing an alkylene having 1 to 8 carbon atoms, and A represents a reactive functional group.
  • R 7 is preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and a methyl group is particularly preferable.
  • R 8 is not particularly limited as long as it is a divalent group containing an alkylene having 1 to 8 carbon atoms.
  • the number of carbon atoms of the alkylene is preferably 1 to 8, more preferably 2 to 7, further preferably 2 to 6, and particularly preferably 2 to 5.
  • R 8 can also include, for example, a heteroatom. Examples of the hetero atom include oxygen, nitrogen and the like.
  • R 8 may have, for example, an ether bond, an amide bond, an amino group, etc., and more preferably has an ether bond (for example,-(CH 2 ) 3- O). -(CH 2 ) -binding is exemplified).
  • a 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 for example, 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 (for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine). Atomic) and the like, and a hydroxy group is particularly preferable.
  • the reactive functional group A can include, for example, an epoxy group, a carboxy group, an amino group, a hydroxyl group, an ester group, etc., and is highly reactive with the guest molecule described later. , Preferably an epoxy group.
  • the content ratio of the structural unit represented by the formula (2) is, for example, 5 to 5 to the total amount of the structural unit represented by the formulas (2), (3) and (4). It can be 95 mol%. From the viewpoint that the hygroscopicity of the polymer material can be easily controlled and the self-repairing performance described later can be easily exhibited, the content ratio of the structural unit represented by the above formula (2) is, for example, the above formula (2).
  • the total amount of the structural units represented by (3) and (4) 20 mol% or more is preferable, 30 mol% or more is more preferable, 40 mol% or more is particularly preferable, and 90 mol% or less is preferable. , 80 mol% or less is more preferable, and 75 mol% or less is particularly preferable.
  • the content ratio of the structural unit represented by the formula (3) is, for example, 0.01 to 30 mol with respect to the total amount of the structural unit represented by the formulas (3) and (4). Can be%. From the viewpoint that the hygroscopicity of the polymer material can be easily controlled and the self-repairing performance described later can be easily exhibited, the content ratio of the structural unit represented by the formula (3) is the above formulas (3) and (4). ), 0.1 mol% or more is preferable, 0.5 mol% or more is more preferable, 1 mol% or more is particularly preferable, and 20 mol% or less is preferable, 15 More preferably mol% or less, and particularly preferably 10 mol% or less.
  • the polysiloxane skeleton can have other structural units in addition to the structural units represented by the above formulas (2), (3) and (4), if necessary. That is, the polymer material of the present invention can be formed of a structural unit represented by the above formulas (2), (3) and (4) and a molecular chain having a structural unit other than these.
  • the other structural units are, for example, 5% by mass or less, preferably 1% by mass or less, more preferably 0.% by mass or less, based on the total amount of the structural units represented by the formulas (2), (3) and (4). It can be 1% by mass or less, particularly preferably 0.05% by mass or less.
  • the polysiloxane skeleton can also be formed only by the structural units represented by the formulas (2), (3) and (4). That is, the polymer material of the present invention can also be formed of a molecular chain having only the structural units represented by the formulas (2), (3) and (4).
  • the polysiloxane skeleton may have any structure such as a random polymer or a block polymer, and is preferably a random polymer because it is easy to produce, for example.
  • the polymer material has a structural unit represented by the formula (1) in the side chain of the polysiloxane skeleton, the hydrophilicity is improved, so that the polymer material has excellent hygroscopicity equal to or higher than that of the conventional silicon material. Can have. Therefore, the polymer material can have excellent hygroscopicity while having a polysiloxane skeleton, and also has flexibility and toughness, which are the characteristics of the polysiloxane skeleton, and thus has excellent mechanical properties.
  • the host group encapsulates a guest group to form an inclusion complex, and the encapsulated guest group chemically bonds (for example, covalently) to the side chain of the polysiloxane skeleton. It may be combined).
  • the guest group is a group derived from the guest molecule, and specifically, is 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.
  • the guest molecule is not particularly limited as long as it can form an inclusion complex with the host group, and is, for example, a compound having 1 or 2 (preferably 1) amino groups, or 1 or 2 (preferably).
  • Compounds with 1 or 2 preferably 1) hydroxyl groups, compounds with 1 or 2 (preferably 1) carboxy groups, compounds with 1 or 2 (preferably 1) epoxy groups, 1 or 2 (preferably 1)
  • Examples thereof include a compound having one or two (preferably one) thiol groups, a compound having one or two (preferably one) thiol groups, and a compound having one or two carboxylated products.
  • Examples of compounds having one or two amino groups include 1-adamantanamine, benzylamine, tert-butylamine, butylamine, 1-aminopyrene, aminoferrocene, 4-aminoazobenzene, 4-aminostylben, cyclohexylamine and hexyl.
  • Examples of the compound having one or two hydroxyl groups include 1-hydroxyadamantan, benzyl alcohol, tert-butyl alcohol, butyl alcohol, 1-hydroxypyrene, 1-hydroxymethylferrocene, 4-hydroxyazobenzene and 4-hydroxystylben.
  • Examples of the compound having one or two carboxy groups include 1-carboxyadamantan, benzoic acid, pivalic acid, butanoic acid, 1-carboxypyrene, 1-carboxyferrocene, 4-carboxyazobenzene, 4-carboxystylben, and cyclohexane.
  • Compounds having one or two carboxylated products include, for example, 1-adamantan carbonyl chloride, terephthaloyl chloride, trimethylacetyl chloride, butyryl chloride, 1-pyrenecarbonyl chloride, 1-ferrocenecarbonyl chloride, 4-.
  • Compounds having one or two epoxy groups include, for example, adamantan oxide, styrene oxide, 1,2-epoxybutane, 1-epoxypyrene, epoxyferrocene, 4-epoxyazobenzene, 4-epoxystylben, cyclohexyl oxide, 1 , 2-Epoxyhexane, 2,2'-bis (4-glycidyloxyphenyl) propane, p-diglycidyloxybenzene, diglycidyl okiisiferocene, 4,4'-diglycidyloxyazobenzene, 4,4'-di Glycidyloxyferrocene, 1,4-diglycidyloxycyclohexane, 1,6-diglycidyloxycyclohexane, ⁇ , ⁇ -diglycidyloxypolyethylene glucol, ⁇ , ⁇ -diglycidyloxypolypropylene glucol, 1,1-bis ( 4-Glysi
  • Examples of the compound having one or two isocyanate groups include 1-adamantan isocyanate, benzyl isocyanate, phenyl isocyanate, tert-butyl isocyanate, butyl isocyanate, 1-pyrene isocyanate, ferrocene isocyanate, azobenzene-4-isocyanate, and stillben-.
  • Examples of compounds having one or two thiol groups include 1-adamantan thiol, benzyl thiol, tert-mercaptan, butane thiol, 1-thiol pyrene, ferrocene thiol, 4-thioazobenzene, 4-thiostylben, cyclohexyl thiol.
  • 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.
  • guest molecules include 1-adamantanamine, benzylamine, tert-butylamine, butylamine, 1-aminopyrene, aminoferrocene, 4-aminoazobenzene, 4-aminostylben, cyclohexylamine, hexylamine, 1-hydroxyadamantan, It is preferably benzyl alcohol, tert-butyl alcohol, butyl alcohol, 1-hydroxypyrene, 1-hydroxymethylferrocene, 4-hydroxyazobenzene, 4-hydroxystylben, etc., preferably 1-adamantanamine, 1-hydroxyadamantan, etc. More preferably, 1-adamantanamine is particularly preferable.
  • the guest group is likely to be bonded to the side chain of the polysiloxane skeleton, and self-repairing property is more
  • the guest molecule can be appropriately selected according to the size of the host group cyclodextrin or cyclodextrin derivative in the ring.
  • the host group is preferably ⁇ -cyclodextrin or ⁇ -cyclodextrin derivative. In this case, the guest group is likely to be included in the host group.
  • the guest group encapsulated in the host group can be chemically bonded to the side chain of the polysiloxane skeleton.
  • another functional group is interposed between the guest group and Si of the polysiloxane skeleton.
  • examples of other functional groups include R 6 in the above formula (3).
  • the guest molecule encapsulated in the host group reacts with the reactive functional group in the structural unit represented by the formula (4).
  • a structure in which the guest group is bonded to the polysiloxane skeleton can be formed.
  • the polysiloxane molecular chain to which the guest group is bonded may be a polysiloxane molecular chain to which the host group enclosing the guest group is bonded.
  • the polysiloxane molecular chain may be different from the polysiloxane molecular chain to which the host group enclosing the guest group is bonded.
  • the inclusion ratio is not particularly limited, and for example, 10 mol% or more of the total amount of the host group in the polysiloxane skeleton can be included. It is preferably 20 mol% or more, more preferably 30 mol% or more, further preferably 40 mol% or more, and particularly preferably 50 mol% or more.
  • the polymer material has various structural units represented by the formula (1) in the side chain of the polysiloxane skeleton (specifically, by having the structural unit represented by the formula (3)). It is possible to form the polymer structure of the above, one of which is the structure formed by the introduction of the guest group 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 has an intramolecular or intermolecular reversible host-guest interaction. Can occur (see FIG. 1 below).
  • the polymer material containing such a polysiloxane skeleton has improved toughness and strength, and can exhibit self-repairing property.
  • the cut polymer material can also have self-healing properties.
  • FIG. 1 is a diagram schematically illustrating a form in which a host group of a side chain of a polysiloxane skeleton is formed by including a guest group in the polymer material of the present invention.
  • the polymeric material has a crosslinked structure, i.e., a three-dimensional network structure.
  • the guest group 20 is bonded to the 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. Moreover, group 40 comprising R 1 bonded to the host group 10 is bonded to the side chain of the polysiloxane skeleton 30.
  • the polymeric material in the form 1, the formula (1) represented by R H -R 1 - is bound to the polysiloxane backbone 30.
  • the polymer material in the form of FIG. 1 has properties as an elastomer, for example.
  • the guest group 20 in the polymer chain and the host group RH may be separated, and the material may be cut.
  • the guest group 20 and the host group RH can be bonded again to form an inclusion complex.
  • the cut surface can be recombined and the polymer material can be repaired.
  • FIG. 2 schematically shows another aspect of the polymer material of the present invention.
  • the polymer material of the form shown in FIG. 2 has a structure in which 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 a polysiloxane having no host group (for example, polydimethylsiloxane).
  • 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 the ring of the host group 10.
  • R 1 bonded to the host group 10 is bonded to the polysiloxane skeleton 30.
  • the host group 10 since the host group 10 can slide while enclosing the polysiloxane skeleton 30, for example, it is excellent in stress relaxation action and can have high toughness and strength, and thus is excellent in mechanical properties. ..
  • Whether or not the polymer material has the form shown in FIG. 2 can be determined from, for example, the result of the swelling test of the polymer material. For example, when a polymer material is prepared without using a chemical cross-linking agent and the obtained polymer material is added to a solvent, a swelling phenomenon is observed without dissolving the polymer material in the form shown in FIG. 2 (so-called). It can be determined that the mobile crosslinked polymer) is formed, and when it is dissolved, it can be determined that the movable crosslinked polymer is not formed.
  • the shape of the polymer material is not particularly limited.
  • the polymer material can take various forms such as a film, a film, a sheet, a particle, a plate, a block, a pellet, a powder, a foamed material, and a liquid.
  • Polymer materials can be used for various purposes.
  • the polymer material can be suitably used for various members such as automobile applications, adhesive applications, electronic component applications, building member applications, food container applications, and transportation container applications.
  • the polymer material since the polymer material has high hygroscopicity, it can also be used for applications such as clothing, medical equipment, and medical equipment (specifically, contact lenses, etc.).
  • the method for producing the polymer material described above is not particularly limited.
  • the above-mentioned polymer material of the present invention has the following general formula (1a).
  • R 2 -R H (1a) A clathrate compound in which a guest molecule is included in the compound represented by Polysiloxane having a reactive functional group in the side chain, Can be provided with a step of reacting.
  • R 2 represents a NH 2 or OH
  • R H is synonymous with R H in the formula (1). That is, RH is the host group.
  • process 1 The process in the above manufacturing method is referred to as "process 1".
  • R 2 is equal to R 2 in the formula (1a), that is, NH 2 or OH
  • R 5 in the formula (21) represents the hydrocarbon group or the like
  • n is 5, 6 or 7.
  • R 5 is one selected from the group consisting of methyl group, an acetyl group, a methyl carbamate group and ethyl carbamate.
  • R 5 is a methyl group or an acetyl group, it is particularly preferable that all of R 5 is a methyl group.
  • Examples of the compound represented by the formula (21) include 6-monodeoxy-6-monoamino-trimethyl-cyclodextrin, 6-monohydroxy-trimethyl-cyclodextrin, and 6-monodeoxy-6-monoamino-triacetyl-cyclodextrin. , 6-Monohydroxy-triacetyl-cyclodextrin, 6-monodeoxy-6-monoamino-triethylcarbamate-cyclodextrin, 6-monohydroxy-triethylcarbamate-cyclodextrin and the like.
  • the type of guest molecule in the clathrate compound is the same as that for forming the guest group described in the above section "1. Polymer material”.
  • the method for producing the clathrate compound used in step 1 is not particularly limited, and a known method for producing the clathrate compound can be widely adopted.
  • the compound represented by the formula (1a) and the guest molecule can be used. It can be produced by a method comprising the steps of mixing to obtain a clathrate compound.
  • the compound: guest molecule represented by the formula (1a) can also be 1: 1 (molar ratio).
  • polysiloxane P The type of polysiloxane having a reactive functional group in the side chain used in step 1 is not particularly limited.
  • polysiloxane P 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, known polysiloxanes can be widely used.
  • the reactive functional group is the same as that of the reactive functional group A in the above formula (4). That is, the reactive functional group 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 in that the reactivity of the inclusion compound is high.
  • the polysiloxane P preferably has a structural unit represented by the formula (2) and a structural unit represented by the formula (4).
  • the polysiloxane P may have any structure such as a random polymer or a block polymer, and is preferably a random polymer because it is easy to produce, for example.
  • the content ratio of the structural unit represented by the formula (2) is determined by the above formula (2).
  • it can be 5 to 95 mol% with respect to the total amount of the structural units represented by 2) and (4).
  • the content ratio of the structural unit represented by the formula (2) is, for example, the formulas (2) and (4).
  • 20 mol% or more is preferable, 30 mol% or more is more preferable, 40 mol% or more is particularly preferable, 90 mol% or less is preferable, and 80 mol% or less is preferable with respect to the total amount of the structural unit represented by). More preferably, 75 mol% or less is particularly preferable.
  • the number average molecular weight Mn of polysiloxane P is not particularly limited, and can be, for example, 500 to 100,000, preferably 1,000 to 50,000.
  • the method for producing polysiloxane P is not particularly limited, and for example, it can be obtained by a known production method, or it can be obtained from a commercially available product.
  • the method of reacting the clathrate compound with polysiloxane having a reactive functional group in the side chain is not particularly limited.
  • a method of mixing the compound represented by the general formula (1a), a guest molecule, and 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 solvent is not particularly limited, and for example, aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; chloroform, 1,2-dichloroethane and the like.
  • Chlorine-based hydrocarbons examples thereof include alcohols such as methanol, ethanol, isopropyl alcohol and t-butanol.
  • the solvent can be used alone or as a mixture of two or more.
  • 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.
  • a polymer material having the desired polysiloxane skeleton can be obtained by performing treatments such as drying as necessary.
  • the polymer material obtained by such a method has, for example, the structure shown in FIG. 1 described above, and has properties as an elastomer.
  • step 2 the step of mixing the compound represented by the formula (1a) with the polysiloxane P (hereinafter referred to as “step 2”) is included.
  • a manufacturing method can be adopted.
  • step 2 of this production method the same conditions as in step 1 described above can be obtained except that the guest molecule is not used.
  • a polysiloxane other than the polysiloxane P that is, a polysiloxane having no reactive functional group A in the side chain
  • a polysiloxane other than the polysiloxane P can be used. It is preferable to use (for example, dimethylpolysiloxane).
  • the method for producing the compound represented by the formula (1a) is not particularly limited, and a known production method can be widely adopted.
  • the compound represented by the formula (1a) is a method for producing a host group-containing polymerizable monomer according to International Publication No. 2018/159791 (specifically, a host group-containing vinyl-based monomer).
  • a production method similar to the production method or the production method of the host group-containing non-vinyl monomer) can be adopted.
  • the obtained solution was dried under reduced pressure with an evaporator, 100 mL of dichloromethane was added, and the mixture was washed with 50 mL of saturated aqueous sodium hydrogen carbonate solution, 50 mL of aqueous solution containing 2.5 g of sodium thiosulfate pentahydrate, and 50 mL of saturated brine.
  • Example 1 The polymer material was synthesized according to the reaction scheme shown in FIG. First, as a polysiloxane P having a reactive functional group in the side chain, Shinetsu Silicone's "epoxy-modified silicone KF-101" (molecular weight of about 1600, epoxy introduction rate of about 33 mol%) was prepared. 360 mg of this polysiloxane P, 72 mg of NH 2- PM ⁇ CD obtained in Production Example 1, and 7.7 mg of 1-adamantanamine (guest molecule) were placed in a sample bottle, and 400 ⁇ L of toluene was added and mixed.
  • Shinetsu Silicone's "epoxy-modified silicone KF-101" molethoxy-modified silicone KF-101" (molecular weight of about 1600, epoxy introduction rate of about 33 mol%) was prepared. 360 mg of this polysiloxane P, 72 mg of NH 2- PM ⁇ CD obtained in Production Example 1, and 7.7 mg of 1-adamantanamine (guest molecule) were placed in
  • FIG. 5 is a 1 H-NMR spectrum (CDCl 3 , 500 MHz, 25 ° C.) of the polymer material obtained in Example 1. From this 1 1 H-NMR spectrum, it was confirmed that the target polymer material was synthesized.
  • Example 2 Same as in Example 1 except that the blending amounts of NH 2- PM ⁇ CD and 1-adamantanamine were both adjusted to 3 mol% with respect to the total number of moles of the epoxy groups of polysiloxane P.
  • a polymer material was obtained by the above method.
  • breaking stress and breaking strain also simply referred to as strain
  • a material showing high values of both breaking stress and breaking strain can be judged to be a material having excellent breaking energy.
  • the polymer material obtained in Example 1 has 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 , which are high in the conventional manner. It was a material having excellent toughness and strength as compared with a molecular material.
  • the polymer material obtained in Example 2 has 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 Jm 2 , which is similar to that of the conventional polymer material. It was a material with excellent toughness and strength.
  • the polymer material (chemical crosslinked structure) obtained in Comparative Example 1 was a material that was so brittle that a sample for tensile test could not be prepared in the first place, and clearly did not have toughness and strength. ..
  • the polymer material obtained in Comparative Example 1 does not have a crosslinked structure due to the host-guest interaction as in Example 1, but has a conventional chemically crosslinked structure, and thus has a polysiloxane skeleton. It can be said that it is not suitable as a means for improving the mechanical properties of polymer materials.
  • Example 1 (Hygroscopic evaluation) The polymer materials obtained in Example 1 and Comparative Example 1 were placed in sample bottles, respectively, and immersed in 6 mL of water for 20 hours. Then, each elastomer was taken out, the surface water was lightly wiped off, the mass was measured, and the water content was calculated from the mass change before and after immersion in water. As a result, the water content of the polymer material obtained in Example 1 was 8.7%, and the water content of the polymer material obtained in Comparative Example 1 was 0.4%. From this result, it was also found that the polymer material obtained in Example 1 had high hygroscopicity.

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021172468A1 (ja) * 2020-02-25 2021-09-02 株式会社 資生堂 ホスト基及び／又はゲスト基を有するシロキサン結合含有高分子化合物を含む樹脂材料
WO2021172463A1 (ja) * 2020-02-25 2021-09-02 株式会社 資生堂 ホスト基及び／又はゲスト基を有するシロキサン結合含有高分子化合物を含む化粧料
CN113388274A (zh) * 2021-06-24 2021-09-14 中国科学院兰州化学物理研究所 一种耐磨水润滑自修复涂层及其制备方法
WO2023003043A1 (ja) 2021-07-21 2023-01-26 国立大学法人大阪大学 シリコーン系高分子化合物及びシリコーン系高分子材料
WO2024128306A1 (ja) * 2022-12-16 2024-06-20 国立大学法人大阪大学 複合ポリマー材料及びその製造方法並びに光学材料

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000506554A (ja) * 1995-12-22 2000-05-30 ノバルティス アクチエンゲゼルシャフト ポリシロキサン／ポリオールマクロマーから製造されるポリウレタン
JP2005536653A (ja) * 2002-08-23 2005-12-02 ワツカー−ケミー　ゲゼルシヤフト　ミツト　ベシユレンクテル　ハフツング シクロデキストリン残基を含む有機ケイ素化合物
JP2014047269A (ja) * 2012-08-30 2014-03-17 Toshiba Corp 自己組織化パターン形成用材料およびパターン形成方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000506554A (ja) * 1995-12-22 2000-05-30 ノバルティス アクチエンゲゼルシャフト ポリシロキサン／ポリオールマクロマーから製造されるポリウレタン
JP2005536653A (ja) * 2002-08-23 2005-12-02 ワツカー−ケミー　ゲゼルシヤフト　ミツト　ベシユレンクテル　ハフツング シクロデキストリン残基を含む有機ケイ素化合物
JP2014047269A (ja) * 2012-08-30 2014-03-17 Toshiba Corp 自己組織化パターン形成用材料およびパターン形成方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
RITTER HELMUT, KNUDSEN BERIT, DURNEV VALERIJ: "Linkage of a-cyclodextrrn- terminated poly(dimethylsiloxanes) by inclusion of quasi bifunctional ferrocene", BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY, vol. 9, September 2013 (2013-09-01), pages 1278 - 1284 p. 1279, XP055798824 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021172468A1 (ja) * 2020-02-25 2021-09-02 株式会社 資生堂 ホスト基及び／又はゲスト基を有するシロキサン結合含有高分子化合物を含む樹脂材料
WO2021172463A1 (ja) * 2020-02-25 2021-09-02 株式会社 資生堂 ホスト基及び／又はゲスト基を有するシロキサン結合含有高分子化合物を含む化粧料
CN113388274A (zh) * 2021-06-24 2021-09-14 中国科学院兰州化学物理研究所 一种耐磨水润滑自修复涂层及其制备方法
WO2023003043A1 (ja) 2021-07-21 2023-01-26 国立大学法人大阪大学 シリコーン系高分子化合物及びシリコーン系高分子材料
JPWO2023003043A1 (https=) * 2021-07-21 2023-01-26
EP4375312A4 (en) * 2021-07-21 2025-07-30 Univ Osaka SILICONE-BASED POLYMER COMPOUND AND SILICONE-BASED POLYMER MATERIAL
WO2024128306A1 (ja) * 2022-12-16 2024-06-20 国立大学法人大阪大学 複合ポリマー材料及びその製造方法並びに光学材料

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