Mechanophores and methods for manufacturing the same

Abstract

To provide mechanophore having high thermostability.SOLUTION: A mechanophore-containing polymerization initiator represented by a general formula (1).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for producing an initiator, an intermediate, and a polymer containing a mechanophore.

Background Art

[0002] A material that exhibits a function originating from a microscale mechanical stimulus acting on a substance is called a mechanical functional material, and its practical application has begun mainly in applications such as adhesion, peeling, self-healing, fracture, and low friction (Non-Patent Document 1). A mechanical functional material in which a single bond is homolytically cleaved by a mechanical stimulus to generate two radical molecules, that is, a mechanophore (a mechanically responsive molecular skeleton) is incorporated into a polymer, has attracted attention as a material exhibiting self-healing properties and self-strengthening properties.

[0003] However, improvement of the heat resistance is required for further expansion of the application range of the mechanical functional material incorporating a mechanophore.

[0004] Non-Patent Document 2 discloses that a diaryl bibenzofuranone (DABBF) skeleton is useful as a mechanophore. The DABBF skeleton is also useful as a mechanical functional material (self-healing material), but the high temperature in the processing process of a polymer material involving injection molding may cause loss of the function of the mechanophore in the material, so the development of a mechanophore with improved heat resistance is required.

Prior Art Documents

Non-Patent Documents

[0005]

Non-Patent Document 1

Non-Patent Document 2

Summary of the Invention

[0006] The present invention aims to provide a novel mechanophore having high heat resistance properties and a mechanically functional material containing the mechanophore. [Means for solving the problem]

[0007] The inventors of this invention conducted extensive research to solve the above problems and found that ditriazine fluorene compounds are useful as highly heat-resistant mechanophores. There have been no previous reports of mechanophores and intermediates consisting of the ditriazine fluorene skeleton of the present invention, and the inventors also discovered the mechanical functional properties of polymers containing this mechanophore, thus completing the present invention.

[0008] In other words, the present invention consists of the following gist.

[0009] [Abstract 1] A polymerization initiator containing a mechanophore represented by the following general formula (1). [ka] [In the formula, R 1 and R 2 Each of these independently represents a hydrogen atom, a C4- to C6 aryl group which may be substituted with one or more C1- to C4 alkyl groups, or a C1- to C4 alkyl group. 3 and R 4 Each of these independently represents a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C1-C4 perfluoroalkyl group, an amino group which may be substituted with one or more C1-C4 alkyl groups, a nitro group, a cyano group, a halogen atom, a C1-C4 alkoxycarbonyl group, a carbamoyl group which may be substituted with C1-C4 alkyl groups, or a C1-C4 acyl group. n represents an integer from 1 to 16. X 1 This is an acyl group represented by the following general formula (2). [ka] (In the formula, Y 1 represents a halogen atom. R 5 and R 6 represent an alkyl group having 1 to 4 carbon atoms. )]

[0010] [Abstract 2] A mechanophore-containing polymerization initiator intermediate represented by the following general formula (3). [Chemical formula] [In the formula, R 1 and R 2 each independently represent a hydrogen atom, an aryl group having 4 to 6 carbon atoms which may be substituted with one or more alkyl groups having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, an amino group which may be substituted with one or more alkyl groups having 1 to 4 carbon atoms, a nitro group, a cyano group, a halogen atom, an alkoxycarbonyl group having 1 to 4 carbon atoms, a carbamoyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, or an acyl group having 1 to 4 carbon atoms. n represents an integer from 1 to 16. ]

[0011] [Abstract 3] A composition comprising the mechanophore-containing polymerization initiator according to Abstract 1 and a vinyl monomer.

[0012] [Abstract 4] A method for producing a polymer, characterized by producing using the composition according to Abstract 3. [Advantages of the Invention]

[0013] The mechanophore-containing polymerization initiator of the present invention can provide a polymer according to the present invention having mechanical functional properties by polymerization with a vinyl monomer. [Modes for Carrying Out the Invention]

[0014] The present invention will be described in detail below.

[0015] R 1 and R 2 Examples of C4- to C6 aryl groups that may be substituted with one or more C1- to C4 alkyl groups include phenyl group, 2-methylbenzene-1,2-diyl group, 3-methylbenzene-1,3-diyl group, 4-methylbenzene-1,4-diyl group, 2-ethylbenzene-1,2-diyl group, 3-ethylbenzene-1,3-diyl group, 4-ethylbenzene-1,4-diyl group, 2-propylbenzene-1,2-diyl group, 3-propylbenzene-1,3-diyl group, 4-propylbenzene-1,4-diyl group, 2-butylbenzene-1,2-diyl group, 3-butylbenzene-1,3-diyl group, 4-butylbenzene-1,4-diyl group, 2-methylpropylbenzene-1,2-diyl group, 3 Examples include the -methylpropylbenzene-1,3-diyl group, 4-methylpropylbenzene-1,4-diyl group, 2-tert-butylbenzene-1,2-diyl group, 3-tert-butylbenzene-1,3-diyl group, 4-tert-butylbenzene-1,4-diyl group, 3,5-tert-butylbenzene-1,3,5-triyl group, thiophene-2-yl group, 3-methylthiophene-2,3-diyl group, 4-methylthiophene-2,4-diyl group, 5-methylthiophene-2,5-diyl group, 2-methylthiophene-2,3-diyl group, 4-methylthiophene-3,4-diyl group, 5-methylthiophene-3,5-diyl group, 2-pyridyl group, 3-pyridyl group, and 4-pyridyl group.

[0016] R 1 and R 2 The alkyl group having 1 to 4 carbon atoms represented by can be linear, branched, or cyclic. Examples include linear alkyl groups such as methyl, ethyl, propyl, and butyl groups; branched alkyl groups such as isopropyl, 2-methylpropyl, 1-methylpropyl, and tert-butyl groups; and cyclic alkyl groups such as cyclopropyl and cyclobutyl groups.

[0017] R1 and R 2 As the group represented by , in terms of the high heat resistance of the mechanophore-containing polymerization initiator intermediate of the present invention (hereinafter also referred to as the intermediate of the present invention), an aryl group or an alkyl group having 1 to 4 carbon atoms which may be substituted with one or more alkyl groups having 1 to 4 carbon atoms is preferred, and includes phenyl group, 2-methylbenzene-1,2-diyl group, 3-methylbenzene-1,3-diyl group, 4-methylbenzene-1,4-diyl group, 2-ethylbenzene-1,2-diyl group, 3-ethylbenzene-1,3-diyl group, 4-ethylbenzene-1,4-diyl group, 2-propylbenzene-1,2-diyl group, 3-propylbenzene-1,3-diyl group, 4-propylbenzene-1,4-diyl group, 2-butylbenzene-1,2-diyl group, 3-butylbenzene-1,3-diyl group, 4-butylbenzene-1,4-diyl group, 2-methylpropylbenzene-1,2-diyl group, 3- Methylpropylbenzene-1,3-diyl group, 4-methylpropylbenzene-1,4-diyl group, 2-tert-butylbenzene-1,2-diyl group, 3-tert-butylbenzene-1,3-diyl group, 4-tert-butylbenzene-1,4-diyl group, 3,5-tert-butylbenzene-1,3,5-triyl group, thiophene-2-yl group, 3-methylthiophene-2,3-diyl group, 4-methylthiophene -2,4-diyl group, 5-methylthiophene-2,5-diyl group, 2-methylthiophene-2,3-diyl group, 4-methylthiophene-3,4-diyl group, 5-methylthiophene-3,5-diyl group, 2-pyridyl group, 3-pyridyl group or 4-pyridyl group are more preferred, phenyl group, thiophene-2-yl group, 2-pyridyl group, 3-pyridyl group or 4-pyridyl group are even more preferred, and phenyl group is particularly preferred.

[0018] R 3 and R 4The alkyl group having 1 to 4 carbon atoms represented by can be linear, branched, or cyclic, and examples include linear alkyl groups such as methyl, ethyl, propyl, and butyl groups; branched alkyl groups such as isopropyl, 2-methylpropyl, 1-methylpropyl, and tert-butyl groups; and cyclic alkyl groups such as cyclopropyl and cyclobutyl groups.

[0019] R 3 and R 4 The alkoxy group having 1 to 4 carbon atoms represented by can be linear, branched, or cyclic, and examples include linear alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups; branched alkoxy groups such as isopropoxy, 1-(2-methylpropyl)oxy, 2-butyloxy, and tert-butoxy groups; and cyclic alkoxy groups such as cyclopropyloxy and cyclobutyloxy groups.

[0020] R 3 and R 4 Examples of perfluoroalkyl groups having 1 to 4 carbon atoms represented by this formula include perfluoromethyl, perfluoroethyl, perfluoropropyl, and perfluorobutyl groups.

[0021] R 3 and R 4 Examples of amino groups that may be substituted with one or more C1 to C4 alkyl groups represented by include N,N-dimethylamino group, N,N-diethylamino group, N,N-dipropylamino group, and N,N-dibutylamino group.

[0022] R 3 and R 4 Examples of halogen atoms represented by include fluorine, chlorine, bromine, and iodine atoms.

[0023] R 3 and R 4Examples of alkoxycarbonyl groups having 1 to 4 carbon atoms represented by this formula include methoxycarbonyl groups, ethoxycarbonyl groups, propoxycarbonyl groups, and the like.

[0024] R 3 and R 4 Examples of carbamoyl groups that may be substituted with one or more C1 to C4 alkyl groups include N-methylcarbamoyl group, N-ethylcarbamoyl group, N-propylcarbamoyl group, N-butylcarbamoyl group, N,N-dimethylcarbamoyl group, and N,N-diethylcarbamoyl group.

[0025] R 3 and R 4 Examples of acyl groups with 1 to 4 carbon atoms represented by include the formyl group, acetyl group, propionyl group, and butyryl group.

[0026] R 3 and R 4 As for the group represented by , a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, isopropyl group, or tert-butyl group is preferred in terms of high production efficiency of the mechanophore-containing polymerization initiator intermediate of the present invention, a hydrogen atom, isopropyl group, or tert-butyl group is more preferred, a hydrogen atom or tert-butyl group is even more preferred, and a hydrogen atom is particularly preferred.

[0027] R 5 and R 6 The alkyl group having 1 to 4 carbon atoms represented by can be linear, branched, or cyclic, and examples include linear alkyl groups such as methyl, ethyl, propyl, and butyl groups; branched alkyl groups such as isopropyl, 2-methylpropyl, 1-methylpropyl, and tert-butyl groups; and cyclic alkyl groups such as cyclopropyl and cyclobutyl groups.

[0028] R 5 and R 6As the C1 to C4 alkyl group represented by , linear or branched alkyl groups are preferred in terms of the high heat resistance of the mechanophore-containing polymerization initiator intermediate of the present invention, methyl, ethyl, propyl, butyl, isopropyl, 1-methylpropyl, or tert-butyl groups are more preferred, methyl, ethyl, propyl, or butyl groups are even more preferred, and methyl groups are particularly preferred.

[0029] n represents an integer from 1 to 16. The integer value of n is preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 6, and particularly preferably 1, in terms of efficient production of the initiator of the present invention.

[0030] Y 1 As the halogen atom represented by , chlorine, bromine, or iodine atoms are preferred, bromine or iodine atoms are more preferred, and bromine atoms are even more preferred, in terms of good production efficiency of the initiator of the present invention.

[0031] X 1 Examples include formulas (2-1) to (2-16) below, but the present invention is not limited thereto.

[0032] [ka]

[0033] [ka]

[0034] [ka]

[0035] [ka]

[0036] X 1In terms of high production efficiency of the polymer according to the present invention, the group represented by formula (2-1), or formulas (2-5) to (2-16) is preferred, the group represented by formulas (2-9) to (2-16) is more preferred, the group represented by formula (2-9), or formula (2-13) is even more preferred, and the group represented by formula (2-9) is particularly preferred.

[0037] Examples of the mechanophore-containing polymerization initiator of the present invention, represented by general formula (1), include formulas (1-1) to (1-24) below.

[0038] [ka]

[0039] [ka]

[0040] [ka]

[0041] [ka]

[0042] [ka]

[0043] [ka]

[0044] [ka]

[0045] [ka]

[0046] [ka]

[0047] [ka]

[0048] As a mechanophore-containing polymerization initiator represented by general formula (1), formulas (1-1) to (1-24) are preferred in terms of high efficiency in producing the polymer according to the present invention, formulas (1-1) to (1-4), formulas (1-9) to (1-10), or formulas (1-19) to (1-24) are more preferred, formulas (1-1) to (1-4), formula (1-21), or formula (1-22) are even more preferred, and formula (1-1) is particularly preferred.

[0049] Examples of intermediates of the present invention represented by general formula (3) include formulas (3-1) to (3-24) below.

[0050] [ka]

[0051] [ka]

[0052] [ka]

[0053] [ka]

[0054] [ka]

[0055] [ka]

[0056] [ka]

[0057] [ka]

[0058] [ka]

[0059] [ka]

[0060] As for general formula (3), formulas (3-1) to (3-4) or formulas (3-6) to (3-24) are preferred in terms of high production efficiency of the initiator of the present invention, formulas (3-1) to (3-4), formulas (3-9) to (3-10), or formulas (3-19) to (3-24) are more preferred, formulas (3-1) to (3-4), formula (3-21), or formula (3-22) are even more preferred, and formula (3-1) is particularly preferred.

[0061] Next, a method for producing the mechanophore-containing polymerization initiator and its intermediates of the present invention will be described. The polymerization initiator and its intermediates of the present invention can be produced through the following manufacturing steps (A) to (F).

[0062] Manufacturing process (A) [ka] (In the formula, R 3 and R 4 (This expresses the same meaning as above.)

[0063] Manufacturing process (A) is a process for producing an alcohol represented by the general formula (100-2) by reacting sodium borohydride with 2-fluorenecarboxyaldehyde.

[0064] Manufacturing process (B) [ka] (In the formula, R 3 and R 4 (This has the same meaning as above. M represents a silicon-containing group.)

[0065] Manufacturing step (B) is a step in which a silicon compound is reacted with an alcohol compound represented by general formula (100-2) in the presence of imidazole to produce a compound represented by general formula (100-3).

[0066] Examples of silicon compounds include trimethylsilyl chloride, t-butyldiphenylchlorosilane, diethylisopropylsilyl chloride, t-butyldimethylsilyl chloride, triphenylsilyl chloride, diphenylmethylchlorosilane, isopropyldimethylchlorosilane, triethylsilyl chloride, chlorodimethylphenylsilane, and triisopropylchlorosilane. Trimethylsilyl chloride, t-butyldimethylsilyl chloride, triisopropylchlorosilane, isopropyldimethylchlorosilane, triethylsilyl chloride, or triisopropylchlorosilane are preferred in terms of the efficiency of producing the compound represented by general formula (100-3), and t-butyldimethylsilyl chloride is more preferred.

[0067] Examples of silicon-containing groups represented by M include trialkylsilyl groups, dialkylarylsilyl groups, alkyldiarylsilyl groups, triarylsilyl groups, trisilylsilyl groups, and more specifically, the groups represented by formulas (procSi-1) to (procSi-8) below.

[0068] [ka]

[0069] [ka]

[0070] As for the silicon-containing group represented by M, the groups represented by formulas (procSi-1) to (procSi-8) are more preferred, the groups represented by formulas (procSi-1) to (procSi-5) are even more preferred, and the group represented by formula (procSi-4) is particularly preferred, in terms of the efficiency of producing the compound represented by the general formula (100-3).

[0071] Manufacturing process (C) [ka] (In the formula, R 1 , R 2 , R 3 , R 4 (And M has the same meaning as above.)

[0072] Manufacturing step (C) is a step to produce a compound represented by general formula (100-5) by reacting a compound represented by general formula (100-3) with a triazine represented by general formula (100-4) in the presence of a base. Preferred bases include alkyllithium, lithium amide, Grignard reagent, etc., lithium amide is more preferred, lithium diisopropylamide or lithium hexamethyldisilazide is even more preferred, and lithium hexamethyldisilazide is particularly preferred.

[0073] Manufacturing process (D) [ka] (In the formula, R 1 , R 2 , R 3 , R 4 (And M has the same meaning as above.)

[0074] Manufacturing step (D) is a process for producing the compound represented by general formula (100-6) by reacting the compound represented by general formula (100-5) with potassium ferricyanide.

[0075] Manufacturing process (E) [ka] (In the formula, R 1 , R 2 , R 3 , R 4 (And M has the same meaning as above.)

[0076] Manufacturing step (E) is a step in which an acid is reacted with a compound represented by general formula (100-6) to produce the intermediate of the present invention represented by general formula (3).

[0077] As the acid, Lewis acids or Brønsted acids are preferred, Brønsted acids are more preferred, sulfuric acid, nitric acid, or hydrochloric acid are even more preferred, and hydrochloric acid is particularly preferred.

[0078] Manufacturing process (F) [ka] (In the formula, R 1 , R 2 , R 3 , R 4 and X 1 This expresses the same meaning as above. X 3 (This represents a halogen atom.)

[0079] Manufacturing step (F) is a step in which an acid halide represented by general formula (1) is reacted with an intermediate of the present invention represented by general formula (3) to produce a mechanophore-containing polymerization initiator of the present invention represented by general formula (1).

[0080] The fluorene represented by general formula (100-1), the triazine represented by general formula (100-4), and the acid halide represented by general formula (100-7) used in the method of producing the polymerization initiator and its intermediate of the present invention are not limited by the method of obtaining them, and commercially available products may be used.

[0081] Furthermore, the polymerizable initiator and its intermediates of the present invention can also be synthesized according to Synthesis Reference Examples 1 to 5 and Examples 1 and 2.

[0082] Next, the composition of the present invention will be described.

[0083] The composition of the present invention comprises a mechanophore-containing polymerization initiator and a main component containing a vinyl monomer.

[0084] Various vinyl monomers can be used as the main component of the composition of the present invention without particular limitations. Specifically, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl acrylate, propyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl Xyl(meth)acrylate, dicyclopentanyloxyethyl(meth)acrylate, isobornyloxyethyl(meth)acrylate, isobornyl(meth)acrylate, adamantyl(meth)acrylate, dimethyladamantyl(meth)acrylate, dicyclopentanyl(meth)acrylate, dicyclopentenyl(meth)acrylate, dicyclopentenyloxyethyl(meth)acrylate, methoxyethyl(meth)acrylate, ethylcarbitol(meth)acrylate, tetrahydro Furfuryl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-phenoxydiethylene glycol (meth)acrylate, ω-carboxy-polycaprolactone (n≒2) monoacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxyethyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate )Acrylate, o-phenylphenolethoxy(meth)acrylate, dimethylamino(meth)acrylate, diethylamino(meth)acrylate, 2,2,3,3,3-pentafluoropropyl(meth)acrylate, 2,2,3,4,4,4-hexafluorobutyl(meth)acrylate, 2,2,3,3,4,4,4-heptafluorobutyl(meth)acrylate, 2-(perfluorobutyl)ethyl(meth)acrylate, 2-(perfluorohexyl)ethyl(meth)acrylate, 1H,1H,3H-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, 1H,1H,7H-dodecafluoroheptyl (meth)acrylate, 1H-1-(trifluoromethyl)trifluoroethyl (meth)acrylate, 1H,1H,3H-hexafluorobutyl (meth)acrylate, 1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl (meth)acrylate, 1H,1H-pentadecaph Luorooctyl (meth)acrylate, 1H,1H,2H,2H-tridecafluorooctyl (meth)acrylate, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, glycidyl (meth)acrylate, 2-(meth)acryloyloxyethyl phosphate, acryloylmorpholine, dimethylacrylamide, dimethylaminopropylacrylamide, ylopropylacrylamide, diethylacrylamide Mono(meth)acrylates such as mid, hydroxyethyl acrylamide, N-acryloyloxyethylhexahydrophthalimide, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyldiol di(meth)acrylate, tripropylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, ethylene oxide-modified bisphenol A di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, glycerin di(meth)acrylate, 2-hydroxy-3-acroyloxypropyl methacrylate, acrylic acid adduct of 1,6-hexanediol diglycidyl ether, 1,Examples include di(meth)acrylates such as acrylic acid adducts of 4-butanediol diglycidyl ether, trimethylolpropane tri(meth)acrylate, ethoxylated isocyanurate triacrylate, pentaerythritol tri(meth)acrylate, tri(meth)acrylates such as ε-caprolactone-modified tris-(2-acryloyloxyethyl) isocyanurate, tetra(meth)acrylates such as pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, oligomeric (meth)acrylates, various urethane acrylates, and various macromonomers. These can be used individually or in mixtures of two or more types.

[0085] Of these, mono(meth)acrylate or di(meth)acrylate is preferred in terms of high production efficiency of the polymer according to the present invention, mono(meth)acrylate is more preferred, methyl(meth)acrylate, ethyl(meth)acrylate, 2-hydroxyethyl acrylate, propyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, butyl(meth)acrylate, isobutyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, octyl(meth)acrylate, or 2-ethylhexyl(meth)acrylate is even more preferred, and methyl(meth)acrylate is particularly preferred.

[0086] There are no restrictions on the amount of vinyl monomer used, but in terms of manufacturing efficiency, the weight ratio of the mechanophore-containing polymerization initiator to the vinyl monomer of the present invention is preferably in the range of 1:1 to 1:10000, and more preferably in the range of 1:1 to 1:1000.

[0087] The composition of the present invention may contain a solvent. The solvents that can be used are not particularly limited as long as they do not inhibit the reaction, and include aliphatic hydrocarbon solvents such as hexane, heptane, decane, and tridecane; ether solvents such as diisopropyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,4-dioxane, and 1,2-dimethoxyethane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, tetralin, and anisole; carbonate ester solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and 4-fluoroethylene carbonate; ester solvents such as ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, and γ-lactone; dimethylformamide (DMF), dimethylacetamide (DMAc), and N-methylpyrrolidone. Examples of solvents include amide solvents such as NMP, urea solvents such as N,N,N',N'-tetramethylurea (TMU) and N,N'-dimethylpropyleneurea (DMPU), sulfoxide solvents such as dimethyl sulfoxide (DMSO), alcohol solvents such as methanol, ethanol, 2-propanol, butanol, octanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and 2,2,2-trifluoroethanol, halogen solvents such as chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, and orthodichlorobenzene, fluorine solvents such as bis(2,2,2-trifluoroethyl)=N,N-diisopropylphosphoramidate (PF-37) and phosphoric acid=tris(2,2,2-trifluoroethyl) (TFEP), nitromethane, and water, and these may be mixed and used in any ratio.

[0088] Of these, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogen solvents, ether solvents, amide solvents, sulfoxide solvents, or fluorine solvents are preferred in terms of yield, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogen solvents, or ether solvents are more preferred, tetralin, toluene, anisole, monochlorobenzene, orthodichlorobenzene, or THF are even more preferred, and anisole is particularly preferred.

[0089] There are no restrictions on the amount of solvent used, but in terms of good manufacturing efficiency, 1 to 100 g / L is preferred, more preferably in the range of 5 to 50 g / L, and even more preferably in the range of 1 to 25 g / L relative to the mechanophore-containing polymerization initiator of the present invention.

[0090] Next, a method for producing a polymer containing the composition of the present invention (hereinafter referred to as "the method for producing the polymer of the present invention") will be described.

[0091] A polymer comprising the composition of the present invention can be produced using the composition of the present invention.

[0092] The polymer production method of the present invention can be carried out in the presence of a copper catalyst. Examples of the copper catalyst include copper iodide, copper bromide, and copper chloride. Copper iodide or copper bromide is preferred, and copper bromide is more preferred, in terms of the production efficiency of the polymer production method of the present invention.

[0093] There are no restrictions on the amount of copper catalyst used, but in terms of good manufacturing efficiency, 0.1 to 10 molar equivalents are preferred, more preferably in the range of 1 to 5 molar equivalents, and even more preferably in the range of 1 to 3 molar equivalents relative to the mechanophore-containing polymerization initiator of the present invention.

[0094] The polymer production method of the present invention can be carried out in the presence of an amine catalyst. Examples of the amine catalyst include 2,2'-bipyridyl, cyclam, 2-dimethylamino-2'-(diphenylphosphino)biphenyl, 4,4'-dimethyl-2,2'-bipyridyl, 4,4'-dinonyl-2,2'-bipyridyl, diphenyl(2-pyridyl)phosphine, 1,1,4,7,10,10-hexatrimethyltriethylenetetramine, N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, tris[2-(dimethylamino)ethyl]amine, tris(2-pyridylmethyl)amine, and the like. In terms of the high production efficiency of the polymer production method of the present invention, 2,2'-bipyridyl, cyclam, 2-dimethylamino-2'-(diphenylphosphino)biphenyl, 4,4'-dimethyl-2,2'-bipyridyl, 4,4'-dinonyl-2,2'-bipyridyl, 1,1,4,7,10,10-hexatrimethyltriethylenetetramine, N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, tris[2-(dimethylamino)ethyl]amine, or tris(2-pyridylmethyl)amine are preferred, and 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 4,4'-dinonyl-2,2'-bipyridyl More preferably, tris[2-(dimethylamino)ethyl]amine or tris(2-pyridylmethyl)amine is used, and more preferably, tris[2-(dimethylamino)ethyl]amine or tris(2-pyridylmethyl)amine is used, and even more preferably, tris[2-(dimethylamino)ethyl]amine or tris(2-pyridylmethyl)amine is used, and tris[2-(dimethylamino)ethyl]amine or tris(2-pyridylmethyl)amine is used, and tris[2-(dimethylamino)ethyl]amine or tris(2-pyridylmethyl)amine is used, and tris[2-(dimethylamino)ethyl]amine or tris(2-pyridylmethyl)amine is used, and especially preferably, tris[2-(dimethylamino)ethyl]amine or tris(2-pyridyl)amine is used.

[0095] There are no restrictions on the amount of amine catalyst used, but in terms of good manufacturing efficiency, 0.1 to 10 molar equivalents are preferred relative to the mechanophore-containing polymerization initiator of the present invention, more preferably in the range of 1 to 5 molar equivalents, and even more preferably in the range of 1 to 3 molar equivalents.

[0096] The polymer production method of the present invention is preferably carried out under an inert gas atmosphere such as argon gas or nitrogen gas, or under vacuum.

[0097] There are no restrictions on the reaction temperature at which the polymer production method of the present invention is carried out, but it is preferable to carry it out in the range of 0°C to 50°C, and more preferably in the range of 0°C to 30°C, in order to obtain a good yield.

[0098] The reaction time for carrying out the polymer production method of the present invention varies depending on the type of (1), the solvent, and the reaction temperature, but is preferably 0.1 to 100 hours, more preferably 1 to 24 hours, even more preferably 1 to 10 hours, and particularly preferably 1 to 6 hours.

[0099] The polymers produced by the polymer production method of the present invention can be obtained by conventional processing after the completion of the production process. If necessary, the polymers may be purified using general methods used by those skilled in the art for the purification of polymers, such as washing, precipitation, filtration, dialysis, column chromatography, preparative HPLC, and Soxhlet extraction. [Examples]

[0100] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0101] The monomers obtained in the examples are 1 Structural analysis was performed by 1H-NMR measurement. The molecular weight and molecular weight distribution of the polymers obtained in the examples were estimated by Gel Permeation Chromatography (GPC) measurement, and the heat resistance was estimated by Eloctron Paramagnetic Resonance (EPR) measurement. Commercially available reagents were used.

[0102] <NMR measurement conditions> Measuring device: Bruker ASCEND TM AVANCE III HD (400 MHz) Measuring solvent: deuterated chloroform (CDCl3) Internal standard substance: tetramethylsilane (TMS)

[0103] <GPC measurement conditions> Measuring device: Tosoh Corporation's high-speed GPC device HLC-8320GPC EcoSEC Column: TSKgel SuperMultipore HZ-H, TSKgel SuperHZ2000 Measuring solvent: THF Measuring temperature: 25 °C Calibration curve: polystyrene standard

[0104] <ESR measurement conditions> Measuring device: JEOL JES-X320 X-band ESR

[0105] [Synthesis reference example 1] [Chemical formula] 2-Fluorene carboxaldehyde (10.5 g, 54.0 mmol) and sodium borohydride (2.49 g, 65.7 mmol) were mixed in 105 mL of ethanol at room temperature for 4 hours. It was concentrated, and the obtained residue was dissolved in ethyl acetate, washed with saturated brine, and dried over anhydrous magnesium sulfate. It was concentrated and purified by column chromatography (silica gel, hexane / ethyl acetate = 2 / 3) to obtain a white solid Fl-OH (9.27 g, 47.2 mmol, 88%). 1 1H-NMR (400 MHz, CDCl3): δ 7.80 - 7.76 (m, 2H), 7.57 - 7.54 (m, 2H), 7.40 - 7.36 (m, 2H), 7.33 - 7.29 (m, 1H), 4.77 (d, J = 5.8 Hz, 2H), 3.91 (s, 2H), 1.68 (t, J = 5.9 Hz, 1H).

[0106] [Synthesis reference example 2] [ka] Fl-OH (3.03 g, 15.4 mmol) and imidazole (1.59 g, 23.4 mmol) were dissolved in 15 mL of anhydrous N,N-dimethylformamide and cooled to 0°C. A solution of tert-butyldimethylchlorosilane (3.59 g, 23.8 mmol) dissolved in 8 mL of anhydrous methylene chloride was added to the reaction vessel at 0°C and mixed overnight at room temperature. Water was added to stop the reaction, and the mixture was extracted with a hexane / ethyl acetate mixed solvent of 1 / 3 and dried over anhydrous magnesium sulfate. The solution was concentrated and purified by column chromatography (silica gel, hexane / ethyl acetate = 10 / 1) to obtain a yellow solid Fl-OTBS (4.50 g, 14.5 mmol, 94%). 1 H-NMR (400MHz, CDCl3): δ7.78-7.73(m,2H),7.54-7.51(m,2H),7.38-7.27(m,3H),4.82(s,2H),3.89(s,2H),0.96(s,9H),0.13(s,6H).

[0107] [Synthesis reference example 3] [ka] Fl-OTBS (4.02 g, 12.9 mmol) was mixed in 516 mL of THF and cooled to -78°C. 1 M lithium hexamethyldisilazide-THF solution (26.0 mL, 26.0 mmol) was added to this mixture and mixed at -78°C for 1 hour. 2-chloro-3,5-diphenyltriazine (3.27 g, 12.2 mmol) was added and mixed overnight at 30°C. Saturated ammonium chloride aqueous solution was added to concentrate the mixture, extracted with chloroform, and dried over anhydrous magnesium sulfate. The mixture was concentrated and purified by column chromatography (silica gel, hexane / ethyl acetate = 25 / 1) to obtain a yellow solid TFl-OTBS (6.08 g, 11.2 mmol, 92%). 1H-NMR (400MHz, CDCl3): δ8.60-8.57(m,4H),7.84-7.79(m,2H),7.71-7.68(m,2H) ,7.59-7.30(s,9H),5.52(s,1H),4.80(s,2H),0.88(s,9H),0.55(d,J=6.9Hz,6H).

[0108] [Synthesis reference example 4] [ka] TFl-OTBS (5.34 g, 9.85 mmol) and K3[Fe(CN)6] (4.06 g, 12.3 mmol) were mixed under an argon atmosphere at room temperature in a THF / H2O (219 mL / 44 mL) mixed solvent. Diazabicycloundecene (DBU) (2.24 g, 2.2 mL, 14.7 mmol) was added dropwise to this mixture, and the mixture was stirred at room temperature for 3 hours. Water was added, and the mixture was extracted with chloroform, washed with water, and dried over anhydrous magnesium sulfate. The mixture was concentrated and purified by column chromatography (silica gel, hexane / ethyl acetate = 25 / 1) to obtain a yellow solid TFl-OTBS2 (4.31 g, 3.98 mmol, 81%). TFl-OTBS2 was dissolved in anisole and temperature-variable EPR measurements were performed. The result showed that the mechanophore dissociation rate at 100°C was 0.00859%. This indicates that the mechanophore has higher heat resistance than DABBF. 1 H-NMR (400MHz, CDCl3): δ8.33-8.31(m,8H),7.47-7.28(m,19H),7.24-6.9 1(m,7H),4.53-4.45(m,4H),0.85(d,J=3.4Hz,18H),-0.04--0.05(m,12H).

[0109] [Example 1] [ka] TFl-OTBS2 (2.52 g, 2.33 mmol) was dissolved in 235 mL of THF at room temperature. 47 mL of 1 M aqueous HCl solution was added to this solution and stirred at room temperature for 3 hours. Water was added, and the mixture was extracted with chloroform and dried over anhydrous magnesium sulfate. The mixture was concentrated, and the resulting product was purified by precipitation (good solvent: chloroform, poor solvent: hexane) to obtain a yellow solid DTF-diol (3-1) (1.444 g, 1.69 mmol, 73%). 1 H-NMR (400MHz, CDCl3): δ8.34-8.32(m,8H),7.52-7.27(m,20H),7.23-7.02(m,6H),4.50-4.38(m,4H),1.28(t,J=6.3Hz,1H),1.20(t,J=6.3Hz,1H).

[0110] [Synthesis reference example 5] [ka] DTF-diol (3-1) (86.3 mg, 0.10 mmol) was dissolved in 4.3 mL of THF and cooled to 0°C. Triethylamine (36.5 mg, 0.05 mL, 0.36 mmol) was added to the mixture, and 2-bromoisobutyryl bromide (71.1 mg, 0.038 mL, 0.31 mmol) was added dropwise. The mixture was warmed to room temperature and reacted for 4 hours. Water was added to the mixture, extracted with chloroform, and dried over anhydrous magnesium sulfate. The mixture was concentrated and purified by column chromatography (silica gel, hexane / Â=6 / 1), followed by precipitation purification (good solvent: chloroform, poor solvent: methanol) to obtain a white solid mechanophore-containing polymerization initiator (1-1) (60.4 mg, 0.05 mmol, 52%). 1 H-NMR (400MHz, CDCl3): δ8.32-8.31(m,8H),7.57(d,J=7.5Hz,1H),7.52-7.28(m,19H),7.2 3-7.15(m,4H),7.05(t,J=7.4Hz,1H),6.79(s,1H),5.01-4.87(m,4H),1.83-1.78(m,12H).

[0111] [Example 2] Formula (1-1) (28.0 mg, 0.024 mmol), anisole (1.15 mL), methyl methacrylate (1.08 g, 1.15 mL, 10.8 mmol), and tris[2-(dimethylamino)ethyl]amine (0.01 mL, 8.5 mg, 0.037 mmol) were mixed at room temperature and freeze-degassed. Under an N2 atmosphere, copper(I) bromide (4.6 mg, 0.032 mmol) was added to this mixture and stirred at room temperature for 100 minutes. Chloroform was added and the mixture was passed through an activated alumina (neutral) column to remove the copper complex. The obtained residue was concentrated and poured into methanol. The solid was filtered and recovered to obtain a white solid (100.3 mg, Mn=19.9 kDa, PDI=1.32, 21%). When the obtained polymer was ground using a mortar and pestle, it showed red coloration. This result indicates that the polymer according to the present invention has mechanical functionality.

[0112] [Example 3] Formula (1-1) (28.3 mg, 0.024 mmol), anisole (1.15 mL), methyl methacrylate (1.08 g, 1.15 mL, 10.8 mmol), and 4,4'-dinonyl-2,2'-bipyridyl (16.1 mg, 0.039 mmol) were mixed at room temperature and freeze-degassed. Under an N2 atmosphere, copper(I) bromide (4.1 mg, 0.029 mmol) was added to this mixture and stirred at room temperature for 100 minutes. Chloroform was added and the mixture was passed through an activated alumina (neutral) column to remove the copper complex. The obtained residue was concentrated and poured into methanol. The solid was filtered and recovered to obtain a white solid (68.2 mg, Mn=11.3 kDa, PDI=1.22, 24%). When the obtained polymer was ground using a mortar, it showed red coloration. This result indicates that the polymer according to the present invention has mechanical functionality. [Industrial applicability]

[0113] The initiator and polymer of the present invention are useful as self-mechanically functional materials.

Claims

1. A polymerization initiator containing a mechanophore represented by the following general formula (1). 【Chemistry 1】 [In the formula, R １ and R ２ Each of these independently represents a hydrogen atom, a C4-C6 aryl group which may be substituted with one or more C1-C4 alkyl groups, or a C1-C4 alkyl group. ３ and R ４ Each of these independently represents a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C1-C4 perfluoroalkyl group, an amino group which may be substituted with one or more C1-C4 alkyl groups, a nitro group, a cyano group, a halogen atom, a C1-C4 alkoxycarbonyl group, a carbamoyl group which may be substituted with C1-C4 alkyl groups, or a C1-C4 acyl group. n represents an integer from 1 to 16. X １ This is an acyl group represented by the following general formula (2). 【Chemistry 2】 (In the formula, Y １ R represents a halogen atom. ５ and R ６ (This represents an alkyl group with 1 to 4 carbon atoms.)

2. R １ and R ２ is an aryl group having 4 to 6 carbon atoms or an alkyl group having 1 to 4 carbon atoms, which may be substituted with one or more alkyl groups having 1 to 4 carbon atoms, R ３ and R ４ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a perfluoroalkyl group having 1 to 4 carbon atoms, n is an integer from 1 to 8, R ５ and R ６ is an alkyl group having 1 or 2 carbon atoms, Y １ is a bromine atom or an iodine atom, The mechanophore-containing polymerization initiator according to claim 1.

3. R １ and R ２ However, it is an aryl group having 4 to 6 carbon atoms that may be substituted with one or more alkyl groups having 1 to 4 carbon atoms, R ３ and R ４ is a hydrogen atom, n is 1, R ５ and R ６ The group is a methyl group, Y １ A mechanophore-containing polymerization initiator according to claim 1 or 2, wherein the atom is a bromine atom.

4. A polymerization initiator intermediate containing a mechanophore represented by the following general formula (3). 【Transformation 3】 [In the formula, R １ and R ２ Each of the following independently represents a hydrogen atom, a C4-C6 aryl group which may be substituted with one or more C1-C4 alkyl groups, or a C1-C4 alkyl group. R3 and R4 each independently represent a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C1-C4 perfluoroalkyl group, an amino group which may be substituted with one or more C1-C4 alkyl groups, a nitro group, a cyano group, a halogen atom, a C1-C4 alkoxycarbonyl group, a C1-C4 carbamoyl group which may be substituted with C1-C4 alkyl groups, or an C1-C4 acyl group. n represents an integer from 1 to 16.

5. R １ and R ２ Each of these is independently an aryl group having 4 to 6 carbon atoms or an alkyl group having 1 to 4 carbon atoms, which may be substituted with one or more alkyl groups having 1 to 4 carbon atoms. ３ and R ４ The mechanophore-containing polymerization initiator intermediate according to claim 4, wherein each of them is independently a hydrogen atom, a C1 to C4 alkyl group, a C1 to C4 alkoxy group, or a C1 to C4 perfluoroalkyl group, and n is 1 to 8.

6. R １ and R ２ Each of these is an aryl group having 4 to 6 carbon atoms, which may be independently substituted with one or more alkyl groups having 1 to 4 carbon atoms, and R ３ and R ４ The mechanophore-containing polymerization initiator intermediate according to claim 4 or 5, wherein n is a hydrogen atom and n is 1.

7. A composition comprising a mechanophore-containing polymerization initiator and a vinyl monomer according to any one of claims 1 to 3.

8. A method for producing a polymer, characterized by using the composition described in claim 7.

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