Mechanophores and methods for producing them

Abstract

To provide a new mechanophore that is not colored even after a mechanical function, and a polymer comprising the mechanophore.SOLUTION: A polymerization initiator is represented by general formula (1) in the figure. A polymer relating to the initiator functions as a mechanical functional material.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to methods for preparing initiators, intermediates and polymers containing mechanophores. [Background technology]

[0002] Materials that exhibit functions in response to microscale mechanical stimuli acting on a substance are called mechanically functional materials, and their practical applications have begun, focusing on adhesion, peeling, self-repair, fracture, low friction, etc. (Non-Patent Document 1). Mechanically functional materials that incorporate mechanophores (mechanically responsive molecular frameworks), molecules that undergo homolytic cleavage of a single bond in response to a mechanical stimulus to generate two radical molecules, are attracting attention as materials that exhibit self-repairing and self-toughening properties. However, further expansion of the range of applications requires improvement in the performance of mechanophores, and improvements in performance, such as heat resistance and luminescence properties, are required. It has been disclosed that diarylbibenzofuranone (DABBF) skeletons are useful as mechanophores (Non-Patent Document 2). DABBF exhibits blue coloration after mechanical functioning, making it useful as a probe to indicate the manifestation of mechanical function. However, coloration of polymer materials can lead to a decrease in UX, and therefore the development of mechanophores that do not exhibit coloration is desired. [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] Chemical Society Reviews, Volume 50, Pages 4100-4140, 2021. [Non-patent document 2] Angewandte Chemie International Edition, Volume 54, Pages 6168-6172, 2015. Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention provides a new mechanophore that does not become discolored even after mechanical function and a polymer comprising said mechanophore. [Means for solving the problem]

[0005] As a result of extensive research aimed at solving the above problems, the present inventors have discovered that dicyanoaryl acetate compounds are useful as uncolored mechanophores. The mechanophores and intermediates thereof comprising the dicyanoaryl acetate skeleton of the present invention have not been reported to date, and the inventors have also discovered the mechanical functional properties of polymers containing the mechanophores, leading to the completion of the present invention.

[0006] That is, the present invention comprises the following gist. [Abstract 1] A mechanophore-containing polymerization initiator represented by general formula (1): [ka] (In the formula, R 1 , R 2 and R 3 each independently represents 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 which may be substituted with an alkyl group having 1 to 4 carbon atoms. n represents an integer of 1 to 16. Y 1 represents an oxygen atom (O), a sulfur atom (S), or NH. 1 is an acyl group represented by the following general formula (2). [ka] (In the formula, Y 2 represents a halogen atom. 4 and R 5 represents an alkyl group having 1 to 4 carbon atoms. [Abstract 2] A mechanophore-containing polymerization initiator intermediate represented by general formula (3): [ka] (In the formula, R 1 , R 2 and R 3 each independently represents 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 which may be substituted with an alkyl group having 1 to 4 carbon atoms. n represents an integer of 1 to 16. Y 1 represents an oxygen atom (O), a sulfur atom (S), or NH. [Abstract 3] A composition comprising the mechanophore-containing polymerization initiator according to Aspect 1 or 2 and a vinyl monomer. [Abstract 4] A method for producing a polymer, characterized by using the composition described in Aspect 3. [Effects of the Invention]

[0007] The mechanophore-containing polymerization initiator of the present invention can give the polymer of the present invention having mechanical functional properties by polymerization with a vinyl monomer. DETAILED DESCRIPTION OF THE INVENTION

[0008] The present invention will be described in detail below. R 1 , R 2 , R 3 , R 4 , and R 5The alkyl group having 1 to 4 carbon atoms represented by the formula (I) may be linear, branched, or cyclic, and examples thereof include linear alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group; branched alkyl groups such as an isopropyl group, a 2-methylpropyl group, a 1-methylpropyl group, and a tert-butyl group; and cyclic alkyl groups such as a cyclopropyl group and a cyclobutyl group. R 1 , and R 3 As the alkyl group represented by the formula (I), a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group or a tert-butyl group is preferred, a methyl group, an isopropyl group or a tert-butyl group is more preferred, a methyl group or a tert-butyl group is even more preferred, and a tert-butyl group is particularly preferred, in view 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). R 2 In view of the high heat resistance of the intermediate of the present invention, the alkyl group represented by the formula (I) is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, or a tert-butyl group, more preferably a hydrogen atom, a methyl group, an isopropyl group, or a tert-butyl group, still more preferably a hydrogen atom, a methyl group, or a tert-butyl group, and particularly preferably a hydrogen atom or a methyl group. R 4 , and R 5 As the alkyl group having 1 to 4 carbon atoms represented by the formula (I), a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, or a tert-butyl group is preferred, a methyl group, an ethyl group, or an isopropyl group is more preferred, a methyl group or an ethyl group is even more preferred, and a methyl group is particularly preferred, from the viewpoint of high production efficiency of the polymer of the present invention. R 1 , R 2 , and R 3The alkoxy group having 1 to 4 carbon atoms represented by the formula (I) may be linear, branched, or cyclic, and examples thereof include linear alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy, branched alkoxy groups such as isopropoxy, 1-(2-methylpropyl)oxy, 2-butyloxy, and tert-butoxy, and cyclic alkoxy groups such as cyclopropyloxy and cyclobutyloxy. In view of the high heat resistance of the intermediate of the present invention, methoxy, ethoxy, propoxy, or butoxy is preferred, methoxy, ethoxy, or butoxy is more preferred, methoxy or ethoxy is even more preferred, and methoxy is particularly preferred. R 1 , R 2 , and R 3 Examples of the perfluoroalkyl group having 1 to 4 carbon atoms represented by the formula (I) include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, and a perfluorobutyl group. R 1 , R 2 , and R 3 Examples of the amino group optionally substituted with one or more alkyl groups having 1 to 4 carbon atoms, represented by the formula (I), include an N,N-dimethylamino group, an N,N-diethylamino group, an N,N-dipropylamino group, an N,N-dibutylamino group, etc. In view of the high heat resistance of the intermediate of the present invention, an N,N-dimethylamino group, an N,N-diethylamino group, or an N,N-dibutylamino group is preferred, an N,N-dimethylamino group or an N,N-diethylamino group is more preferred, and an N,N-dimethylamino group is even more preferred. R 1 , R 2 , and R 3 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R 1 , R 2 , R 3 Examples of the alkoxycarbonyl group having 1 to 4 carbon atoms represented by the formula (I) include a methoxycarbonyl group, an ethoxycarbonyl group, a propylcarbonyl group, and a butoxycarbonyl group. R 1 , R2 , and R 3 Examples of the carbamoyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, represented by the following formula (I), include an N-methylcarbamoyl group, an N-ethylcarbamoyl group, an N-propylcarbamoyl group, an N-butylcarbamoyl group, an N,N-dimethylcarbamoyl group, and an N,N-diethylcarbamoyl group. R 1 , R 2 , and R 3 Examples of the acyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, represented by the formula (I), include a formyl group, an acetyl group, a propionyl group, a butyryl group, and a valeryl group. The mechanophore polymerization initiator of the present invention has a high polymerization initiation efficiency. 1 , and R 3 The group represented by the formula (I) is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or a tert-butyl group, and even more preferably a hydrogen atom or a tert-butyl group. R 2 In view of the high heat resistance of the intermediate of the present invention, the group represented by the formula (I) is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an amino group which may be substituted with an alkyl group having 1 to 4 carbon atoms, a nitro group, a cyano group, or an alkoxycarbonyl group having 1 to 4 carbon atoms; more preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, an N,N-dimethylamino group, an N,N-diethylamino group, a methoxy group, or a nitro group; still more preferably a hydrogen atom, a methyl group, an N,N-dimethylamino group, an N,N-diethylamino group, a methoxy group, or a nitro group; and particularly preferably a hydrogen atom, a methyl group, an N,N-dimethylamino group, an N,N-diethylamino group, or a methoxy group. n represents an integer of 1 to 16. In terms of high production efficiency of the polymer according to the present invention, n is preferably an integer of 1 to 10, more preferably an integer of 2 to 6, even more preferably an integer of 2 to 4, and particularly preferably 2. Y 1represents an oxygen atom (O), a sulfur atom (S), or NH. In terms of high production efficiency of the polymer according to the present invention, O and NH are preferred, and O is more preferred. X 1 Examples of the compound include the following formulas (2-1) to (2-16). [ka] [ka] [ka] [ka] In terms of high production efficiency of the polymer according to the present invention, formula (2-1) or formula (2-5) to formula (2-16) are preferred, formula (2-9) to formula (2-16) are more preferred, formula (2-9) or formula (2-13) are even more preferred, and formula (2-9) is particularly preferred. Examples of the mechanophore-containing polymerization initiator of the present invention represented by general formula (1) include those represented by the following formulae (1-1) to (1-17). [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] As general formula (1), in terms of high production efficiency of the polymer of the present invention, formulas (1-1) to (1-17) are preferred, formulas (1-1) to (1-6), formula (1-11), formula (1-12), or formulas (1-15) to (1-17) are more preferred, formulas (1-1) to (1-3), formula (1-6), formula (1-11), or formula (1-17) are even more preferred, and formulas (1-1) to (1-3), formula (1-6), or formula (1-11) are particularly preferred. Examples of the intermediate of the present invention represented by general formula (3) include the following formulae (3-1) to (3-17). [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] As the general formula (3), in terms of high production efficiency of the polymer according to the present invention, the formulas (3-1) to (3-17) are preferred, the formulas (3-1) to (3-6), (3-11), (3-12), or the formulas (3-15) to (3-17) are more preferred, the formulas (3-1) to (3-3), (3-6), (3-11), or (3-17) are even more preferred, and the formulas (3-1) to (3-3), (3-6), or (3-11) are particularly preferred. Next, a method for producing the mechanophore-containing polymerization initiator and intermediate of the present invention will be described. The polymerization initiator and intermediate thereof of the present invention can be produced through the following production steps (A) to (F). Manufacturing process (A)

[0009] [ka] (In the formula, Y 1 has the same meaning as above.) The production process (A) is a process for producing an alcohol compound represented by general formula (100-3) by reacting an alcohol represented by general formula (100-2) with cyanoacetic acid in the presence of an acid. Manufacturing process (B)

[0010] [ka] (In the formula, Y 1 represents the same meaning as above.) In the production process (B), a cyano compound represented by the general formula (100-4) is produced by reacting an alcohol compound represented by the general formula (100-3) with dihydropyran in the presence of an acid. Manufacturing process (C)

[0011] [ka] (In the formula, Y 1 , R 1 , R 2 , and R 3 has the same meaning as above. X 2 represents a halogen atom.) In the production process (C), a cyano compound represented by the general formula (100-4) is reacted with an aryl halide represented by the general formula (100-6) in the presence of a palladium catalyst to produce a cyano compound represented by the general formula (pre-1-THP). Manufacturing process (D)

[0012] [ka] (In the formula, Y 1 , R 1 , R 2 , and R 3 represents the same meaning as above.) The production process (D) is a process for producing a cyano compound represented by the general formula (3-THP) by reacting potassium ferricyanide with a cyano compound represented by the general formula (pre-1-THP). Manufacturing process (E)

[0013] [ka] (In the formula, Y 1 , R 1 , R 2 , and R 3 has the same meaning as above. X 3 represents a halogen atom.) The production process (E) is a process for producing the intermediate of the present invention represented by general formula (3) by reacting an acid with a cyano compound represented by general formula (3-THP). Manufacturing process (F)

[0014] [ka] (In the formula, Y 1 , R 1 , R 2 , R 3 , and X 1 represents the same meaning as above.) Production process (F) is a process for producing the mechanophore-containing polymerization initiator of the present invention represented by general formula (1) by reacting the intermediate of the present invention represented by general formula (3) with an acid halide represented by general formula (100-7). The cyanoacetic acid, alcohol represented by general formula (100-2), aryl halide represented by general formula (100-6), and acid halide represented by general formula (100-7) used in the production method of the present invention may be obtained by any method without any limitation, and commercially available products may be used. Next, the polymer of the present invention will be described. The composition of the present invention comprises the initiator of the present invention and a base agent containing a vinyl monomer. The vinyl monomer that can be used as the main component of the composition of the present invention can be used without any particular limitation. 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 (meth)acrylate, etc. Acrylate, dicyclopentanyloxylethyl (meth)acrylate, isobornyloxylethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dimethyl adamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethyl carbitol (meth)acrylate, tetrahydrofurfuryl (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, o-phenylphenol ethoxy ( (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-Pentadecafluorooctyl (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, isopropylacrylamide, diethylacrylamide, hydroxyethyl acrylic Amides, mono(meth)acrylates such as 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, tricyclodecane dimethanol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, glycerin di(meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, acrylic acid adduct of 1,6-hexanediol diglycidyl ether, 1,Diacrylates such as acrylic acid adduct of 4-butanediol diglycidyl ether, tri(meth)acrylates such as trimethylolpropane tri(meth)acrylate, ethoxylated isocyanuric acid triacrylate, pentaerythritol tri(meth)acrylate, and 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 can be used alone or in combination of two or more. In terms of high production efficiency of the polymer according to the present invention, mono(meth)acrylates and diacrylates are preferred, 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, and 2-ethylhexyl(meth)acrylate are even more preferred, and methyl(meth)acrylate is particularly preferred. The composition of the present invention may contain a solvent. The solvent that can be used is not particularly limited as long as it does not inhibit the reaction, and examples thereof 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, and tetralin; 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; dimethyl sulfoxide (DMF), dimethylacetamide (DMAc), and N-methylpyrrolidone (NMPC). Examples of solvents include amide solvents such as N,N,N',N'-tetramethylurea (TMU) and N,N'-dimethylpropyleneurea (DMPU), urea solvents such as N,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, halogenated solvents such as chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, and orthodichlorobenzene, fluorinated solvents such as bis(2,2,2-trifluoroethyl)N,N-diisopropylphosphoramidate (PF-37) and tris(2,2,2-trifluoroethyl)phosphate (TFEP), nitromethane, water, and the like, and these may be mixed and used in any ratio. Among these, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated solvents, ether solvents, amide solvents, sulfoxide solvents, and fluorinated solvents are preferred in terms of good yield, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated solvents, and ether solvents are more preferred, tetralin, toluene, monochlorobenzene, orthodichlorobenzene, and THF are even more preferred, and toluene is particularly preferred. There is no limitation on the amount of solvent used, but in terms of good production efficiency, it is preferably 1 to 100 g / L relative to the initiator of the present invention, more preferably in the range of 5 to 50 g / L, and even more preferably in the range of 1 to 15 g / L. Next, the production method of the present invention will be described. A method for producing a polymer comprising the composition of the present invention (hereinafter referred to as the method for producing the polymer of the present invention) can be prepared using the composition of the present invention. The method for producing the polymer of the present invention can be carried out in the presence of a copper catalyst, such as copper iodide, copper bromide, or copper chloride. In terms of the high production efficiency of the method for producing the polymer of the present invention, copper iodide or copper bromide is preferred, and copper bromide is more preferred. There is no limitation on the amount of copper catalyst used, but in terms of production efficiency, it is preferably 0.1 to 10 equivalents relative to the initiator of the present invention, more preferably 1 to 5 equivalents, and even more preferably 1 to 3 equivalents. The method for producing a polymer of the present invention can be carried out in the presence of an amine catalyst. Examples of such an 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, and tris(2-pyridylmethyl)amine. In view of the high production efficiency of the 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, and tris(2-pyridylmethyl)amine are preferred. N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, tris[2-(dimethylamino)ethyl]amine, and tris(2-pyridylmethyl)amine are more preferred, 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 4,4'-dinonyl-2,2'-bipyridyl, tris[2-(dimethylamino)ethyl]amine, and tris(2-pyridylmethyl)amine are even more preferred, and 4,4'-dinonyl-2,2'-bipyridyl is particularly preferred. Although there is no limitation on the amount of the amine catalyst used, from the viewpoint of good production efficiency, 0.1 to 10 equivalents, more preferably in the range of 1 to 5 equivalents, and even more preferably in the range of 1 to 3 equivalents are preferred with respect to the mechanophore-containing polymerization initiator of the present invention. The 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. Although there is no limitation on the reaction temperature for carrying out the production method of the polymer of the present invention, it is preferably carried out in the range of 20°C to 100°C, and more preferably 40°C to 80°C, from the viewpoint of good yield. The reaction time 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. The polymer that can be produced by the production method of the polymer of the present invention can be obtained by performing ordinary treatment after the completion of the production process. If necessary, it may be purified by appropriately using general means used by those skilled in the art for polymer purification, such as washing, precipitation, filtration, dialysis, column chromatography, preparative HPLC, Soxhlet extraction, etc. For the purpose of improving the mechanical functionality of the polymer that can be produced by the production method of the polymer of the present invention, a polymer in which a hydrogen atom is introduced at the end of the polymer that can be produced by the production method of the polymer of the present invention can also be produced by adding a radical initiator or an organotin compound during or after the reaction.

Examples

[0015] Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

[0016] The monomers obtained in the examples 1 were subjected to structural analysis 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 products were used for the reagents. <NMR measurement conditions> Measuring device: Bruker ASCEND TM ADVANCE III HD (400 MHz) Measurement solvent: deuterated chloroform (CDCl3) or deuterated acetone (Acetone-d6) Internal standard substance: tetramethylsilane (TMS) <GPC measurement conditions> Measuring device: Tosoh Corporation's high-speed GPC device HLC-8320GPC EcoSEC Column: TSKgel SuperMultipore HZ-H, TSKgel SuperHZ2000 Measurement solvent: THF Measurement temperature: 25 °C Calibration curve: polystyrene standard <ESR measurement conditions> Measuring device: JEOL JES-X320 X-band ESR [Synthesis reference example 1]

[0017] [Chem.] Cyanoacetic acid (5.0 g, 59 mmol), ethylene glycol (7.3 g, 6.6 mL, 120 mmol), and p-toluenesulfonic acid monohydrate (0.3 g, 1.6 mmol) were mixed in 20 mL of toluene at room temperature. The mixture was heated to 130 °C overnight in a round-bottom flask equipped with a Dean-Stark apparatus. The mixture was cooled to room temperature. By distillation under reduced pressure, 2-hydroxyethyl-2-cyanoacetate (3.0 g, 24 mmol, 40%) was obtained as a colorless oily liquid. 1 H-NMR (400 MHz, CDCl3): δ 4.27 (t, J = 4.62 Hz, 2H), 3.81 (t, J = 4.62 Hz, 2H), 3.48 (s, 2H), 2.27 (s, 1H). [Synthesis reference example 2]

[0018] [Chem.] 2-Hydroxyethyl-2-cyanoacetate (1.1 g, 8.3 mmol) and toluenesulfonic acid monohydrate (16 mg, 0.08 mmol, 1 mol%) were dissolved in 20 mL of CHCl3 at 0 °C. To this solution, 3,4-dihydro-2H-pyran (910 mg, 11 mmol) was added dropwise. The mixture was reacted at room temperature overnight. NaHCO3 was added to quench the reaction, and the resulting mixture was transferred to a separatory funnel. The organic layer was washed with saturated brine, dried over anhydrous MgSO4, concentrated, and purified by column chromatography (silica gel, EtOAc / hexane = 1 / 2) to give HECA-THP (0.98 g, 4.6 mmol, 57%) as a colorless oily liquid. 1 H-NMR (400MHz, CDCl3): δ4.57(t,J=6.85Hz,1H),4.32(m,2H),3.84-3.93(m,1H),3 .75-3.83(m,1H),3.56-3.67(m,1H),3.45(m,1H),3.43(s,2H),1.39-1.86(m,6H). [Synthesis reference example 3]

[0019] [ka] HECA-THP (980 mg, 4.6 mmol), 1-bromo-3,5-di-tert-butylbenzene (1.2 g, 4.6 mmol), and trisodium phosphate (2.3 g, 14 mmol) were mixed in 30 mL of toluene. N2 was bubbled through the mixture at room temperature for 30 minutes. Tris(dibenzylideneacetone)dipalladium(0) (42 mg, 0.046 mmol) and tri-tert-butylphosphonium tetrafluoroborate (53 mg, 0.18 mmol) were added to the mixture. N2 was bubbled through the mixture for an additional 30 minutes and then heated to 80 °C overnight. After cooling to room temperature, the mixture was transferred to a separatory funnel. The organic layer was washed with saturated brine, dried over anhydrous MgSO4, concentrated in vacuo, and purified by column chromatography (silica gel, EtOAc / hexane = 1 / 10) to give a colorless oily liquid PCA-THP (1.3 g, 3.2 mmol, 72%). 1 H-NMR(400MHz,Acetone-d6):δ7.55(t,J=1.72Hz,1H),7.39(s,2H),5.28(s,1H),4.55(s,1H),4.36(m, 2H),3.84(m,1H),3.72(m,1H),3.62(m,1H),3.41(m,1H),1.71(m,1H),1.38-1.62(m,5H),1.34(s,18H). [Synthesis reference example 4]

[0020] [ka] PCA-THP (550 mg, 1.4 mmol) and K3[Fe(CN)6] (580 mg, 1.8 mmol) were mixed in a THF / HO (12 mL / 3 mL) mixed solvent at room temperature under a N2 atmosphere. Diazabicycloundecene (DBU) (830 mg, 810 μL, 5.4 mmol) was added dropwise to this mixture, and the mixture was stirred at room temperature for 30 min. The mixture was then transferred to a separatory funnel. The organic layer was diluted with EtOAc, washed with saturated brine, concentrated, dried over anhydrous MgSO4, concentrated, and purified by column chromatography (silica gel, 1 / 4 EtOAc / hexane) to give DPCA-THP (350 mg, 1.7 mmol, 65%) as a white solid containing two isomers. Isomer 1: 1 H-NMR (400MHz, Acetone-d6): δ7.51(s,2H),7.28(s,4H),4.56(s,2H),4.48(s,4H),3.7 8-3.90(m,2H),3.56-3.72(m,4H),3.19-3.38(m,2H),1.30-1.78(m,12H),1.25(s,36H). Isomer 2: 1H-NMR(400MHz,Acetone-d6):δ7.54(t,J=1.56Hz,2H),7.09(s,4H),4.48-4.68(m,6H),3. 80-3.96(m,2H),3.61-3.79(m,4H),3.21-3.44(m,2H),1.30-1.82(m,12H),1.23(s,36H). [Example 1]

[0021] [ka] DPCA-THP (160 mg, 0.20 mmol) was dissolved in 10 mL of THF at room temperature. To this solution was added 10 mL of 1 M aqueous HCl. The mixture was stirred at room temperature overnight. After quenching the acid with NaHCO, the organic layer was extracted with EtOAc, collected, dried over anhydrous MgSO, concentrated, and purified by column chromatography (silica gel, 1:1 EtOAc / hexane) to give DPCA-diol (3-6) (120 mg, 0.19 mmol, 92%) as a white solid. Isomer 1: 1 H-NMR (400MHz, Acetone-d6): δ7.48(t,J=1.52Hz,2H),7.21(s,4H),4.29-4.55(m,4H),3.99(t,J=5.54Hz,2H)3.78(q,J=5.18Hz,4H),1.23(s,36H). [Synthesis reference example 5]

[0022] [ka] HECA-THP (1.5 g, 7.0 mmol), 4-bromotoluene (1.2 g, 7.0 mmol), and trisodium phosphate (3.5 g, 21 mmol) were mixed in 30 mL of toluene. N2 was bubbled through the mixture at room temperature for 30 minutes. Tris(dibenzylideneacetone)dipalladium(0) (65 mg, 0.070 mmol) and tri-tert-butylphosphonium tetrafluoroborate (82 mg, 0.28 mmol) were added to the mixture. N2 was bubbled through the mixture for an additional 30 minutes and then heated to 80 °C overnight. After cooling to room temperature, the mixture was transferred to a separatory funnel. The organic layer was washed with saturated brine, collected, dried over anhydrous MgSO4, concentrated in vacuo, and purified by column chromatography (silica gel, 1 / 10 EtOAc / hexane) to give TCA-THP (500 mg, 1.7 mmol, 24%) as a colorless oil. 1 H-NMR (400MHz, Acetone-d6): δ7.41(d,J=8.06Hz,2H),7.28(d,J=7.93Hz,2H),5.27(s,1H),4.54(t,J=3.02Hz,1H),4.35(t, J=4.71Hz,2H),3.79-3.88(m,1H),3.65-3.73(m,1H),3.55-3.64(m,1H),3.35-3.42(m,1H),2.35(s,3H),1.36-1.78(m,6H). [Synthesis reference example 6]

[0023] [ka] TCA-THP (480 mg, 1.6 mmol) and K3[Fe(CN)6] (680 mg, 2.1 mmol) were placed in a THF / HO (20 mL / 5 mL) mixed solvent and mixed at room temperature under a N2 atmosphere. DBU (960 mg, 940 μL, 6.3 mmol) was added dropwise to the mixture, and the resulting mixture was stirred at room temperature for 30 min. The mixture was then transferred to a separatory funnel. The organic layer was diluted with EtOAc, washed with saturated brine, dried over anhydrous MgSO4, concentrated, and purified by column chromatography (silica gel, 1 / 4 EtOAc / hexane) to give DTCA-THP (160 mg, 0.26 mmol, 33%) as a white solid. 1 H-NMR(400MHz,Acetone-d6):δ7.23(d,J=8.04z,4H),7.01(dd,J=8.48,J=2.40Hz,4H),4.49-4.64 (m,6H),3.86-3.96(m,2H),3.59-3.76(m,4H),3.31-3.42(m,2H),2.37(s,6H),1.25-1.72(m,12H). [Example 2]

[0024] [ka] DTCA-THP (140 mg, 0.23 mmol) was dissolved in 20 mL of THF at room temperature. To this solution, 20 mL of 1 M aqueous HCl was added. The mixture was stirred at room temperature overnight. After quenching with NaHCO, the organic layer was extracted with EtOAc, collected, dried over anhydrous MgSO, concentrated, and purified by column chromatography (silica gel, EtOAc / hexane = 1 / 1) to give 3-1 (90 mg, 0.20 mmol, 87%) as a white solid. 1 H-NMR(400MHz,Acetone-d6):δ7.22(d,J=8.02Hz,4H),7.00(d,J=8.40Hz,4H), 4.43-4.52(m,4H),4.00(t,J=5.55Hz,2H),3.81(t,J=5.15Hz,4H),2.37(s,6H). Formula (3-1) was dissolved in anisole and subjected to variable-temperature ESR measurements. As a result, no signal was observed at 25°C. A slight signal was observed at 100°C, and the estimated dissociation rate of the mechanophore was 0.00284%. This indicates that the mechanophore has extremely high heat resistance. Furthermore, since no coloration was observed after dissociation, it is useful as a colorless mechanically functional material. [Synthesis reference example 7]

[0025] [ka] HECA-THP (2.0 g, 9.4 mmol), 4-bromoaniline (1.9 g, 9.4 mmol), and sodium phosphate (4.6 g, 28 mmol) were mixed in 30 mL of toluene. N2 was bubbled through the mixture at room temperature for 30 min. Tris(dibenzylideneacetone)dipalladium(0) (86 mg, 0.094 mmol) and tri-tert-butylphosphonium tetrafluoroborate (110 mg, 0.38 mmol) were added to the mixture. N2 was bubbled through the mixture for an additional 30 min and then heated to 80 °C overnight. After cooling to room temperature, the mixture was transferred to a separatory funnel. The organic layer was washed with saturated brine, collected, dried over anhydrous MgSO4, concentrated in vacuo, and purified by column chromatography (silica gel, 1 / 10 EtOAc / hexane) to give ACA-THP (600 mg, 1.8 mmol, 19%) as a yellow oily liquid. 1 H-NMR(400MHz,Acetone-d6):δ7.31(d,J=8.29Hz,2H),6.78(d,J=8.91Hz,2H),5.11(s,1H),4.54(q,J=3.43Hz,1H),4.33(t, J=4.72Hz,2H),3.77-3.89(m,1H),3.66-3.75(m,1H),3.54-3.64(m,1H),3.35-3.42(m,1H),2.96(s,6H),1.36-1.80(m,6H). [Synthesis reference example 8]

[0026] [ka] ACA-THP (600 mg, 1.8 mmol) and K3[Fe(CN)6] (770 mg, 2.4 mmol) were placed in a THF / HO (24 mL / 6 mL) mixed solvent and mixed at room temperature under a N2 atmosphere. DBU (820 mg, 810 μL, 5.4 mmol) was added dropwise to the mixture, and the resulting mixture was stirred at room temperature for 30 min. The mixture was then transferred to a separatory funnel. The organic layer was diluted with EtOAc, washed with saturated brine, dried over anhydrous MgSO4, concentrated, and purified by column chromatography (silica gel, 1 / 3 EtOAc / hexane) to give DACA-THP (460 mg, 1.4 mmol, 76%) as a brown solid. 1 H-NMR(500MHz,Acetone-d6):δ6.95(dd,J=8.38Hz,J=2.98Hz,4H),6.68(dd,J=9.13Hz,J=2.78Hz,4H),4.61(m,2H), 4.53(t,J=9.60Hz,4H),3.86-3.94(m,2H),3.65-3.80(m,4H),3.33-3.41(m,2H),2.98(s,12H),1.32-1.86(m,12H). [Example 3]

[0027] [ka] DACA-THP (320 mg, 0.48 mmol) was dissolved in 40 mL of THF at room temperature. To this solution was added 40 mL of 1 M aqueous HCl. The mixture was stirred at room temperature overnight. After quenching the acid with NaHCO, the organic layer was extracted with EtOAc, collected, dried over MgSO, concentrated, and purified by column chromatography (silica gel, EtOAc / hexane = 1 / 1) to give (3-3) (200 mg, 0.41 mmol, 85%) as a white solid. 1H-NMR(500MHz,Acetone-d6):δ6.94(d,J=9.06Hz,4H),6.67(d,J=9.08Hz,4H),4.4 2(t,J=5.55Hz,4H),3.98(t,J=5.64Hz,2H),3.81(q,J=4.89Hz,4H),2.99(s,12H). Formula (3-3) was dissolved in anisole and subjected to variable-temperature EPR measurements. As a result, almost no signal was observed at 25°C. A slight signal was observed at 100°C, and the mechanophore dissociation rate was estimated to be 0.175%. Furthermore, no coloration was observed after dissociation, indicating its usefulness as a colorless mechanically functional material. [Example 4]

[0028] [ka] (3-6) (130 mg, 0.20 mmol) and 2-bromoisobutyryl bromide (190 mg, 0.82 mmol) were dissolved in 10 mL of dichloromethane. The mixture was cooled to 0 °C. Triethylamine (120 mg, 170 μL, 1.2 mmol) was added dropwise to the mixture. The mixture was warmed to room temperature and reacted overnight. The mixture was transferred to a separatory funnel, and the organic layer was extracted with EtOAc, washed with saturated brine, dried over anhydrous MgSO4, concentrated, and purified by column chromatography (silica gel, EtOAc / hexane = 1 / 8) to give (1-6) (160 mg, 0.17 mmol, 84%) as a yellow solid. 1 H-NMR (400MHz, Acetone-d6): δ7.53(s,2H),7.06(s,4H),4.32-4.49(m,4H),4.50-4.74(m,4H),1.79(s,12H),1.22(s,36H). [Example 5]

[0029] Formula (1-6) (52 mg, 0.056 mmol) and methyl methacrylate (4.5 g, 4.8 mL, 45 mmol) were mixed in 5 mL of toluene at room temperature. N2 was bubbled through the mixture for 30 minutes. Copper(I) bromide (16 mg, 0.11 mmol) and 4,4'-dinonyl-2,2'-bipyridyl (46 mg, 0.11 mmol) were added to the mixture. N2 was bubbled through the mixture for an additional 30 minutes. The mixture was heated to 60 °C for 3 hours. The mixture was cooled to room temperature, and CHCl3 was added. The mixture was passed through an activated alumina (neutral) column to remove the copper complex. The resulting residue was concentrated and poured into methanol. The solid was collected by filtration to give a white solid (990 mg, Mn = 40.6 kDa, PDI = 1.1, 44%). 400 mg (0.010 mmol) of the resulting white solid was dissolved in 8 mL of toluene at room temperature. N2 was bubbled through the solution for 30 minutes. AIBN (0.80 mg, 0.005 mmol) and tributyltin hydride (8.7 mg, 0.030 mmol) were added to the solution. N2 was bubbled through the mixture for an additional 30 minutes. The mixture was heated at 60 °C for 3 hours. After cooling to room temperature, the mixture was concentrated and precipitated with methanol. The solid was collected by filtration to obtain the polymer of the present invention (250 mg, 0.0062 mmol, 62%). The resulting polymer was ground using a ball mill (Retsch Mixer Mill MM 400, 30 Hz). EPR measurements showed that the radical generation rate increased with grinding time. 22% of the mechanophores were cleaved and radicals were generated after 10 minutes of grinding, and 30% after 25 minutes. Furthermore, the fact that no coloration was observed even after the separation indicates that the polymer according to the present invention has colorless mechanical functionality. [Industrial Applicability]

[0030] The initiator and polymer of the present invention are useful as self-mechanical functional materials.

Claims

1. A mechanophore-containing polymerization initiator represented by general formula (1): 【Chemical 1】 (In the formula, R １ , R ２ and R ３ each independently represents 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 which may be substituted with an alkyl group having 1 to 4 carbon atoms. n represents an integer of 1 to 16. Y １ represents an oxygen atom (O), a sulfur atom (S), or NH. １ is an acyl group represented by the following general formula (2). 【Chemistry 2】 (In the formula, Y ２ represents a halogen atom. ４ and R ５ represents an alkyl group having 1 to 4 carbon atoms.

2. R １ and R ３ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ２ is a hydrogen atom, a methyl group, a methoxy group, a dimethylamino group, or a diethylamino group, and Y １ is an oxygen atom, and R ４ and R ５ is a methyl group, and Y ２ 2. The mechanophore-containing polymerization initiator according to claim 1, wherein is a bromine atom and n is 2.

3. A mechanophore-containing polymerization initiator intermediate represented by general formula (3): 【Chemistry 3】 (In the formula, R １ , R ２ and R ３ each independently represents 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 which may be substituted with an alkyl group having 1 to 4 carbon atoms. n represents an integer of 1 to 16. Y １ represents an oxygen atom (O), a sulfur atom (S), or NH.

4. R １ and R ３ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ２ is a hydrogen atom, a methyl group, a methoxy group, a dimethylamino group, or a diethylamino group, and Y １ 4. The mechanophore-containing polymerization initiator intermediate according to claim 3, wherein is an oxygen atom and n is 2. End

5. A composition comprising the mechanophore-containing polymerization initiator according to claim 1 or 2 and a vinyl monomer.

6. A method for producing a polymer, which comprises using the composition according to claim 5.

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