Fluorescent self-repairing material

Abstract

The present invention addresses the problem of providing a tough, fluorescent self-repairing elastomer. The present invention provides a copolymer having a first unit and a second unit that are at least two different types of olefin-derived repeating units, and a third unit that is at least one type of compound-derived repeating unit having at least one type of light-emitting unit in a side chain.

Description

Fluorescent self-healing materials

[0001] The present invention relates to the synthesis of luminescent (e.g., fluorescent) self-healing materials, and more particularly to the synthesis of tough, fluorescent, self-healing materials via scandium-catalyzed terpolymerization of pyrenylethenylstyrene, ethylene, and anisylpropylene.

[0002] Polymers capable of self-healing mechanical damage have attracted considerable attention over the past few decades due to their potential to improve the lifetime, safety, and environmental impact of many applications. Incorporating fluorescent materials into self-healing polymers offers an exciting and important research area, enabling the creation of fluorescent self-healing materials with even greater added value. However, research in this field has been quite limited to date. Most fluorescent self-healing materials reported to date have been primarily based on gels or polymer composites (Non-Patent Documents 1-4), and typically exhibited relatively weak mechanical strength, poor self-healing capabilities, or low fluorescence quantum yields. Therefore, the development of tough, fluorescent self-healing materials is highly desirable.

[0003] On the other hand, in recent studies on the copolymerization of nonpolar and polar olefins using organic rare earth catalysts, the present inventors have found that copolymerization of ethylene and anisyl-substituted propylene using a highly sterically hindered scandium catalyst leads to the production of unique multiblock copolymers consisting of ethylene-alt-anisylpropylene segments and short ethylene-ethylene blocks. These sequence-controlled copolymers exhibit excellent elasticity and unprecedented self-healing properties due to nanophase separation of the short ethylene-ethylene blocks from the flexible ethylene-alt-anisylpropylene matrix, without relying on any special chemical interactions (Non-Patent Documents 5, 6).

[0004] Bhattacharya, S.; Phatake, R. S.; Nabha Barnea, S.; Zerby, N.; Zhu, J.-J.; Shikler, R.; Lemcoff, N. G.; Jelinek, R. Fluorescent self-healing carbon dot / polymer gels. ACS Nano 2019, 13, 1433-1442.Sun, J.; Wang, J.; Chen, M.; Pu, X.; Wang, G.; Li, L.; Chen, G.; Cai, Y.; Gu, X.; Tang, B. Z. Fluorescence turn-on visualization of microscopic processes for self-healing gels by AIEgens and anticounterfeiting application. Chem. Mater. 2019, 31, 5683-5690.Yao, Y.; Xu, Z.; Liu, B.; Xiao, M.; Yang, J.; Liu, W. Multiple H-bonding chain extender-based ultrastiff thermoplastic polyurethanes with autonomous self-healability, solvent-free adhesiveness, and AIE fluorescence. Adv. Funct. Mater. 2021, 31, 2006944.Liu, Y.; Chen, T.; Jin, Z.; Li, M.; Zhang, D.; Duan, L.; Zhao, Z.; Wang, C. Tough, stable and self-healing luminescent perovskite-polymer matrix applicable to all harsh aquatic environments. Nat. Commun. 2022, 13, 1338.Wang, H.; Yang, Y.; Nishiura, M.; Higaki, Y.; Takahara, A.; Hou, Z.Synthesis of self-healing polymers by scandium-catalyzed copolymerization of ethylene and anisylpropylenes. J. Am. Chem. Soc. 2019, 141, 3249-3257.Yang, Y.; Wang, H.; Huang, L.; Nishiura, M.; Higaki, Y.; Hou, Z. Terpolymerization of ethylene and two different Methoxyaryl-substituted propylenes by scandium catalyst makes tough and fast self-healing elastomers. Angew. Chem., Int. Ed. 2021, 60, 26192-26198.

[0005] In view of the above circumstances, an object of the present invention is to provide a tough, fluorescent, self-repairing material.

[0006] The present inventors have conducted extensive research to solve the above-mentioned problems. The approach of synthesizing a tough, fluorescent, self-healing polymer by incorporating a fluorescent dye-containing olefin into a polyolefin backbone through catalyst-controlled multicomponent olefin copolymerization has not been reported to date. However, this approach is extremely interesting in principle and is also important from a practical perspective. Based on previous findings of sequence-controlled copolymers using scandium catalysts, the present inventors attempted to create a new fluorescent self-healing polymer by terpolymerization of ethylene, anisylpropylene, and a fluorescent dye-containing olefin monomer. As a result, they succeeded in producing a scandium-catalyzed terpolymer of 4-[2-(1-pyrenyl)ethenyl]styrene (Pyr), ethylene (E), and anisylpropylene (AP), and found that this copolymer met the above-mentioned problems. Based on these findings, the present invention was completed.

[0007] That is, the gist of the present invention relates to the following: [1] A copolymer having at least first and second units, which are at least two different repeating units derived from an olefin, and a third unit, which is a repeating unit derived from at least one compound having at least one light-emitting group in its side chain. [2] The copolymer, which comprises: a soft segment in which the first unit and the second unit are repeated alternately, and a hard segment in which blocks of the first unit are aggregated. [3] The copolymer, in which the third unit is derived from a polymerizable compound having: a polymerizable ethylene group, at least one light-emitting group, and a linking group connecting the polymerizable ethylene group and the at least one light-emitting group. [4] The copolymer, wherein the linking group contains at least one double bond not involved in polymerization, and when irradiated with light of a predetermined wavelength λ1, a cyclization reaction between the at least one double bond not involved in polymerization proceeds, thereby shifting the maximum excitation wavelength and / or maximum emission wavelength, and when irradiated with light of a predetermined wavelength λ2 (λ2 > λ1), the ring formed by the cyclization reaction is cleaved. [5] The copolymer, wherein the first unit is derived from a non-polar olefin and the second unit is derived from a polar olefin. [6] The copolymer, wherein the second unit is derived from a compound represented by the following formula (II):

[0008]

[0009] wherein Z is a heteroatom selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, and selenium; １ is a substituted or unsubstituted hydrocarbyl group having 1 to 30 carbon atoms, n is an integer of 1 or 2 depending on the atomic type of Z, and R ３ is a hydrocarbylene group having 1 to 5 carbon atoms, and R ４ is a halogen atom, a hydrocarbyl group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkylamino group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; R ４is a hydrocarbyl group, they may be bonded to form a fused ring, and m is an integer of 0 to 4. [7] The copolymer, wherein the molar ratio of the first unit to the second unit (first unit / second unit) in the copolymer is greater than 1 and less than 2. [8] The copolymer, wherein the molar ratio of the third unit to all structural units in the copolymer is less than 2 mol%. [9] A molded article comprising at least one of the copolymers.

[10] The molded article is a film.

[11] A device having a layer comprising at least one of the copolymers.

[12] The device, wherein the layer functions as at least one of a light-emitting layer and a recording layer.

[13] The molded article comprises at least first and second units, which are at least two different repeating units derived from an olefin, and a third unit, which is a repeating unit derived from at least one compound having at least one luminescent group in its side chain, and at least one copolymer containing at least soft segments in which the first units and the second units are alternately repeated, and hard segments in which blocks of the first units are aggregated, wherein the copolymer has at least a phase-separated region in which a phase formed by the hard segments and a phase formed by the aggregated third units are present and separated from a phase formed by the soft segments.

[14] The device comprises at least first and second units, which are at least two different repeating units derived from an olefin, and a third unit, which is a repeating unit derived from at least one compound having at least one light-emitting group in its side chain, and at least one copolymer comprising at least soft segments in which the first units and the second units are alternately repeated, and hard segments in which blocks of the first units are aggregated, wherein the copolymer has at least a phase-separated region in which a phase constituted by the hard segments and a phase constituted by the aggregated third units are present and separated from a phase constituted by the soft segments.

[0010] The present invention provides a tough, fluorescent, self-healing material.

[0011] Figure 1 shows the NMR spectra of the E-AP-Pyr terpolymer P5 and the monomer Pyr in C2D2Cl4. 1 H NMR spectrum of Figure 1B: P5 13 C 1 Aliphatic portion of the {H} NMR spectrum. Figure 1C: Monomer Pyr 1H NMR spectrum. Figure 2 shows the UV-Vis absorption and fluorescence properties of terpolymer P5. Figure 2A: UV-Vis absorption spectrum of P5 (0.25 mg / mL) in THF. Figure 2B: Normalized fluorescence spectra of P5 in different concentrations of THF and in the solid state (film) under UV irradiation (350 nm wavelength). Figure 2C: Photographs of P5 in different concentrations of THF and in the solid state (film) under daylight (top panel) and a 254 nm UV lamp (bottom panel). Figure 3 shows the physical and mechanical properties of P1-P7. Figure 3A: Table summarizing the mechanical properties of P1-P7. Figure 3B: Stress-strain curves of P1-P7. Figure 3C: Self-healing test of P5 in air at 25°C. Figure 3D: Self-healing test of P5 in various aqueous environments (1 M HCl (ii), water (iii), seawater (iv), and 1 M NaOH (v)) at 25 °C. Figure 3E: Optical microscope images (photographs) of a film sample of P5 scratched with a razor blade in air (left) and after 20 seconds of self-healing (right). Figure 3F: TEM image (photograph) of an unstained ultrathin film of P5 deposited on a 400-mesh carbon-coated copper grid. Figure 4 is a schematic diagram of the multiphase morphology of the E-AP-Pyr terpolymer and its self-healing mechanism. E = ethylene, AP = anisylpropylene, Pyr = 4-[2-(1-pyrenyl)ethenyl]styrene. Figure 5 shows the photoinduced reversible cycloaddition reaction of the terpolymer P5 (0.25 mg / mL) in THF. Figure 5A: Schematic diagram of the photochemical reversible cycloaddition of the Pyr units in P5. Figure 5B: UV-Vis spectral changes of P5 in THF upon irradiation at λ = 405 nm for different times. Figure 5C: Fluorescence spectral changes of P5 in THF upon irradiation at λ = 405 nm for different times. Figure 5D: UV-Vis spectral changes of the THF solution formed in B (after 4 hours of irradiation at 405 nm) upon irradiation at λ = 365 nm for different times. Figure 5E: Fluorescence spectral changes of the THF solution formed in B (after 4 hours of irradiation at 405 nm) upon irradiation at λ = 365 nm for different times. Figure 6 shows the photoirradiation of a film sample of P5 and the properties of the product. Figure 6A, top panel: Schematic diagram of the photoinduced [2+2] cycloaddition of the Pyr units in P5 on a surface.Figure 6A, center: Photographs of P5 (left) and a film sample (P5', right) formed by irradiating P5 with 405 nm light for 5 minutes, under daylight and UV lamp, respectively. Figure 6A, bottom: Photographs of a toluene-insoluble thin film (P5A, left) obtained by immersing P5' in toluene, and a film sample of the toluene-soluble portion of P5' (P5B, right), under daylight and UV lamp, respectively. Figure 6B: Table summarizing the mechanical properties of P5, P5', and P5B. Figure 6C: Stress-strain curves of P5, P5', and P5B. Figure 6D: Self-repair test of P5' in air at 25°C. Figure 7 shows information storage in P5 film by photolithography. Scale bar: 0.5 cm. Figure 7A: The film was covered with a floral photomask and irradiated with 405 nm light for 5 minutes. This results in a floral pattern printed on the film, which is invisible in daylight but discernible under UV lamp. Figure 7B: Photographs of the floral-printed film under UV lamp during its cutting, self-repair, stretching, and final recovery; a daylight photograph of the stretched, repaired film is also shown (bottom right). Figure 8 shows a scheme for the scandium-catalyzed terpolymerization of ethylene (E), 3-(o-anisyl)propylene (AP), and 4-[2-(1-pyrenyl)ethenyl]styrene (Pyr) and the photodecomposition of the terpolymer.

[0012] Hereinafter, the embodiments of the present invention will be described in detail. However, the present invention is not limited to the following preferred embodiments, and can be freely modified within the scope of the present invention.

[0013] In this specification, when a numerical range is expressed as "lower limit to upper limit," the upper limit may be "equal to or less than" or "less than," and the lower limit may be "equal to or greater than" or "greater than."

[0014] A polymer is composed of one or more types of "repeating units." A low molecular weight compound before the repeating unit is incorporated into a polymer is called a "monomer." In this specification, "repeating unit" (or sometimes simply "unit") means this "repeating unit."

[0015] As used herein, "alkyl" refers to a monovalent group formed by removing one hydrogen atom from any carbon atom of a straight-chain, branched, or cyclic saturated hydrocarbon. Examples of alkyl include methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, t-butyl, isobutyl, pentyl, isopentyl, 2,3-dimethylpropyl, hexyl, and cyclohexyl.

[0016] As used herein, "alkenyl" refers to a monovalent group formed by removing one hydrogen atom from any carbon atom of a straight-chain, branched, or cyclic unsaturated hydrocarbon having one or more carbon-carbon double bonds. For example, vinyl, propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 1-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 1-methylidenebutyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl, 2-methylidenebutyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl nyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-methylidenepentyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl, 2-methyl-4-pentenyl, 2-methylidenepentyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-methylidenepentyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1-heptenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 5-heptenyl, 6-heptenyl, octenyl, nonenyl, and decenyl.

[0017] As used herein, the term "alkynyl" refers to a monovalent group obtained by removing one hydrogen atom from any carbon atom of a straight-chain, branched, or cyclic unsaturated hydrocarbon having one or more carbon-carbon triple bonds. Examples of alkynyl include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, pentynyl, hexynyl, and phenylethynyl.

[0018] In this specification, for example, "aryl having 6 to 10 carbon atoms" refers to an aromatic hydrocarbon group having 6 to 10 carbon atoms, and examples thereof include benzene and naphthalene.

[0019] In this specification, for example, "heteroaryl having 3 to 10 carbon atoms" refers to a 3- to 10-membered monocyclic heterocyclic group or a 5- to 10-membered fused heterocyclic group containing at least one heteroatom selected from a nitrogen atom, an oxygen atom, and a sulfur atom. The number of heteroatoms contained in the heteroaryl may be, for example, 1 to 5, 1 to 4, 1 to 3, 1 to 2, 2, or 1. For example, various combinations exist, such as a heterocyclic group containing one nitrogen atom, a heterocyclic group containing two nitrogen atoms, a heterocyclic group containing three nitrogen atoms, a heterocyclic group containing one oxygen atom, a heterocyclic group containing two oxygen atoms, a heterocyclic group containing one oxygen atom and one nitrogen atom, and a heterocyclic group containing one sulfur atom. The heterocyclic group may be aromatic or non-aromatic. The monocyclic heterocyclic group is preferably a 5- or 6-membered ring. The fused heterocyclic group is preferably an 8- to 10-membered ring.Examples of heteroaryl having 5 to 10 carbon atoms include piperidyl, piperazyl, morpholyl, quinuclidyl, pyrrolidinyl, azetidyl, oxetyl, azetidin-2-one-yl, aziridinyl, tropanyl, furyl, tetrahydrofuryl, thienyl, pyrrolyl, pyrrolinyl, pyrrolidinyl, dioxolanyl, oxazolyl, oxazolinyl, isoxazolyl, thiazolyl, thiazolinyl, isothiazolyl, imidazolyl, imidazolinyl, Imidazolidinyl, oxazolidinyl, thiazolidinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, oxadiazolyl, furazanyl, thiadiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, pyranyl, pyridyl, piperidinyl, pyridazinyl, pyrimidinyl, pyrazinyl, piperazinyl, dioxanyl, oxazinyl, morpholinyl, thiazinyl, triazinyl, benzofuranyl, isobenzofuranyl, di Hydrobenzofuranyl, dihydroisobenzofuranyl, benzothienyl, isobenzothienyl, dihydrobenzothienyl, dihydroisobenzothienyl, tetrahydrobenzothienyl, quinolyl, isoquinolyl, quinazolinyl, phthalazinyl, pteridinyl, coumaryl, chromonyl, 1,4-benzodiazepinyl, indolyl, isoindolyl, benzimidazoyl, benzofuryl, purinyl, acridinyl, phenoxazinyl, phenothiazinyl Examples of the alkyl group include benzoxazolyl, benzothiazolyl, indazolyl, benzimidazolyl, benzodioxolanyl, benzodioxanylchromenyl, chromanyl, isochromanyl, chromanonyl, cinnolinyl, quinoxalinyl, indolizinyl, quinolidinyl, imidazopyridyl, naphthyridinyl, dihydrobenzoxazinyl, dihydrobenzoxazolinonyl, dihydrobenzoxazinonyl, and benzothioxanyl.

[0020] In this specification, "alkoxy" refers to a group in which the above-mentioned "alkyl" is bonded via an oxygen atom (O).

[0021] In this specification, "alkylene" means a divalent group obtained by removing one hydrogen atom from the carbon atom of the aforementioned "alkyl", "alkenylene" means a divalent group obtained by removing one hydrogen atom from the carbon atom of the aforementioned "alkenyl", "alkynylene" means a divalent group obtained by removing one hydrogen atom from the carbon atom of the aforementioned "alkynyl", "arylene" means a divalent group obtained by removing one hydrogen atom from the ring carbon atom of the aforementioned "aryl", and "heteroarylene" means a divalent group obtained by removing one hydrogen atom from the ring atom of the aforementioned "heteroaryl".

[0022] As an example of our invention, we have successfully synthesized a terpolymer (ternary copolymer) of 4-[2-(1-pyrenyl)ethenyl]styrene (Pyr), ethylene (E), and anisylpropylene (AP) using a scandium catalyst (Figure 8). 4-[2-(1-pyrenyl)ethenyl]styrene (Pyr) has an excellent fluorescence quantum yield of 97%. This styrene unit was successfully copolymerized with ethylene and anisylpropylene as a fluorescent dye monomer under scandium catalysis. More specifically, we found that the half-sandwich scandium catalyst facilitated the ternary copolymerization (1) at room temperature, yielding a unique sequence-controlled terpolymer consisting of E-alt-AP, independent Pyr, and an E-E sequence. The resulting terpolymer not only exhibited excellent fluorescence properties, but also remarkable mechanical and self-healing properties. In other words, a tough, fluorescent, self-healing material was developed. Furthermore, the terpolymer film was photolithographically processed to produce self-healing fluorescent 2D images via a photoinduced cycloaddition reaction of the styrenyl C=C double bond. This research provides an efficient and selective protocol for the synthesis of novel fluorescent self-healing materials that are difficult to synthesize by other methods, demonstrating the high potential of catalyst-controlled multicomponent copolymerization for the creation of novel functional polymers. Based on these findings, the present invention was completed.

[0023] <Copolymer> One aspect of the present invention relates to a copolymer (hereinafter, sometimes referred to as "copolymer of the present invention") having at least first and second units, which are at least two different repeating units derived from olefins, and a third unit, which is a repeating unit derived from at least one compound having at least one light-emitting group in a side chain.

[0024] (First Unit) The first unit constituting the copolymer of the present invention is a repeating unit derived from an olefin (more specifically, an olefin monomer). Here, repeating blocks of the first unit (preferably, only the first unit) are aggregated in the copolymer by intermolecular interactions to form hard segments. In the copolymer of the present invention, it is believed that such hard components act as crosslinking points, thereby exhibiting elastomeric properties and self-repairing properties. Furthermore, when breakage occurs, it is believed that the first units re-aggregate through intermolecular interactions, thereby exhibiting elastomeric properties and self-repairing properties.

[0025] The olefin monomer serving as a precursor of the first unit is not particularly limited as long as it exhibits the effects of the present invention, but is preferably a non-polar olefin monomer. The non-polar olefin monomer is not particularly limited as long as it is addition-polymerizable and copolymerizable with other raw material monomers of the copolymer of the present invention, and examples thereof include ethylene, α-olefins, substituted (substituents include, for example, alkyl groups, alkenyl groups, or alkynyl groups having 1 to 10 carbon atoms) and unsubstituted styrenes, dienes, and cyclic olefins having 3 to 20 carbon atoms (preferably, 6 to 12 carbon atoms) (including norbornenes such as 2-norbornene and dicyclopentadiene, and cyclohexadiene).

[0026] Specific examples of the α-olefin include linear α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene, and branched α-olefins having 4 to 20 carbon atoms, such as 4-methyl-1-pentene, 3-methyl-1-pentene, and 3-methyl-1-butene.

[0027] Examples of dienes include linear dienes having 3 to 20 carbon atoms such as 1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, and 2,4-hexadiene; branched dienes having 4 to 20 carbon atoms such as 2-methyl-1,3-butadiene, 2,4-dimethyl-1,3-pentadiene, and 2-methyl-1,3-hexadiene; and cyclic dienes having 4 to 20 carbon atoms such as cyclohexadiene.

[0028] The non-polar olefin monomer may be used alone or in combination of two or more kinds.

[0029] The non-polar olefin monomer is preferably, but not limited to, ethylene.

[0030] (Second Unit) The second unit constituting the copolymer of the present invention is a structural unit different from the first unit, and is a repeating unit derived from an olefin (specifically, an olefin monomer). Here, the second unit generates a flexible (soft) segment in the copolymer in which the first unit and the second unit are alternately repeated. In the copolymer of the present invention, such soft components disperse the hard components, and it is thought that the copolymer exhibits elastomeric properties and self-repairing properties when stress is applied or breakage occurs.

[0031] The olefin monomer that serves as the precursor of the second unit is not limited as long as it exhibits the effects of the present invention, but is preferably a polar olefin monomer.

[0032] The polar olefin monomer is a polar olefin monomer containing a polar group. The polar olefin monomer is not particularly limited as long as it is addition polymerizable and copolymerizable with other raw material monomers of the copolymer of the present invention. The polar olefin monomer is preferably a compound represented by the following general formula (II):

[0033]

[0034] In general formula (II), Z is a heteroatom selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, and selenium; R １ is a substituted or unsubstituted hydrocarbyl group having 1 to 30 carbon atoms, n is an integer of 1 or 2 depending on the atomic type of Z, and R ３ is a hydrocarbylene group having 1 to 5 carbon atoms, and R ４ is a halogen atom, a hydrocarbyl group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkylamino group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; R ４ When are hydrocarbyl groups, they may be linked to form a condensed ring; m is an integer of 0 to 4.

[0035] In the method for producing the copolymer of the present invention, it is believed that the heteroatom in the polar olefin monomer interacts with the central metal of the catalyst to form an intramolecular chelate, thereby promoting the interaction between the catalyst and the olefin unit, promoting the polymerization activity of the polar olefin monomer, and also exhibiting unique stereoselectivity.

[0036] R in the above general formula (II) １ is not limited as long as an intramolecular interaction is formed between the heteroatom in the polar group of the polar olefin monomer and the olefin unit and the central metal of the catalyst in the polymerization reaction. １is a substituted or unsubstituted hydrocarbyl group having 1 to 30 carbon atoms, preferably a linear, branched, or cyclic alkyl group, linear, branched alkenyl group, or linear, branched alkynyl group having 1 to 20, 1 to 10, or 1 to 6 carbon atoms; a cyclic alkyl group substituted with an alkyl, alkenyl, or alkynyl group having 1 to 10 carbon atoms (the number of alkyl, alkenyl, or alkynyl groups as substituents and the substitution positions on the cyclic alkyl group are not particularly limited); an aryl group having 6 to 10 carbon atoms; or an aryl group substituted with an alkyl, alkenyl, or alkynyl group having 1 to 10 carbon atoms (the number of alkyl, alkenyl, or alkynyl groups as substituents and the substitution positions on the aryl group are not particularly limited). Here, the cyclic alkyl group or aryl group may form a saturated or unsaturated fused ring.

[0037] The hydrocarbyl group in the substituted hydrocarbyl group is the same as the hydrocarbyl group described above. The substituted hydrocarbyl group is a hydrocarbyl group in which at least one hydrogen atom of the hydrocarbyl group has been substituted.

[0038] Z in the general formula (II) is preferably oxygen. １ is preferably a linear, branched or cyclic alkyl group having 1 to 3 carbon atoms. １ ) ｎ The bonding position of is not limited, but is preferably the o-position.

[0039] Usually, R ３ is a hydrocarbylene group having 1 to 5 carbon atoms. More preferred are linear or branched alkylene groups having 1 to 3 carbon atoms, and cyclic alkylene groups having 3 to 5 carbon atoms.

[0040] R is a substituent of the aromatic ring ４ is a halogen atom, a hydrocarbyl group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkylamino group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; R ４ When R is a hydrocarbyl group, they may be linked to form a saturated, unsaturated or hetero-fused ring. ４The substitution position of is not limited, but is preferably the m-position, where m is an integer of 0 to 4. More preferably, m is 0 to 2.

[0041] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. The hydrocarbyl group having 1 to 10 carbon atoms is preferably a linear or branched alkyl group, alkenyl group, or alkynyl group having 1 to 6 carbon atoms. The alkylthio group having 1 to 10 carbon atoms is more preferably an alkylthio group having 1 to 6 carbon atoms, such as a methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, n-pentylthio group, or n-hexylthio group. The alkylamino group having 1 to 10 carbon atoms is more preferably an alkylamino group having 1 to 6 carbon atoms. The alkylamino group is preferably a dialkylamino group, and the alkyls substituting the amino groups may be the same or different. More preferred alkylamino groups include dialkylamino groups such as dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, di-n-butylamino, diisobutylamino, di-sec-butylamino, and di-tert-butylamino. More preferred alkoxy groups having 1 to 10 carbon atoms are alkoxy groups having 1 to 3 carbon atoms. R ４ are bonded to each other, and R ４ Examples of the saturated fused ring formed by condensing R with the aromatic ring that it substitutes include a naphthalene ring. ４ are bonded to each other, and R ４ Examples of the hetero fused ring formed by condensing with the aromatic ring substituted by R include an indole ring, an isoindole ring, a quinoline ring, an isoquinoline ring, a carbazole ring, an acridine ring, a benzofuran ring, a benzopyran ring, and a benzothiophene ring. The fused ring may have 1 to 6 substituents, and the substituents may be any of the above-mentioned R １ is the same as:

[0042] Specific examples of the compound represented by general formula (II) include, but are not limited to, substituted 2-allylanisoles such as 2-allyl-4-fluoroanisole, 2-allyl-4,5-difluoroanisole, 2-allyl-4-methylanisole, 2-allyl-4-tert-butylanisole, 2-allyl-4-hexylanisole, 2-allyl-4-methoxyanisole, and 3-(2-methoxy-1-naphthyl)-1-propylene; and unsubstituted 2-allylanisole (3-(2-anisyl)-1-propylene) (hereinafter also referred to as "AP").

[0043] The polar olefin monomer may be used alone or in combination of two or more.

[0044] (Third Unit) The third unit constituting the copolymer of the present invention is a repeating unit derived from at least one compound having at least one luminescent group in its side chain. The third unit may be a luminescent unit and also constitute a hard segment in the copolymer. The third unit may be a unit that can aggregate through intermolecular interactions to form a hard segment in the copolymer. One characteristic of a third unit that can become a hard segment is that it contains multiple aromatic rings as luminescent groups in its molecule. This makes the third unit more likely to aggregate in the copolymer and become hard. In the copolymer of the present invention, the hard components formed by the aggregation of repeating blocks of the first unit, along with these hard components, function as crosslinking points, thereby exhibiting improved elastomeric properties and self-healing properties. Furthermore, in the event of fracture, it is believed that the first unit and, for example, the third unit functioning as a hard segment, re-aggregate through intermolecular interactions, thereby exhibiting elastomeric properties and self-healing properties.

[0045] The monomer that serves as the precursor of the third unit (hereinafter, sometimes referred to as a "luminescent monomer" or "fluorescent dye monomer") is addition-polymerizable, copolymerizable with other raw material monomers of the copolymer of the present invention, and is not limited as long as it exhibits luminescent activity in the copolymer, but is preferably a polymerizable compound having a polymerizable ethylene group, at least one type of luminescent group, and a linking group that links the polymerizable ethylene group and the at least one type of luminescent group.

[0046] The luminescent group is not particularly limited, and it is possible to use existing low molecular weight fluorescent compounds that have been used as luminescent materials in organic thin film EL devices. Examples of low molecular weight fluorescent compounds include, but are not limited to, pyrene and its derivatives, anthracene and its derivatives, triphenylene and its derivatives, fluorene and its derivatives, carbazole and its derivatives, dibenzothiophene and its derivatives, dibenzofuran and its derivatives, dibenzoquinoxaline and its derivatives, quinoxaline and its derivatives, pyridine and its derivatives, pyrimidine and its derivatives, phenanthrene and its derivatives, and naphthalene and its derivatives. In particular, pyrene and its derivatives are preferred because of their high luminescence quantum yield. Specific examples of the pyrene derivative include N,N'-bis(3-methylphenyl)-N,N'-bis[3-(9-phenyl-9H-fluoren-9-yl)phenyl]pyrene-1,6-diamine (abbreviation: 1,6mMemFLPAPrn), N,N'-diphenyl-N,N'-bis[4-(9-phenyl-9H-fluoren-9-yl)phenyl]pyrene-1,6-diamine (abbreviation: 1,6FLPAPrn), N,N'-bis(dibenzofuran-2-yl)-N,N'-diphenylpyrene-1,6-diamine (abbreviation: 1,6FrAPrn), N,N'-bis(dibenzothiophen-2-yl)-N, Examples thereof include N'-diphenylpyrene-1,6-diamine (abbreviation: 1,6ThAPrn), N,N'-(pyrene-1,6-diyl)bis[(N-phenylbenzo[b]naphtho[1,2-d]furan)-6-amine] (abbreviation: 1,6BnfAPrn), N,N'-(pyrene-1,6-diyl)bis[(N-phenylbenzo[b]naphtho[1,2-d]furan)-8-amine] (abbreviation: 1,6BnfAPrn-02), and N,N'-(pyrene-1,6-diyl)bis[(6,N-diphenylbenzo[b]naphtho[1,2-d]furan)-8-amine] (abbreviation: 1,6BnfAPrn-03).

[0047] The linking group linking the polymerizable ethylene group and the at least one kind of light-emitting group is not particularly limited as long as it does not affect the polymerizability and can link the polymerizable ethylene group and the light-emitting group, and may be, for example, a substituted or unsubstituted hydrocarbylene group having 1 to 30 carbon atoms, and preferably a divalent saturated or unsaturated aliphatic hydrocarbon group (specifically, for example, a linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 6 carbon atoms, a linear, branched alkenylene group, or a linear, branched alkynylene group), a divalent aromatic hydrocarbon group aromatic ring residue (specifically, for example, an arylene group having 6 to 10 carbon atoms), a divalent heterocyclic hydrocarbon group heterocyclic residue (specifically, for example, a heteroarylene group having 2 to 10 carbon atoms, a cyclic heteroalkylene group having 2 to 9 carbon atoms), and a divalent group selected from the group consisting of a combination thereof. Preferred examples include a combination of a linear, branched, or cyclic alkylene group having 1 to 6 carbon atoms, or a linear or branched alkenylene group having 2 to 6 carbon atoms, with an arylene group having 6 to 10 carbon atoms. Examples of the substituent include an alkyl group, alkenyl group, or alkynyl group having 1 to 10 carbon atoms, and the number and positions of the alkyl group, alkenyl group, or alkynyl group that is the substituent are not particularly limited.

[0048] As will be described later, when the linking group has a double bond that is not involved in polymerization, cycloaddition between third units in the copolymer can be induced by irradiating the copolymer with light (photoinduced cycloaddition).

[0049] The light-emitting monomer that serves as a precursor of the third unit is preferably a compound represented by the following general formula (I).

[0050]

[0051] Specific examples of the compound represented by general formula (I) include, but are not limited to, 4-[2-(1-pyrenyl)ethenyl]styrene.

[0052] The light-emitting monomer may be used alone or in combination of two or more kinds.

[0053] The polar olefin monomer, non-polar olefin monomer, and luminescent monomer may be synthesized by a conventional method in the field of organic chemistry, or may be commercially available.

[0054] (Composition and Properties of Copolymer) The proportion of the first unit in the copolymer of the present invention, as the proportion of the first unit to all structural units in the copolymer, is not limited, but may be, for example, in molar ratio, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, or 80 mol% or more, or may be less than 100 mol%, 80 mol% or less, 70 mol% or less, or 60 mol% or less, or any compatible combination thereof. In addition, the molar ratio may be, for example, 30 to less than 100 mol%.

[0055] The proportion of the second units in the copolymer of the present invention, as the proportion of the second units relative to all structural units in the copolymer, is not limited, but may be, for example, in molar ratio, 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, or 70 mol% or more, or 60 mol% or less, 50 mol% or less, 40 mol% or less, or 30 mol% or less, or any compatible combination thereof. The molar ratio may be, for example, 20 to 60 mol% or less.

[0056] Here, the molar ratio of the first unit to the second unit in the copolymer (first unit / second unit) is not limited, and may be, for example, greater than 1, 1 or greater, 1.1 or greater, 1.2 or greater, or 1.3 or greater, or less than 2, 1.9 or less, 1.8 or less, 1.7 or less, 1.6 or less, 1.5 or less, or 1.4 or less, or any combination thereof that is not contradictory. In addition, the molar ratio may be, for example, greater than 1 and less than 2.

[0057] The proportion of the third unit in the copolymer of the present invention, as the proportion of the third unit relative to all structural units in the copolymer, is not limited, but may be, for example, in molar ratio, 0.01 mol% or more, 0.1 mol% or more, 0.2 mol% or more, 0.3 mol% or more, 0.5 mol% or more, or 1 mol% or more, or 10 mol% or less, 5 mol% or less, 2 mol% or less, or 1 mol% or less, or any compatible combination thereof. The molar ratio may be, for example, 0.01 to 10 mol% or less.

[0058] The molecular weight distribution of the polymer may be any, but polymers with a relatively narrow molecular weight distribution can also be preferably used. Here, the molecular weight distribution may be a value (Mw / Mn) measured by a GPC method (measured at 140°C using polystyrene as a standard substance and 1,2-dichlorobenzene as an eluent), and can be measured using, for example, a GPC measurement device (TOSOH HLC 8321 GPC / HT). The molecular weight distribution of the polymer is usually expressed as an index, Mw / Mn, of 5.0 or less, preferably 4.0 or less, 3.0 or less, or 2.0 or less.

[0059] The number-average molecular weight of the copolymer is arbitrary, but copolymers having a relatively high number-average molecular weight can also be preferably used. The number-average molecular weight (kg / mol) varies depending on the structure of the repeating units, the ratio of each repeating unit, etc., but from the viewpoint of achieving properties such as high mechanical properties and autonomous self-repairing action, it may usually be 30 or more, 40 or more, 50 or more, 60 or more, 70 or more, 80 or more, 90 or more, 100 or more, 150 or more, or 200 or more.

[0060] The glass transition point (Tg) of the copolymer can vary depending on the structure of the structural units derived from the polar olefin monomer. The glass transition point is not particularly limited, but is usually about -40 to 100°C. The glass transition point can be measured by differential scanning calorimetry (DSC) or the like. In order to obtain a self-repairing molded product, the Tg of the copolymer used as a raw material is preferably room temperature (generally 25°C, but may vary depending on the mode and conditions of use) or lower.

[0061] When the copolymer has a melting point, it may be usually 100° C. or higher, preferably 110° C. or higher, 120° C. or higher, or 130° C. or higher, although it may vary depending on the structure of the repeating units, the ratio of each repeating unit, etc. The melting point can be measured, for example, by differential scanning calorimetry (DSC).

[0062] Photophysical properties of copolymers, such as absorption and emission maximum wavelengths, emission quantum yield (Φ f ) and luminescence lifetime (τ f ) can be measured by known measurement methods. For example, the absorption / emission maximum wavelength and the emission quantum yield can be measured using an emission quantum yield measurement device or the like, using a sample in which the copolymer is dissolved in a solvent or a solid sample. ｆ ) can be measured using a luminescence lifetime measurement device, using a sample in which the copolymer is dissolved in a solvent or a solid sample.

[0063] Luminescence quantum yield (Φ f ) can be changed depending on the structure of the repeating unit (particularly, the light-emitting unit), the ratio of each repeating unit (particularly, the light-emitting unit), the concentration of the copolymer, the type of solvent, etc., and is not particularly limited, but is, for example, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more.

[0064] As an embodiment of the copolymer, a copolymer of the polar olefin monomer, ethylene (a non-polar olefin monomer), and 4-[2-(1-pyrenyl)ethenyl]styrene (a light-emitting monomer) will be described as an example. The copolymer has a structural unit derived from the polar olefin monomer represented by the following formula (A), a structural unit derived from ethylene represented by the following formula (B), and a structural unit derived from 4-[2-(1-pyrenyl)ethenyl]styrene represented by the following formula (C).

[0065] Here, Z and R in formula (A) １ , n is Z, R as defined above in the general formula (II). １ , n. ２ is the moiety of the following formula in general formula (II):

[0066]

[0067]

[0068] In the copolymer, the structural units represented by the above formula (A) and formula (B) may be arranged in any order. That is, they may be arranged randomly, or may be arranged with some regularity (for example, the structural units (A) and (B) are arranged alternately, are arranged in a certain degree of continuity, or are arranged in some other fixed order). Therefore, the copolymer portion of the structural units represented by formula (A) and formula (B) may be a random copolymer, an alternating copolymer, a block copolymer, or other ordered copolymer. The copolymer portion is preferably an alternating copolymer.

[0069] Here, the alternating copolymer has a main sequence in which structural units (A) and (B) are alternately arranged (hereinafter also referred to as an "alternating (A)-(B) sequence" or "(A)-alt-(B) sequence"), but may contain a subsequence in which two or more of each structural unit are arranged consecutively to a certain extent. Preferably, the copolymer portion is an alternating copolymer, and the proportion of the alternating (A)-(B) sequence in the entire sequence of the copolymer (when the copolymer contains structural units of two or more polar olefin monomers and structural units of two or more non-polar olefin monomers, the proportion of the alternating sequences consisting of structural units of polar olefin monomers and structural units of non-polar olefin monomers) in terms of molar ratio is usually 30 mol% or more, preferably 40 mol% or more, 50 mol% or more, 60 mol% or more, or 70 mol% or more.

[0070] More specifically, in the alternating polymer embodiment, the alternating sequence -(A)-alt-(B)- may be present along with the polymerization sequence of each of (A) and (B), and the inclusion of the polymerization sequence -(B)-(B)- of (B) along with the alternating sequence -(A)-alt-(B)- is believed to contribute to the expression of functionality of the molded article of the present invention, as described below. The proportion of the polymerization sequence -(B)-(B)- of (B) (including random copolymers, alternating copolymers, block copolymers, and other ordered copolymers composed of structural units of two or more non-polar olefin monomers when structural units of two or more non-polar olefin monomers are contained) in the total sequence of the copolymer, in terms of molar ratio, is usually 60 mol% or less, preferably 50 mol% or less, 40 mol% or less, 30 mol% or less, or 20 mol% or less. The proportion of the polymerization sequence (A) -(A)-(A)- (when the copolymer contains structural units of two or more polar olefin monomers, this includes random copolymers, alternating copolymers, block copolymers, and other ordered copolymers composed of structural units of two or more polar olefin monomers) in the entire copolymer sequence is, in terms of molar ratio, preferably 20 mol % or less, 10 mol % or less, 5 mol % or less, or 3 mol % or less, and may even be 0 mol %.

[0071] Furthermore, the inclusion of the structural unit represented by formula (C) in the copolymer is believed to contribute to the development of functionality in the molded article of the present invention, as described below. In the copolymer, the structural unit represented by formula (C) may be arranged in any order relative to the structural units represented by formulas (A) and (B). The proportion of the (C) unit in the entire sequence of the copolymer, in terms of molar ratio, is usually 2 mol% or less, preferably 1 mol% or less, or 0.5 mol% or less.

[0072] The luminescence quantum yield (Φ) of the copolymer having the structural units represented by formula (A), formula (B), and formula (C) fThe luminescence (e.g., fluorescence) content can be varied depending on the ratio of repeating units (especially, luminescent units), the concentration of the copolymer, the type of solvent, etc., and is not particularly limited, but is, for example, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more. The maximum excitation wavelength of the copolymer can be varied depending on the ratio of repeating units (especially, luminescent units), the concentration of the copolymer, the type of solvent, etc., and is not particularly limited, but is, for example, 320 to 425 nm. The maximum emission (e.g., fluorescence) wavelength can also be varied depending on the ratio of repeating units (especially, luminescent units), the concentration of the copolymer, the type of solvent, etc., and is not particularly limited, but is, for example, 370 to 550 nm.

[0073] The proportion of the sequence can be, for example, １ H-NMR, １３ It can be measured by C-NMR or the like. １ It can be determined by comparing the integral ratio of the peaks at 1.0-1.5 ppm by H-NMR.

[0074] The content of the structural units of formula (A) and the structural units of formula (B) contained in the copolymer may be any desired content. For example, the molar ratio of the structural units of formula (A) among all structural units can be 1 to 99 mol%. Furthermore, the above-described production method can also produce a copolymer having a relatively high proportion of polar olefin structural units. Here, in the molded article of the present invention, by having a sufficiently high proportion of structural units of formula (A), the copolymer contained in the molded article can have a sufficiently high proportion of alternating (A)-(B) arrangement, which is believed to result in properties such as autonomous self-repairing action and excellent mechanical properties. Due to these copolymer properties, the molded article of the present invention is believed to have autonomous self-repairing action and higher toughness. Furthermore, it can be said that this mechanical property, such as high toughness, is a well-balanced combination of sufficiently high tensile strength and sufficiently high elongation at break. From the viewpoint of achieving the above-mentioned high mechanical properties, autonomous self-repairing action, and other properties, the proportion of polar olefin structural units in the copolymer contains the structural unit of formula (A) in molar ratio, usually 20 mol% or more, preferably 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, and, for example, 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less. The proportion of the structural units is, for example, １ H-NMR, １３ It can be measured by C-NMR or the like. １ This can be determined by comparing the integral ratio of the methylene or methyl hydrogen adjacent to the heteroatom to the hydrocarbon at 1-1.8 ppm using H-NMR. The proportion of this structural unit is controlled by adjusting the ratio of each monomer used as a raw material in the production of the copolymer. Furthermore, increasing the content of the structural unit of formula (A) can effectively exhibit the adhesiveness and compatibility with polar materials, which are characteristics of the polar group of the polar olefin monomer. Furthermore, since the copolymer can be made to have a high molecular weight, the number of entanglement points increases, which is advantageous in that improved compatibility and adhesiveness can be expected.

[0075] One embodiment of the copolymer according to the present invention contains structural units represented by the following formulas (III), (IV), and (V), respectively: In the formulas, a, b, and c represent the proportion (molar ratio) of each structural unit in the entire sequence of the copolymer.

[0076]

[0077] In the formula, R １ , R ３ , R ４ , Z, m, and n have the same meanings as in formula (II), and the preferred ranges are also the same. a, b, and c represent the proportions of each structural unit and are positive numbers satisfying a > 0, b > 0, c > 0, b > a > c, and 80% ≦ a + b < 100%. a + b is preferably 85% or more, 90% or more, 95% or more, or 97% or more.

[0078] <Method for Producing Copolymer> Hereinafter, a method for producing the copolymer of the present invention will be described.

[0079] (Catalyst composition) The copolymer of the present invention can be obtained by polymerizing the monomers that are the raw materials for the first, second, and third units using a catalyst composition containing, for example, a metallocene complex and an ionic compound. Known monomers other than the monomers that are the raw materials for the first, second, and third units may also be copolymerized.

[0080] (Metallocene Complex) The metallocene complex is not limited to, but examples thereof include the scandium complex (C5Me4SiMe3)Sc(CH2C6H4NMe2-o)2 described in the Examples.

[0081] Metallocene complexes can be prepared using the methods described above, such as (1) X. Li, M. Nishiura, K. Mori, T. Mashiko, Z. Hou, Chem. Commun. 4137-4139 (2007), (2) M. Nishiura, J. Baldamus, T. Shima, K. Mori, Z. Hou, Chem. Eur. J. 17, 5033-5044 (2011)., (3) F. Guo, M. Nishiura, H. Koshino, Z. Hou, Macromolecules. 44, 6335-6344 (2011)., (4) References: Tardif, O.; Nishiura, M.; Hou, ZM Organometallics 22, 1171, (2003)., (5) References: Hultzsch, KC; Spaniol, TP; Okuda, J. Angew. Chem. Int. Ed., 38, 227, (1999). (6) Reference: International Publication No. WO2006 / 004068 pamphlet, (7) Reference: Japanese Patent Publication No. 2008-222780, and (8) Reference: Japanese Patent Publication No. 2008-095008.

[0082] (Ionic Compound) When combined with the metallocene complex, the ionic compound allows the metallocene complex to exhibit activity as a polymerization catalyst. The mechanism of this is thought to be that the ionic compound reacts with the metallocene complex to generate a cationic complex (active species).

[0083] The ionic compound contained in the catalyst composition is not limited, but examples thereof include a combination of non-coordinating anions and cations. Preferred examples include triphenylcarbonium tetrakis(pentafluorophenyl)borate, triphenylcarbonium tetrakis(tetrafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, and 1,1'-dimethylferrocenium tetrakis(pentafluorophenyl)borate. One type of ionic compound may be used, or two or more types may be used in combination.

[0084] Among these ionic compounds, particularly preferred is triphenylcarbonium tetrakis(pentafluorophenyl)borate.

[0085] In the catalyst composition, the molar ratio of the ionic compound to the metallocene complex varies depending on the type of the complex and the ionic compound, and can be appropriately set. For example, the molar ratio is set to 1 / 2 when the ionic compound is composed of a carbonium cation and a boron anion (e.g., [Ph ３ C] [B(C ６ F ５ ) ４ ]), the ratio is preferably 0.5 to 1 relative to the central metal of the metallocene complex, and in the case of an alkylaluminum compound such as methylaluminoxane, the ratio is preferably about 10 to 4000 relative to the central metal of the metallocene complex. The ionic compound is thought to ionize, i.e., cationize, the metallocene complex to form a catalytically active species, and within the above-mentioned ratio range, the metallocene complex can be sufficiently activated, and the ionic compound consisting of a carbonium cation and a boron anion does not become excessive, reducing the risk of an undesired reaction with the monomer to be polymerized.

[0086] (Method for Producing a Copolymer of the Present Invention) The above catalyst composition can be used as a polymerization catalyst composition to polymerize (addition polymerize) monomers that serve as raw materials for the first, second, and third units to produce a copolymer. For example, the polymerization catalyst composition can be used by 1) providing a composition containing each constituent component (such as a metallocene complex and an ionic compound) in a polymerization reaction system, or 2) providing each constituent component separately in a polymerization reaction system and forming a composition in the reaction system. In the above 1), "providing as a composition" includes providing a metallocene complex (active species) that has been activated by reaction with an ionic compound.

[0087] Specifically, the method for producing a copolymer can be carried out, for example, by the following procedure. 1. Polymerizable monomers are supplied to a system (preferably in a liquid phase) containing the catalyst composition used in the method for producing a copolymer, and polymerized. If the monomer is a liquid, it can be supplied by dropping it, and if it is a gas, it can be supplied through a gas pipe (by bubbling, etc., in a liquid phase reaction system). 2. Polymerization is carried out by adding the catalyst composition used in the method for producing a copolymer to a system (preferably in a liquid phase) containing the polymerizable monomer, or by adding the components of the catalyst composition separately. The catalyst composition to be added may be prepared in advance (preferably in a liquid phase) and activated (in this case, it is preferable to add it so as not to come into contact with the outside air).

[0088] The production method may be any method such as gas phase polymerization, solution polymerization, suspension polymerization, liquid phase bulk polymerization, emulsion polymerization, or solid phase polymerization. When using solution polymerization, the solvent used is not particularly limited as long as it is inert to the polymerization reaction, can dissolve the monomer and catalyst, and does not interact with the catalyst. Examples include saturated aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; saturated alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene and toluene; and halogenated hydrocarbons such as methylene chloride, chlorobenzene, bromobenzene, and chlorotoluene. A solvent that is not toxic to living organisms is preferred. Specifically, aromatic hydrocarbons, particularly toluene, are preferred. One solvent may be used alone, or a mixed solvent of two or more solvents may be used. The amount of solvent used is optional. For example, when the concentration of the complex contained in the polymerization catalyst is 1.0 × 10 －５ ~1.0 x 10 －１ It is preferable that the amount is 100 mol / L.

[0089] The amount of the monomer to be subjected to the polymerization reaction can be appropriately set depending on the copolymer to be produced. For example, the amount of the monomer is preferably 50 times or more, 100 times or more, 200 times or more, or 500 times or more by molar ratio relative to the metallocene complex constituting the polymerization catalyst composition.

[0090] When polymerization is carried out by solution polymerization, the polymerization temperature can be any temperature, for example, in the range of −90 to 100° C. The temperature can be appropriately selected depending on the type of monomer to be polymerized, and is usually around room temperature, i.e., about 25° C. The polymerization time is about several seconds to several days and can be appropriately selected depending on the type of monomer to be polymerized. It may be 1 hour or less, or in some cases 1 minute or less. However, these reaction conditions can be appropriately selected depending on the polymerization reaction temperature, the type and molar amount of monomer, the type and amount of catalyst composition, and the like, and are not limited to the ranges exemplified above.

[0091] In addition, in the mode of producing a copolymer, 1) if it is a random copolymer or an alternating copolymer, it can be produced by polymerizing a mixture of two or more types of monomers in the presence of a catalyst composition, and 2) if it is a block copolymer, it can be produced by supplying each monomer in turn to a reaction system containing a catalyst composition.

[0092] In addition, after the polymerization step, for example, a purification step, R in the polar group １ It is also possible to carry out an optional step such as a step of introducing a polar group, such as a step of elimination of the above.

[0093] <Molded Article> The molded article of the present invention is a molded article containing at least one copolymer of the present invention. One embodiment of the molded article is a self-healing molded article or a self-healing luminescent molded article. One embodiment of the molded article of the present invention has a hard component formed by the aggregation of ethylene-ethylene sequences and 4-[2-(1-pyrenyl)ethenyl]styrene through intermolecular interactions, and a soft component formed by alternating ethylene-(substituted)anisylpropylene sequences, and has autonomous self-healing properties and excellent mechanical properties. The mechanism behind the autonomous self-healing properties and excellent mechanical properties is thought to be that the copolymer of the present invention has a phase-separated region in which phases formed by aggregation of ethylene-ethylene sequences and 4-[2-(1-pyrenyl)ethenyl]styrene are separated from a phase formed by flexible alternating ethylene-(substituted)anisylpropylene sequences. This may have enhanced molecular entanglement between damaged surfaces and between polymer chains, without being seriously affected by water, seawater, acids, or bases. In one embodiment of the molded article of the present invention, self-repair (i.e., autonomous self-repair) is possible not only in air but also in water, seawater, acid, or alkaline solution without the need for external energy or stimuli (pressure, temperature, etc.). The self-repairing action of the molded article of the present invention does not particularly require external energy or stimuli (pressure, temperature, etc.), but these can also be applied. Applying external energy or stimuli (pressure, temperature, etc.) is thought to have advantages such as an improved self-repair rate.

[0094] Here, "self-repair" refers to the process whereby damage such as scratches or cut surfaces on a molded article or the like is brought into contact with each other, causing copolymer chains to intertwine again, restoring the shape, physical properties, etc. of the molded article, etc., before the damage. The self-repair effect can be confirmed, for example, by bringing the damaged areas into contact, leaving them at a predetermined temperature under a predetermined environment for a predetermined time, and comparing the shape, physical properties, etc. after the damage with those before the damage. Specifically, it can be confirmed, for example, by the method described in the Examples below. The self-repair efficiency of the molded article of the present invention varies depending on the type of copolymer used, etc., and is not limited. For example, in a self-repair property test measured by the method described in the Examples below, damage on a molded article is brought into contact with the damaged area and left in air at room temperature (e.g., 25°C), and the molded article autonomously self-repairs, and the breaking elongation 24 hours after the damage is usually 50% or more, preferably 60% or more, 70% or more, 80% or more, 90% or more, 95% or more, 99% or more, or 100% of the breaking elongation before the damage.

[0095] One embodiment of the self-repairing molded article is a molded article containing a copolymer having structural units represented by the formulas (III), (IV), and (V), respectively, and whose Tg is equal to or lower than the use temperature (for example, when the use temperature is room temperature, generally 25°C). In one embodiment of the molded article of the present invention used as a self-repairing material, a self-repair rate of 80% or more can be achieved. The time required to achieve the self-repair rate is not particularly limited, and can be adjusted by the type of copolymer used (more specifically, in an embodiment including a copolymer having structural units represented by the formulas (III), (IV), and (V), respectively, the type of substituent on the benzene ring in formula (III), the range of a and b, and the molecular weight). In one example, a self-repair rate of 80% or more can be achieved in 24 hours.

[0096] One embodiment of the molded article of the present invention is a (luminescent) molded article having a luminescent effect. Here, the term "luminescent effect" means a property of emitting light when the molded article is irradiated with light having a wavelength near the excitation wavelength of the luminescent unit contained in the copolymer of the present invention, and the luminescent unit is excited and changes to the ground state.

[0097] The luminescence effect can be confirmed, for example, by irradiating the molded article with light at a predetermined temperature and then measuring the luminescence. Specifically, it can be confirmed, for example, by the method described in the Examples below. The maximum luminescence wavelength and luminescence quantum yield of the molded article of the present invention vary depending on the type of copolymer used, and are not limited. For example, in the luminescence quantum yield measurement measured by the method described in the Examples below, when the molded article is irradiated with light and measured at room temperature (e.g., 25°C), the luminescence quantum yield is usually 40% or more, preferably 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, 95% or more, or 99% or more.

[0098] One embodiment of the luminescent molded article is a molded article containing a copolymer having structural units represented by the formulas (III), (IV), and (V), respectively, and whose Tg is equal to or lower than the use temperature (e.g., generally 25°C when the use temperature is room temperature). In one embodiment of the molded article of the present invention used as a luminescent material, a luminescence quantum yield of 80% or more can be achieved. The luminescence quantum yield is not particularly limited and can be adjusted by the type of copolymer used (more specifically, in embodiments including copolymers having structural units represented by the formulas (III), (IV), and (V), respectively, the range of c and molecular weight), concentration, type of luminescent group, etc. In one example, a luminescence quantum yield of 80% or more can be achieved. Furthermore, the maximum emission (e.g., fluorescence) wavelength can also be changed by the type of copolymer used (more specifically, in embodiments including copolymers having structural units represented by the formulas (III), (IV), and (V), respectively, the range of c and molecular weight), concentration, type of luminescent group, etc., and is not particularly limited, but is, for example, 370 to 550 nm.

[0099] One embodiment of the molded article of the present invention is a luminescent molded article with variable luminescence properties. By including a double bond that is not involved in polymerization in the linking group of the luminescent unit contained in the copolymer of the present invention, cycloaddition of the carbon-carbon double bond of the luminescent unit in the copolymer proceeds upon light irradiation of the copolymer, thereby making it possible to shift the maximum excitation wavelength and / or maximum emission wavelength. Furthermore, ring cleavage (reversible change) can be achieved by irradiating the copolymer with light near the excitation wavelength of the cyclized luminescent unit. In this embodiment, the molded article of the present invention functions as a molded article with information recording properties. One example is a copolymer in which the third unit is derived from a polymerizable compound having a polymerizable ethylene group, at least one luminescent group, and a linking group connecting the polymerizable ethylene group and the at least one luminescent group, the linking group containing at least one double bond not involved in polymerization, and when irradiated with light of a predetermined wavelength λ1, a cyclization reaction between the at least one double bond not involved in polymerization proceeds, thereby shifting the maximum excitation wavelength and / or maximum emission wavelength, and when irradiated with light of a predetermined wavelength λ2 (λ2 > λ1), the ring formed by the cyclization reaction is cleaved. This example can be used as an information recording material.

[0100] The copolymers of the present invention contained in the molded articles of the present invention have a wide glass transition temperature range and exhibit a variety of mechanical properties (hard plastic, soft plastic, elastomer, and stress-softening material) at room temperature (e.g., 25°C) depending on the glass transition temperature. For example, as described in the Examples below, P4 to P7, which have glass transition temperatures of 2.3 to 6.8°C, are elastomers at room temperature (Table 1). These elastomers exhibit excellent mechanical properties, particularly excellent toughness, tensile strength, and elongation at break.

[0101] The toughness value of the molded article varies depending on the type of copolymer used (more specifically, in an embodiment including a copolymer having structural units represented by the above formulas (III), (IV), and (V), the type of substituent on the benzene ring in formula (III), the ranges of a and b, and the molecular weight), and is not limited. It can be adjusted to an appropriate range depending on the application. When a polar olefin copolymer with a large molecular weight (Mn) is used as a raw material, the toughness value of the obtained molded article tends to be high. For example, the molded article of the present invention has a toughness of typically 0.25 MJ / m when measured at a temperature above the glass transition temperature at which the copolymer exhibits a rubbery state (for example, at room temperature (e.g., 25°C)). ３ Exceeding 0.5MJ / m ３ In order to obtain a self-repairing molded product, it is preferable to use a pressure of 1 MJ / m ３ Above, 5MJ / m ３ Above, 10MJ / m ３ Above, 20MJ / m ３ or more, or 30 MJ / m ３ The toughness may be in the above range not only at room temperature but also at the temperature at which the molded article is used.

[0102] The tensile strength of the molded article is not limited and varies depending on the type of copolymer used (more specifically, in embodiments including copolymers having structural units represented by the above formulas (III), (IV), and (V), the type of substituent on the benzene ring in formula (III), the range of a and b, and the molecular weight). It can be adjusted to an appropriate range depending on the application. The tensile strength of the molded article tends to be high when a copolymer with a high glass transition point is used as the raw material. For example, the molded article of the present invention can achieve a tensile strength of about 0.1 MPa or more when measured at a temperature above the glass transition temperature at which the copolymer exhibits a rubbery state (e.g., room temperature (e.g., 25°C)). The tensile strength is preferably greater than 0.4 MPa, 0.5 MPa or more, 1 MPa or more, 2 MPa or more, 3 MPa or more, 4 MPa or more, 5 MPa or more, 6 MPa or more, or 7 MPa or more. The tensile strength may be in the above range not only at room temperature but also at the temperature at which the molded article is used.

[0103] The breaking elongation of the molded article varies depending on the type of copolymer used (more specifically, in an embodiment including a copolymer having structural units represented by the above formulas (III), (IV), and (V), the type of substituent on the benzene ring in formula (III), the range of a and b, and the molecular weight), and is not limited. It can be adjusted to an appropriate range depending on the application. When a copolymer with a high glass transition point is used as a raw material, the breaking elongation of the molded article tends to be small. For example, the molded article of the present invention can achieve a breaking elongation of about 10% or more when measured at a temperature above the glass transition temperature at which the copolymer exhibits a rubbery state (for example, room temperature (e.g., 25°C)). In order to obtain a self-repairing molded article, preferably, it is more than 100%, 500% or more, 1000% or more, 1200% or more, 1500% or more, or 2000% or more. In order to stably obtain self-repairing properties, the upper limit is about 10,000%. Note that the breaking elongation may be in the above range not only at room temperature, but also at the temperature at which the molded article is used.

[0104] The mechanical properties of the molded article of the present invention can be measured by a conventional tensile test. Specifically, for example, a dumbbell-shaped test piece (width: 2 mm; length: 12 mm; thickness: 1 mm) based on the method described in the Examples below (JIS K-6251-7) is used, and the test method is performed according to ASTM 882-09. The breaking stress-breaking strain test is determined by breaking using a uniaxial tensile test at a strain rate of 200 mm / min. The toughness value can be calculated by calculating the area under the stress-strain curve.

[0105] The molded article of the present invention may be a molded article containing the copolymer of the present invention as a major component (50% by mass or more) or as a minor component (less than 50% by mass). The molded article of the present invention may be composed solely of the copolymer of the present invention, or may contain polymeric materials such as (co)polymers other than the copolymer of the present invention, as well as various additives commonly used in molded articles, such as excipients, lubricants, UV absorbers, weathering agents, antistatic agents, antioxidants, heat stabilizers, nucleating agents, flow improvers, colorants, etc.

[0106] The molded article of the present invention is preferably one obtained by melt molding the copolymer of the present invention. Melt molding can be carried out by a known method. Such melt molded articles are not limited to, but include, for example, injection molded articles, vacuum molded articles, pressure molded articles, extrusion molded articles, blow molded articles, hot press (melt press) molded articles, and cast molded articles, and specific examples thereof include pellets, fibers and cloths, films, sheets, nonwoven fabrics, and the like. In addition, molded articles can also be produced using laser processing, 3D printer technology, and the like.

[0107] (Film) The present invention also relates to a film containing the copolymer of the present invention. One embodiment of the film is a transparent film, a self-repairing film, or a self-repairing luminescent film. The film, which is the molded product of the present invention, can be molded by a known method. For example, molding techniques such as extrusion molding, heat press molding, and cast molding can be used. In the case of extrusion molding, a molten film material can be extruded using an extruder equipped with a T-die, a circular die, or the like, and can be molded by further stretching and heat treatment as desired. In the case of heat press molding, a molten film material can be pressed using a hot plate press, cooled, and can be molded by further stretching and heat treatment as desired.

[0108] Alternatively, the film material may be dissolved in a cosolvent, cast, dried, and solidified to form an unstretched film, which may then be stretched and heat-treated as desired.

[0109] The formed unstretched film can be used as it is. Alternatively, a material obtained by melt-kneading the copolymer of the present invention and the various additives described above can be used as the film material, or the film can be formed by melt-kneading the copolymer and the various additives.

[0110] An unstretched film can be uniaxially stretched longitudinally in the mechanical flow direction or uniaxially stretched transversely in the direction perpendicular to the mechanical flow direction. Alternatively, a biaxially stretched film can be produced by stretching the film using a sequential biaxial stretching method involving roll stretching and tenter stretching, a simultaneous biaxial stretching method involving tenter stretching, or a biaxial stretching method involving tubular stretching. Furthermore, the film can be generally heat-set after stretching to suppress heat shrinkage, etc. The obtained film may be subjected to a surface activation treatment or the like by a known method, if desired. After being formed into a long film, it may be stored and transported in a rolled state.

[0111] The film of the present invention may be used as a molded article as it is, or may be used in combination with other types of films, etc. Examples of combinations include combinations with other types of films, such as laminates and stacks, or combinations with other molded articles by coating or the like.

[0112] The present invention also relates to a device having a layer containing at least one copolymer of the present invention. One embodiment of the device is a light-emitting device or an information recording (or sometimes referred to as "information storage") device. In one embodiment, the layer containing at least one copolymer of the present invention functions as at least one of a light-emitting layer and a recording layer in the device.

[0113] (Light-emitting device) Examples of light-emitting devices include, but are not limited to, organic EL display devices, organic EL lighting, etc. In one embodiment, the present invention is a light-emitting device comprising a first electrode, a second electrode, and at least one light-emitting layer between the first electrode and the second electrode, wherein the at least one light-emitting layer comprises at least one copolymer of the present invention as a light-emitting material.

[0114] The light-emitting layer is a layer that serves as a main light source when the copolymer of the present invention, which is a light-emitting material, is excited by recombination of holes injected from the anode and electrons injected from the cathode between electrodes (anode and cathode) to which an electric field is applied, and is used as the light-emitting material. There are no particular limitations on the excipients, additives, film thickness, etc. that are used in combination, as long as light can be emitted. A light-emitting device can be produced according to a conventional method, except for using the copolymer of the present invention.

[0115] (Information Recording Device) Information recording devices include, but are not limited to, optical discs, and specific examples thereof include rewritable (writable) optical discs (CDs, DVDs, Blu-ray discs, etc.) on which a recording layer is laminated by a known method. In one embodiment, the present invention is an information recording device comprising a substrate and, on the substrate, at least one information recording layer and a light-reflecting layer, wherein the at least one information recording layer comprises at least one copolymer of the present invention as an information recording material. The information recording layer is a layer in which the copolymer of the present invention, which serves as the information recording material, is excited, undergoes a phase change, or changes to its ground state upon irradiation with laser light, thereby optically changing with recording and readout laser light to record information. As long as information can be recorded, the excipients, additives, film thickness, etc. used are not particularly limited. The information recording device can be manufactured according to conventional methods, except for using the copolymer of the present invention.

[0116] The present invention will be specifically described below with reference to examples, but these are merely examples of the present invention and the scope of the present invention is not limited to these examples.

[0117] Terpolymerization of ethylene (E), anisylpropylene (AP), and 4-[2-(1-pyrenyl)ethenyl]styrene (Pyr) with a half-sandwich scandium catalyst. First, we investigated the two-component copolymerization of each pair of three olefin monomers, ethylene (E), 3-(o-anisyl)propylene (AP), and 4-[2-(1-pyrenyl)ethenyl]styrene (Pyr), using scandium catalyst 1 (Table 1) cocatalyzed with [PhC][B(CF)]. Similar to previous observations, copolymerization of 200 equivalents of anisylpropylene (AP, per Sc) and ethylene (E, 1 atm) at room temperature for 5 min selectively afforded the corresponding copolymer with an AP / E molar ratio of 34.4 / 65.6 (Table 1, run 1). Copolymerization of ethylene (E, 1 atm) and 4-[2-(1-pyrenyl)ethenyl]styrene (Pyr, 100 equivalents per Sc) gave an insoluble polymer product within 1 min, but quenching the reaction with MEOH within 10 s gave a copolymer with an E / Pyr molar ratio of 84.5 / 15.5 (soluble in hot toluene) (Table 1, run 2). Copolymerization of AP (200 equivalents per Sc) and Pyr (100 equivalents per Sc) was very slow, yielding only trace amounts (<5% yield) of polymer product within 48 h (Table 1, run 3). In the coexistence of E (1 atm), AP (200 equivalents per Sc), and Pyr (50 equivalents per Sc), terpolymerization occurred smoothly, producing a monomodal GPC curve (M n = 76 kD, M w / M n A terpolymer product (P1) was obtained with a comonomer ratio of AP / E / Pyr = 31.9 / 67.6 / 0.5 (Table 1, run 4). Increasing the Pyr feed from [AP] / [Pyr] / [1] = 200 / 50 / 1 to 200 / 100 / 1 resulted in a terpolymer (P2) with a higher Pyr content (0.9 mol% for P2 vs. 0.5 mol% for P1) (Table 1, run 5). Increasing the polymerization time from 5 to 6 minutes resulted in a terpolymer with an even higher Pyr content (3.1 mol%) but a very broad molecular weight distribution (M w / M nA terpolymer (P3) with a molecular weight of 6.1 (AP) was formed (Table 1, run 6). In this case, the AP monomer was almost completely consumed (conversion > 96%). Increasing the AP feed from [AP] / [Pyr] / [1] = 200 / 50 / 1 to 500 / 50 / 1 and 1000 / 50 / 1 increased the molecular weight (M n The AP content increased from 76 kD (P1) to 112 kD (P4) and 172 kD (P6), and the Pyr content decreased from 0.5 mol% to 0.2 mol% and 0.1 mol% (Table 1, runs 4, 7, and 9). Similarly, increasing the AP feed from [AP] / [Pyr] / [1] = 200 / 100 / 1 to 500 / 100 / 1 and 1000 / 100 / 1 increased the molecular weight of the polymer (M n ) increased from 61 kD (P2) to 147 kD (P5) and 218 kD (P7), and the AP content increased from 35.1 mol% to 38.5 mol% and 42.4 mol%, respectively, with a concomitant decrease in Pyr content from 0.9 mol% to 0.5 mol% and 0.3 mol% (Table 1, runs 5, 8, and 10).

[0118]

[0119] Table 1. Scandium-catalyzed terpolymerization of ethylene (E), anisylpropylene (AP), and 4-[2-(1-pyrenyl)ethenyl]styrene (Pyr) a a Conditions: [1] = [Ph3C][B(C6F5)4] = 0.01 mmol, ethylene (1 atm), toluene 25 mL. b Weight of the resulting terpolymer. c The AP conversion was calculated by (AP in the terpolymer) / (input AP), and the Pyr conversion was calculated by (Pyr in the terpolymer) / (input Pyr). d1 Identified by H NMR analysis. e Determined by gel permeation chromatography (GPC) against polystyrene standards in tetrahydrofuran at 40°C or in o-dichlorobenzene at 140°C. f Identified by differential scanning calorimetry (DSC). gThe quantum yield Φ was measured in CHCl3 under an argon atmosphere using quinine sulfate in 1N H2SO4 as a standard. h no = not observed. i No ethylene. j Conditions: [Sc] = [Ph3C][B(C6F5)4] = 0.05 mmol, ethylene (1 atm), toluene 125 mL. k Conditions: [Sc] = [Ph3C][B(C6F5)4] = 0.03 mmol, ethylene (1 atm), toluene 75 mL.

[0120] The microstructure of terpolymers P1 to P7 was investigated by NMR analysis ( 1 H, 13 The compounds were carefully characterized by various methods (C, DEPT135, H-H COSY, HSQC, HMBC, and HETCOR). 1 H and 13 C 1 The H NMR spectra of the Pyr monomer are shown in Figures 1A and 1B, respectively. 1 The H NMR spectrum is shown in Figure 1C. It shows that P5 is mainly composed of alternating sequences of E-alt-AP (63.0 mol%) and AP-EE (22.2 mol%), with small amounts of AP-EE-E (4.8 mol%) and AP-(E) n (n = 4.5 on average) (7.2 mol%) and AP-AP sequences (2.3 mol%), as well as independent Pyr units (0.5 mol%).

[0121] Absorption and Fluorescence Properties of E-AP-Pyr Terpolymers. The UV-Vis absorption and fluorescence properties of the terpolymers (P1–P7) were investigated in THF solution and solid state (thin film). The UV-Vis absorption spectrum of P5 (0.25 mg / mL) in THF at room temperature showed strong absorption in the range of 320–425 nm, with a maximum peak at 381 nm (Figure 2A). The fluorescence spectrum of P5 in THF was concentration-dependent. Under UV irradiation (350 nm), a THF solution of P5 at a concentration of 0.25 mg / mL exhibited strong blue emission in the range of 400–550 nm, with peak maxima at 418 and 442 nm (Figure 2B). Increasing the concentration to 10 mg / mL resulted in a significant red shift, with the emission maximum appearing at 471 nm. The maximum fluorescence peak of a film sample (1 mm thick) further red-shifted to 510 nm and emitted strong green light (Figures 2B and 2C). These results suggest that even when the Pyr content in the terpolymer is very low (0.5 mol%), π-π stacking interactions between the Pyr units in P5 should exist in both solution and the solid state.

[0122] All terpolymers P1–P7 exhibited high fluorescence quantum yields (up to 87%) in chloroform (Table 1). The polymer with a higher Pyr content (P3) exhibited a relatively low fluorescence quantum yield (69%), likely due to a higher probability of aggregation of Pyr units in the polymer, leading to fluorescence quenching. However, P5 in the solid state (film) exhibited a high fluorescence quantum yield of 40%, which is significantly higher than the previously reported fluorescence quantum yield of a pyrene-crosslinked polyamide film (14%).

[0123] Mechanical and self-healing properties of E-AP-Pyr terpolymers The mechanical properties of the terpolymers were strongly affected by the molecular weight (Fig. 3). The relatively low molecular weight terpolymers P1 and P2 (M n = 61 kD and 76 kD) behave like a viscoelastic stress-softening material, while M nP4–P7, with molecular weights ranging from 112 to 218 kD, exhibited typical elastomer characteristics (Figures 3A and 3B). The higher the molecular weight, the higher the tensile strength, reaching as high as 7.7 megapascals (MPa) for P7. Furthermore, all terpolymers exhibited excellent self-healing properties. For example, when a dumbbell-shaped film sample of P5 (sample size: 1 mm thick, 2 mm wide, and 12 mm long at the center) was cut into two pieces and then glued together at room temperature, complete healing was achieved within 24 hours (Figure 3C). The repaired sample exhibited a high tensile strength of 4.0 MPa and an elongation at break of 1270%. It is also noteworthy that this terpolymer exhibited a significantly faster self-healing rate compared to a similar ethylene (E)-anisylpropylene (AP) binary copolymer with similar molecular weight and tensile strength. For example, M n = 90 to 173 (M w / M n Two-component E-AP copolymers with a pH of 1.58–1.94 and tensile strengths of 3.1–4.6 MPa required more than 5 days to achieve complete self-healing at room temperature after mechanical damage, whereas this terpolymer required only less than 1 day to reach a similar tensile strength. When a film sample of P5 was scratched with a razor blade in air at room temperature, the scratch disappeared in 20 seconds (Figure 3E). Even more surprisingly, this terpolymer was able to efficiently self-heal against mechanical damage not only in air but also in water, seawater, acidic (1 M HCl), and alkaline (1 M NaOH) environments (Figure 3D), demonstrating its potential for practical applications in a wide variety of real-world environments.

[0124] Transmission electron microscopy (TEM) images of ultrathin films of P5 showed nanoscale multiphase morphology, confirming the formation of nanodomains (Figure 3F). Similar to the case of E-AP binary copolymers, this E-AP-Pyr terpolymer may also form a 3D network structure through multiphase separation of nanodomains of crystalline E-E segments and Pyr aggregates from a highly flexible E-alt-AP segment matrix (Figure 4). Therefore, the exceptional elasticity of the terpolymer may be attributed to the formation of a nanoscale 3D network. Upon mechanical damage, the E-alt-AP segments, E-E segments, and Pyr units rapidly reaggregate, leading to the reconstruction of the network structure and repair of the damage. Apparently, the Pyr component not only served as an efficient fluorophore but also played an important role in network formation and enhanced polymer mobility, resulting in even faster self-healing compared to similar E-AP copolymers.

[0125] Photoinduced Cycloaddition of P5 and Information Storage by Photolithography. When a THF solution of terpolymer P5 (0.25 mg / mL) was irradiated at 405 nm, the UV-Vis spectrum showed a gradual decrease in the absorption peak at 381 nm and a simultaneous increase in the absorption peak at 336 nm, suggesting the dimerization of Pyr units in P5 (cycloaddition of the styrenyl C=C bond) (Figures 5A and 5B). Consistent with the observed changes in the UV-Vis spectrum, the fluorescence emission at 418 and 442 nm of the THF solution of P5 weakened, and a new emission peak at 378 nm appeared and gradually increased (Figure 5C). When the resulting solution was again irradiated at 365 nm, both the UV-Vis and fluorescence spectra recovered, suggesting that the photoinduced cycloaddition of P5 was somewhat reversible (Figures 5A, 5D, and 5E).

[0126] When a film sample of P5 was irradiated at 405 nm for 5 minutes, the resulting film, P5', exhibited slightly dimmer (blue-shifted compared to P5) fluorescence under a UV lamp (Figure 6A, center). Immersing P5' in toluene released a very thin, insoluble film, P5A, while the rest of the film dissolved in the solvent. This insoluble thin film exhibited blue-shifted emission compared to P5 (Figure 6A, bottom left). Evaporation of the toluene solvent yielded a pale yellow solid, P5B, whose color was nearly identical to P5 in both daylight and UV lamp light (Figure 6A, bottom right).

[0127] The P5' film was also stretchable and highly self-healing, although its elongation at break was slightly shorter than that of the original P5 sample (Figures 6B, 6C, and 6D). The mechanical and self-healing properties of the toluene-soluble portion P5B were nearly identical to those of the original P5 sample (Figure 6B).

[0128] The above observations suggest that irradiation of P5 film at 405 nm may have induced crosslinking at the sample surface through cycloaddition of Pyr units, resulting in a toluene-insoluble thin film, P5A, while the sample below (or further from) the surface may have remained largely unchanged. Based on these results, we further investigated the possibility of information storage in polymers by photolithography. Covering a P5 film with a photomask bearing a 2D floral pattern and irradiating it at 405 nm for 5 minutes resulted in a successful printing of the floral pattern onto the film. The resulting image was indistinguishable under daylight but clearly recognizable under a UV lamp (Figure 7A), demonstrating the possibility of information encryption. Surprisingly, the floral-printed film still possessed high elasticity and self-healing properties. When two pieces of a fully cut sample were glued together, spontaneous self-healing occurred rapidly in air at room temperature. The repaired sample could be stretched to more than 500% of its original length after 2 hours and subsequently returned to its original shape upon release of the force (Figure 7B).

[0129] Thus, in accordance with the present invention, a tough, fluorescent, self-healing material has been developed.

[0130] The fluorescent self-healing material of the present invention can be used for, but is not limited to, materials, surface coating materials, devices, parts, products, etc. in various industries (e.g., medical, construction, transportation, electronics, electricity, etc.), and is particularly suitable for use in fields where damage is difficult to detect or repair is expensive or impossible, such as devices on the seabed and devices, medical materials, and devices in outer space.

Claims

1. A copolymer comprising: first and second units that are repeating units derived from olefins and are at least two different repeating units from each other; and a third unit that is a repeating unit derived from at least one compound having at least one light-emitting group in a side chain.

2. The copolymer according to claim 1, comprising: a soft segment in which the first unit and the second unit alternately repeat; and a hard segment in which blocks in which the first unit repeats aggregate.

3. The copolymer according to claim 1, wherein the third unit is derived from a polymerizable compound having: a polymerizable ethylene group; at least one light-emitting group; and a linking group that links between the polymerizable ethylene group and the at least one light-emitting group.

4. The copolymer according to claim 3, wherein the linking group contains at least one double bond that does not participate in polymerization, and upon irradiation with light having a predetermined wavelength λ1, a cyclization reaction between at least one double bond that does not participate in polymerization proceeds, whereby the maximum excitation wavelength and / or the maximum emission wavelength is shifted, and upon irradiation with a predetermined wavelength λ2 (λ2> λ1), the ring formed by the cyclization reaction cleaves.

5. The copolymer according to claim 1, wherein the first unit is derived from a nonpolar olefin and the second unit is derived from a polar olefin.

6. The copolymer according to claim 1, wherein the second unit is derived from a compound represented by the following formula (II). (In the formula, Z is a heteroatom selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, and selenium, and R １ is a substituted or unsubstituted hydrocarbyl group having 1 to 30 carbon atoms, n is an integer of 1 or 2 according to the atomic species of Z, and R ３ is a hydrocarbylene group having 1 to 5 carbon atoms, R ４ is a halogen atom, a hydrocarbyl group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkylamino group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. When R ４ is a hydrocarbyl group, they may be bonded to form a condensed ring, and m is an integer of 0 to 4.) 7. The copolymer according to claim 1, wherein the molar ratio (first unit / second unit) of the first unit and the second unit in the copolymer is more than 1 and less than 2.

8. The copolymer according to claim 1, wherein the molar ratio of the third unit to all structural units in the copolymer is less than 2 mol%.

9. A molded article comprising the copolymer according to any one of claims 1 to 8.

10. The molded article according to claim 9, which is a film.

11. A device having a layer containing the copolymer according to any one of claims 1 to 8.

12. The device according to claim 11, wherein the layer functions as at least one of a light-emitting layer and a recording layer.

13. At least one copolymer comprising at least a first unit and a second unit which are repeating units derived from olefins and are at least two different repeating units from each other, and a third unit which is a repeating unit derived from at least one compound having at least one light-emitting group in a side chain, and further comprising a soft segment in which the first unit and the second unit alternate in repetition, and a hard segment in which blocks of the first unit in repetition aggregate, and in the copolymer, having at least a phase separation region in which a phase formed by the hard segment and a phase formed by aggregation of the third unit are separated from a phase formed by the soft segment. The molded article according to claim 9.

14. At least one copolymer comprising at least a first unit and a second unit which are repeating units derived from olefins and are at least two different repeating units from each other, and a third unit which is a repeating unit derived from at least one compound having at least one light-emitting group in a side chain, and further comprising a soft segment in which the first unit and the second unit alternate in repetition, and a hard segment in which blocks of the first unit in repetition aggregate, and in the copolymer, having at least a phase separation region in which a phase formed by the hard segment and a phase formed by aggregation of the third unit are separated from a phase formed by the soft segment. The device according to claim 11.

Images