Novel monomer and chemically recyclable polymer material comprising same

Abstract

The present invention comprises a novel monomer formed by binding of a pentagonal ring-structured olefin molecule and a photosensitive molecule, and thus can provide new functionality and control mechanical properties and thermal properties, and provides a novel monomer formed by binding of chemical formula 1 and any one of chemical formulas 2-4 in order to enable chemical recycling through a reversible chemical change in response to an external stimulus.

Description

Novel monomer and chemically recyclable polymer material containing the same

[0001] The present invention relates to a novel monomer and a polymer material containing the same, wherein the polymer material has controllable physical properties and can be chemically recycled.

[0002] Polymer materials are substances composed of very large molecular chains, possessing a structure in which multiple small molecules called monomers are repeatedly connected. The types of repeatedly connected structures include linear structures, where molecules are connected in a single line; branched structures, where chains branch out from a main chain; and network structures, where polymers are connected like a net by crossing each other in various directions.

[0003] Among these, polymer materials with damage detection and self-repair capabilities are a special type of polymer that can restore itself in response to external physical damage or thermal and chemical stress. Since these polymer materials can automatically repair damaged areas, they can extend material lifespan and reduce maintenance costs. Polymer materials with damage detection and self-repair functions are attracting significant interest in fields such as aerospace, automotive, and electronics.

[0004] However, polymer materials with damage detection and self-repair functions are frequently exposed to external impacts or damage, and due to the varying degrees of impact or damage, they are difficult to use semi-permanently, which can lead to an increase in waste plastics. Polymer materials with damage detection and self-repair functions that have been studied previously are manufactured by injecting a substance capable of expressing functionality in the form of capsules or channels; however, in this case, the physical properties of the material itself may be significantly degraded, and it is difficult to respond to repeated damage in the same area. The prior art US 2023-0365743 A1 discloses condensed ring monomers as polymers that can be chemically recycled, but it does not disclose new monomers with damage detection and self-repair functions.

[0005] Recently, there have been cases of realizing polymer materials with damage detection and self-repair capabilities using dynamic covalent bonding; however, due to the nature of requiring the introduction of different functional molecules, there is a problem involving complex synthesis and manufacturing methods. Accordingly, there is an emphasis on the need for new polymer materials that can be used semi-permanently and possess damage detection and self-repair capabilities through chemical recycling without complex synthesis and manufacturing processes.

[0006] The objective of the present invention is to provide a novel monomer formed by the combination of a pentagonal ring olefin molecule and a photosensitive molecule, and a polymer material having a novel functionality comprising the novel monomer.

[0007] Another objective of the present invention is to provide a polymer material comprising a novel monomer capable of controlling mechanical and thermal properties.

[0008] Another objective of the present invention is to provide a polymer material comprising a novel monomer that is chemically recyclable through a reversible chemical change in response to an external stimulus.

[0009] To achieve the above-mentioned purpose, a novel monomer formed by the combination of the following chemical formula 1 and any one of the following chemical formulas 2 to 4 is provided.

[0010] [Chemical Formula 1]

[0011] C5H4R1R2

[0012] Here, the above chemical formula 1 is cyclic, R1 is a hydroxyl group, a carboxyl group, an amine group, chlorine (Cl), bromine (Br), or iodine (I), and R2 is a hydroxyl group or hydrogen.

[0013] [Chemical Formula 2]

[0014] C 13 H9R3

[0015] Here, R3 is a carboxyl group, an isocyanate group, a halogen group, a methyl halide group, an amine group, a hydroxymethyl group, a boronic acid group, an aldehyde group, a phenylmethanimine group, or an ethylene group, and the halogen element is chlorine, bromine, or iodine.

[0016] [Chemical Formula 3]

[0017] C6H3R4R5R6C2H2Y

[0018] Here, R4 is hydrogen, a methoxy group, an acetoxy group, a trifluoromethyl group, a methylseleno group, a hydroxyl group, bromine, chlorine, or an amine group, R5 is a hydroxyl group or hydrogen, R6 is a methoxy group or hydrogen, and Y is a carboxyl group, an acyl chloride, or chlorine.

[0019] [Chemical Formula 4]

[0020] C6H2R7R8C3HR9O2

[0021] Here, R7 is a hydroxyl group, amine group, bromine, or chlorine, R8 is hydrogen, methoxy group, acetyl group, methyl group, hydroxyl group, or chlorine, and R9 is a trifluoromethyl group, methyl group, or hydrogen.

[0022] The effects of the present invention obtained through the above-described solution are as follows.

[0023] The novel monomer provided in the present invention is in a form combined with a pentagonal ring olefin molecule and a photosensitive molecule having fluorescent properties, and can provide a novel monomer having new functionality different from the physical properties of the pentagonal ring olefin molecule.

[0024] In addition, the polymer material provided in the present invention can be copolymerized by controlling the content of a novel monomer, which is a combined form of a pentagonal ring olefin molecule and a photosensitive molecule, and a cyclopentene derivative, thereby allowing for easy control of mechanical and thermal properties.

[0025] In addition, the polymer material provided in the present invention can be reversibly depolymerized through external stimuli such as heat or mechanical stress to return to its original molecular structure, and the polymer material has damage detection and self-repair functions, allowing it to be chemically recycled.

[0026] FIGS. 1a and 1b are conceptual diagrams showing the structure of cyclopentene and anthracene, which are one example of the novel monomers provided in the present invention, bonded by substituents, and polymerization and depolymerization under specific conditions.

[0027] FIG. 2 is a conceptual diagram showing the formation of a polymer material, the depolymerization of a polymer material, and the characteristics of a polymer material provided by the present invention.

[0028] Figure 3 is a figure showing the process of manufacturing a polymer material in the form of a film according to an embodiment provided in the present invention.

[0029] Figure 4 is a figure showing the process of forming a polymer film that is chemically cross-linked by ultraviolet light transmission from a polymer material prepared according to an example.

[0030] FIGS. 5a to 5c show the heat flow, storage modulus, and tangent as a function of temperature from the difference in copolymerization ratio of polymer materials prepared according to the examples. This is a graph showing the change of.

[0031] Figures 6a and 6b are graphs showing ultraviolet absorption and fluorescence characteristics according to wavelength from the difference in copolymerization ratio of polymer materials prepared according to the example.

[0032] FIGS. 7a to 7c show the storage modulus and tangent as a function of temperature derived from the difference in copolymerization ratio of a chemically cross-linked polymer network composed of a polymer material prepared according to the example. This is a graph showing the change of.

[0033] Figure 8 is a graph for verifying the photodimerization efficiency of a chemically cross-linked polymer network prepared according to an example.

[0034] Figure 9 is a graph for verifying the photodimerization efficiency of chemically crosslinked polymer networks with different copolymerization ratios prepared according to the example.

[0035] FIGS. 10a to 10c are graphs for determining the hardness and mechanical properties of polymer materials with different copolymerization ratios and chemically crosslinked polymer networks prepared according to the examples.

[0036] Figures 11a and 11b are photographs showing the self-repair ability of polymer materials with different copolymerization ratios prepared according to the example in response to external stimulation.

[0037] FIGS. 12a and FIGS. 12b are figures showing the dual-shape memory properties of a polymer material prepared according to an example.

[0038] Figure 13 is a figure showing the recycling process through depolymerization of a polymer material manufactured according to an example.

[0039] Hereinafter, a novel monomer related to the present invention and a chemically recyclable polymer material containing the same will be described in more detail with reference to the drawings.

[0040] In this specification, identical or similar reference numbers are assigned to identical or similar components even in different embodiments, and redundant descriptions thereof are omitted.

[0041] In describing the embodiments disclosed in this specification, if it is determined that a detailed description of related prior art could obscure the essence of the embodiments disclosed in this specification, such detailed description is omitted.

[0042] The attached drawings are intended only to facilitate understanding of the embodiments disclosed in this specification, and the technical concept disclosed in this specification is not limited by the attached drawings; it should be understood that all modifications, equivalents, and substitutions included within the concept and technical scope of the present invention are included.

[0043] In the following description, singular expressions include plural expressions unless the context clearly indicates otherwise.

[0044] In this application, terms such as “comprising” or “having” are intended to specify the existence of the features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, and should be understood as not precluding the existence or addition of one or more other features, numbers, steps, actions, components, parts, or combinations thereof.

[0045] Hereinafter, a chemically recyclable polymer material proposed in the present invention will be described.

[0046] The novel monomer can be formed by combining the following chemical formula 1 and any one of the following chemical formulas 2 to 4.

[0047] [Chemical Formula 1]

[0048] C5H4R1R2

[0049] Here, the above chemical formula 1 is cyclic, R1 is a hydroxyl group, a carboxyl group, an amine group, chlorine (Cl), bromine (Br), or iodine (I), and R2 is a hydroxyl group or hydrogen.

[0050] Chemical formula 1 may be a form having one or two substituents on cyclopentene, a pentagonal ring-shaped olefin molecule.

[0051] [Chemical Formula 2]

[0052] C 13 H9R3

[0053] Here, R3 is a carboxyl group, an isocyanate group, a halogen group, a methyl halide group, an amine group, a hydroxymethyl group, a boronic acid group, an aldehyde group, a phenylmethanimine group, or an ethylene group, and the halogen element is chlorine, bromine, or iodine.

[0054] Chemical formula 2 may be a form having one substituent on anthracene.

[0055] [Chemical Formula 3]

[0056] C6H3R4R5R6C2H2Y

[0057] Here, R4 is hydrogen, a methoxy group, an acetoxy group, a trifluoromethyl group, a methylseleno group, a hydroxyl group, bromine, chlorine, or an amine group, R5 is a hydroxyl group or hydrogen, R6 is a methoxy group or hydrogen, and Y is a carboxyl group, an acyl chloride, or chlorine.

[0058] Chemical formula 3 may be a form having 1 to 3 substituents on cinnamic acid, or a form in which the carboxyl group of cinnamic acid with 1 to 3 substituents attached is substituted with acyl chloride or chlorine.

[0059] [Chemical Formula 4]

[0060] C6H2R7R8C3HR9O2

[0061] Here, R7 is a hydroxyl group, amine group, bromine, or chlorine, R8 is hydrogen, methoxy group, acetyl group, methyl group, hydroxyl group, or chlorine, and R9 is a trifluoromethyl group, methyl group, or hydrogen.

[0062] Chemical formula 4 may be a form having 1 to 3 substituents on coumarin.

[0063] Here, Chemical Formula 1 can be represented by any one of the following Chemical Formulas 1-1 to 1-5.

[0064]

[0065] Meanwhile, Chemical Formula 2 can be represented by any one of the following Chemical Formulas 2-1 to 2-10.

[0066]

[0067] In addition, Chemical Formula 3 can be represented by any one of the following Chemical Formulas 3-1 to 3-14.

[0068]

[0069] Also, the following chemical formula 4 can be represented by any one of the following chemical formulas 4-1 to 4-11.

[0070]

[0071] The novel monomer provided in the present invention can be formed as any one of the following chemical formulas 5-1 to 5-20 through the combination of any one of chemical formulas 1-1 to 1-5, which is a substituent form of cyclopentene, and any one of chemical formulas 2-1 to 2-10, which is a substituent form of anthracene.

[0072]

[0073]

[0074] Among the above chemical formulas 5, chemical formulas 5-1 to 5-4 may include chemical formula 1-1 as part of the monomer, and chemical formulas 5-5 to 5-8 may include chemical formula 1-2 as part of the monomer. In addition, chemical formulas 5-8 to 5-11 may include chemical formula 1-3 as part of the monomer, and chemical formulas 5-1 and 5-4 may include chemical formula 1-4 as part of the monomer. Furthermore, chemical formulas 5-12 to 5-20 may include chemical formula 1-5 as part of the monomer.

[0075] In addition, the novel monomer provided in the present invention may be formed as any one of the following chemical formulas 6-1 to 6-65 through the combination of any one of chemical formulas 1-1 to 1-5, which is a substituent form of cyclopentene, and any one of chemical formulas 3-1 to 3-14, which is a substituent form of cinnamic acid.

[0076]

[0077]

[0078]

[0079] The above chemical formulas 6-1 to 6-39 correspond to chemical formulas formed by combining any one of chemical formulas 1-1 and 1-5, which have a hydroxyl group (-OH) as a substituent in chemical formula 1, and any one of chemical formulas 3-1 to 3-13, which have a carboxyl group (-COOH) or an acyl chloride group as a substituent in chemical formula 3.

[0080]

[0081]

[0082] The above chemical formulas 6-40 to 6-55 correspond to chemical formulas formed by combining any one of chemical formulas 1-2 and 1-5, which have a carboxyl group (-COOH) or a halogen group as a substituent in chemical formula 1, with any one of chemical formulas 3-3, 3-4, 3-5, 3-9, 3-11, 3-12, and 3-14, which have a hydroxyl group (-OH) as a substituent in chemical formula 3.

[0083]

[0084]

[0085] The above chemical formulas 6-56 to 6-64 correspond to chemical formulas formed by combining either one of chemical formulas 1-1 and 1-5, which have a hydroxyl (-OH) group as a substituent in chemical formula 1, and any one of chemical formulas 3-6 to 3-8, which have bromine or chlorine among the halogen groups as a substituent in chemical formula 3.

[0086]

[0087] The above chemical formula 6-65 corresponds to the chemical formula represented by the combination of chemical formula 1-2, which has a carboxyl group (-COOH) as a substituent in chemical formula 1, and chemical formula 3-10, which has an amine group (-NH2) as a substituent in chemical formula 3.

[0088] In addition, the novel monomer provided in the present invention may be formed as any one of the following chemical formulas 7-1 to 7-27 through the combination of any one of chemical formulas 1-1 to 1-5, which is a substituent form of cyclopentene, and any one of chemical formulas 4-1 to 4-11, which is a substituent form of coumarin.

[0089]

[0090]

[0091] The above chemical formulas 7-1 to 7-18 correspond to chemical formulas formed by combining any one of chemical formulas 1-2 and 1-4, which have a carboxyl group (-COOH) or a halogen group as a substituent in chemical formula 1, with any one of chemical formulas 5-1 to 5-7, which have a hydroxyl group (-OH) as a substituent in chemical formula 5.

[0092]

[0093] The above chemical formulas 7-19 to 7-21 correspond to chemical formulas formed by combining any one of chemical formula 1-2, which has a carboxyl group (-COOH) as a substituent in chemical formula 1, and chemical formulas 5-8 to 5-10, which have an amine group (-NH2) as a substituent in chemical formula 5.

[0094]

[0095]

[0096] The above chemical formulas 7-22 to 7-27 correspond to chemical formulas formed by combining either one of chemical formulas 1-1 and 1-5, which have a hydroxyl group (-OH) as a substituent in chemical formula 1, and either one of chemical formulas 5-5 and 5-11, which have bromine or chlorine among the halogen groups as a substituent in chemical formula 5.

[0097] The ring strain of the novel monomer provided in the present invention may be greater than 2 kcal / mol and less than 8 kcal / mol.

[0098] FIGS. 1a and 1b are conceptual diagrams showing the structure of cyclopentene and anthracene, which are one example of the novel monomers provided in the present invention, bonded by substituents, and polymerization and depolymerization under specific conditions.

[0099] Referring to FIG. 1a, cyclopentene can undergo ring-open metathesis polymerization and ring-closed metathesis depolymerization under specific catalytic conditions, and cyclopentene can control polymerization and depolymerization depending on the reaction temperature. In order for a novel monomer formed by combining Formula 1, which is cyclopentene having a substituent, with any one of Formulas 2 to 4 to be polymerized into a polymer material, or for the polymerized polymer material to be reversibly depolymerized, the ring strain of the novel monomer must be greater than 2 kcal / mol and less than 8 kcal / mol.

[0100] If the ring strain value is greater than 8 kcal / mol, depolymerization of the polymer material is difficult and chemical recycling is not possible, and if the ring strain value is less than 2 kcal / mol, the structure of the cyclopentene ring is very stable and it is difficult to form the polymer material.

[0101] Referring to FIG. 1b, it can be confirmed that anthracene, which corresponds to a component of one embodiment of the novel monomers provided in the present invention, is dimerized at a specific wavelength, and that the anthracene dimer returns to its original structure by mechanical force, heat, or a specific wavelength. The molecule capable of attaching to the substituent position of cyclopentene in the polymer material must be a photosensitive molecule; in order to attach to the substituent, the molecule in its original state must possess optical properties, such as having a specific color or fluorescence properties, prior to the formation of cross-linking bonds. Furthermore, the molecule capable of attaching to the substituent position of cyclopentene must be a molecule that loses its original optical properties by forming covalent bonds and changing into a dimer form when irradiated with light of a specific wavelength. Additionally, the molecule must be able to exhibit optical properties when the covalent bonds within the dimer form are broken by mechanical force, or possess a self-repair function when the covalent bonds within the molecule are broken by heat treatment or light of a different wavelength. Formulas 2 to 4 in the present invention can satisfy the conditions of a molecule that can be attached to a substituent position of cyclopentene.

[0102] The polymer material proposed in the present invention is a chemically recyclable material and may include a novel monomer formed by the combination of Chemical Formula 1 and any one of Chemical Formulas 2 to 4.

[0103] More specifically, the polymer material proposed in the present invention may include a novel monomer formed by combining any one of formulas 1-1 to 1-5 and any one of formulas 2-1 to 2-10, formulas 3-1 to 3-14, or formulas 4-1 to 4-11.

[0104] In this case, the polymer material containing the novel monomer can be formed by homopolymerization of the novel monomer or copolymerization between the novel monomer and a cyclopentene derivative. Here, the substituents in the cyclopentene derivative are not limited, and any derivative of cyclopentene can be used as long as conditions allow for copolymerization between the novel monomer and the cyclopentene derivative.

[0105] FIG. 2 is a conceptual diagram showing the formation of a polymer material, the depolymerization of a polymer material, and the characteristics of a polymer material provided by the present invention.

[0106] Referring to FIG. 2, the polymer material provided in the present invention is based on a novel monomer formed by the bonding of a pentagonal ring-shaped olefin molecule and a photosensitive molecule, and can form various linear polymers through copolymerization with other cyclopentene derivatives, and the polymer material can control mechanical and thermal properties depending on the copolymerization ratio.

[0107] Here, the polymer material can form supramolecular polymer networks with enhanced thermal and mechanical properties through interactions between photosensitive molecules located laterally. These supramolecular polymer networks form reversible covalent bonds upon photosensitization and convert into chemically cross-linked polymer networks, which can exhibit enhanced properties. Furthermore, by locally irradiating the chemically cross-linked polymer networks with a specific wavelength, it is possible to realize shape memory properties capable of fixing the shape locally based on the enhanced properties.

[0108] The cross-linked structure within a chemically cross-linked polymer network can be broken by physical force through the destruction of covalent bonds, and the fluorescent properties of photosensitive molecules can be re-expressed at the exposed sites resulting from the destruction of covalent bonds, thereby exhibiting damage detection and self-repair properties. Furthermore, the polymer material proposed in this invention can be easily depolymerized when heated to a temperature above the ceiling temperature under catalytic conditions, allowing for conversion back to the original monomer; additionally, the polymer material allows for selective depolymerization, enabling the recovery of only specific monomers.

[0109] In the polymer material provided in the present invention, the molar ratio of the novel monomer within the polymer material may be 1 mol% or more. This means that the polymer material comprises a novel monomer and a cyclopentene derivative, wherein the molar ratio of the novel monomer is 1 mol% or more. If the molar ratio of the novel monomer within the polymer material is less than 1 mol%, it is difficult to exhibit the damage detection and self-repair functions of the polymer material.

[0110] Hereinafter, the novel monomer proposed in the present invention and the polymer material containing the novel monomer will be described in more detail with reference to the examples and drawings.

[0111] [Example 1]

[0112] Anth-CP(M A,0 ) and Grubbs 2 nd 8.4 mg of generation catalyst (I0) is added to the flask and purged with argon. Subsequently, 0.1 ml of anhydrous chloroform is injected to uniformly dissolve the monomer and catalyst. Immediately thereafter, Ethyl-CP(M E,0) is additionally injected, and the contents are stirred for 24 hours at a temperature between approximately 0-5°C. Next, 0.2 ml of ethyl vinyl ether is added, and stirring is maintained for 1 hour to deactivate the catalyst; subsequently, chloroform is added to dilute the reaction solution. The diluted solution is passed through a basic activated aluminum oxide column to remove the inactivated catalyst, after which the solution is condensed to an appropriate amount. Subsequently, unreacted monomers are removed by precipitating them in an excess amount of dimethyl ether or methanol, and the finally obtained polymer is dried under reduced pressure and redissolved for use.

[0113] Figure 3 is a figure showing the process of manufacturing a polymer material in the form of a film according to an embodiment provided in the present invention.

[0114] Referring to Fig. 3, the synthesized anthracene-containing cyclopentene derivative (Anth-CP) and ethyl-3-cyclopente-1-carboxylate (Ethyl-CP) can be prepared into various copolymers of the ExAy type as shown in Table 1 below by varying the mixing ratios. The polymer material obtained through precipitation is dissolved in a solvent, and then subjected to a casting process to slowly evaporate the solvent, thereby obtaining a free-standing film due to the π-π interactions of the anthracene molecules. Here, x and y represent the binding ratio of ethyl-CP and anth-CP.

[0115]

[0116] Here, a) and b) are the number of moles of Ethyl-CP(E) and Anth-CP(A), respectively, added at reaction time t=0, and c) represents the ratio of the number of moles of monomer to the number of moles of catalyst.

[0117] [Example 2]

[0118] After placing the polymer film formed in Example 1 onto a Teflon film, the polymer films, ExAy, are maintained for approximately 15 minutes using a heating plate at a temperature 30 degrees higher than their respective glass transition temperatures. Subsequently, the ExAy are subjected to approximately 0.4 W / cm² using a UV lamp having a single long wavelength (365 nm). 2 It is irradiated with ultraviolet rays for 15 minutes at an intensity.

[0119] Figure 4 is a figure showing the process of forming a polymer film that is chemically cross-linked by ultraviolet light transmission from a polymer material prepared according to an example.

[0120] Referring to Fig. 4, when a polymer film having a supramolecular polymer network structure (ExAy) is irradiated with ultraviolet light of a long wavelength greater than 300 nm under inert gas conditions, new covalent bonds are formed between two anthracene molecules, and the polymer film can be transformed into a polymer film with a chemically cross-linked polymer network (c-ExAy), and polymers with different compositions can all be prepared in the same way.

[0121] FIGS. 5a to 5c show the heat flow, storage modulus, and tangent as a function of temperature from the difference in copolymerization ratio of polymer materials prepared according to the examples. This is a graph showing the change of.

[0122] A total of five types of polymers were produced by mixing Ethyl-CP and Anth-CP in different ratios, and the values ​​for the molecular weight and storage modulus of the monomers are shown in Table 2 below.

[0123]

[0124] Referring to Fig. 5a, it was observed that the heat flow value decreased as the anthracene content in the polymer increased. Additionally, referring to Fig. 5b, it was observed that as the anthracene content in the polymer increased, ExAy with a high glass transition temperature was formed. In the graph of Fig. 5b, the inflection point was formed at a higher temperature, indicating that ExAy with a higher anthracene content has a higher glass transition temperature. It is believed that the reason for the high glass transition temperature is that the fluidity of the polymer chains decreased due to the higher degree of crosslinking.

[0125] Referring to Fig. 5c, the highest tan It was observed that the position of the peak representing the value varied depending on the difference in anthracene content, and the highest tan It was confirmed that the value and the corresponding temperature value correspond to the glass transition temperature.

[0126] From Figures 5a to 5c, it was confirmed via a rheometer that all polymers except E1A0 formed supramolecular polymer networks due to strong interactions between anthracenes. Additionally, it was observed that as the anthracene content increased, the storage modulus increased, and similar behavior was observed in the rubber plateau region after the glass transition temperature.

[0127] Figures 6a and 6b are graphs showing the ultraviolet absorption and fluorescence characteristics according to wavelength from the difference in copolymerization ratios of polymer materials prepared according to the examples. Since the molecular structure of anthracene is maintained in the supramolecular polymer network structure, it is necessary to confirm the ultraviolet absorption and fluorescence characteristics according to the anthracene content.

[0128] Referring to Fig. 6a, in all ExAy samples except E1A0, the characteristic ultraviolet absorption peak of anthracene molecules appeared over the range of 330–400 nm, and no difference was observed depending on the anthracene molecule content. On the other hand, referring to Fig. 6b, regarding fluorescence characteristics, as the anthracene content increased, light of increasingly higher wavelengths was emitted, which is judged to be a result of the redshift phenomenon caused by the formation of j-aggregates between anthracene molecules.

[0129] FIGS. 7a to 7c show the storage modulus and tangent as a function of temperature derived from the difference in copolymerization ratio of a chemically cross-linked polymer network composed of a polymer material prepared according to the example. This is a graph showing the change. Since the polymer material prepared according to Example 1 is a material in which the supramolecular polymer network can transform into a chemically cross-linked polymer network as in Example 2 under long-wavelength ultraviolet light, the changes in thermal and mechanical properties accompanying this were examined.

[0130] Referring to Fig. 7a, depending on the anthracene content, the chemically cross-linked polymer network exhibited a storage modulus increased by as little as 3.5 times to as much as 25 times. Additionally, referring to Fig. 7b, it was confirmed that a second glass transition temperature appeared in addition to the glass transition temperature of the existing network. Furthermore, it was observed that the temperature difference between the first and second glass transition temperatures widened with increasing anthracene content. In Fig. 7c as well, unlike Fig. 5c, the highest tan It was confirmed that two peaks representing the value appeared, and from this, it was confirmed that two glass transition temperatures appeared in the chemically cross-linked polymer network.

[0131] Figure 8 is a graph to verify the photodimerization efficiency of a chemically cross-linked polymer network prepared according to the example. Considering that the intrinsic UV absorption characteristics of the molecule disappear when the photodimerization reaction between anthracene molecules is carried out, changes in the photoabsorption characteristics of the polymer according to the UV irradiation time were observed in solution, with E0A1 as a representative.

[0132] Referring to Fig. 8, the chemically cross-linked polymer network is approximately 33 mW / cm² 2 It was confirmed that a high photodimerization efficiency of approximately 97% was achieved in about 5 minutes when using a single long wavelength (365 nm) ultraviolet lamp with an intensity of .

[0133] Figure 9 is a graph for verifying the photodimerization efficiency of chemically crosslinked polymer networks with different copolymerization ratios prepared according to the examples.

[0134] Considering that the photodimerization reaction between anthracene molecules breaks the conjugation structure of the molecule and does not exhibit the previously observed fluorescence emission characteristics, the photodimerization efficiency of all ExAy molecules, including anthracene, in the solid phase was evaluated.

[0135] Referring to Figure 9, it was calculated through the fluorescence emission intensity that all polymers showed a dimer conversion rate of over 90%, and based on this, it was confirmed that a chemically cross-linked supramolecular polymer network was formed without problems.

[0136] FIGS. 10a to 10c are graphs for determining the hardness and mechanical properties of polymer materials with different copolymerization ratios and chemically crosslinked polymer networks prepared according to the examples. In order to determine whether the polymer material synthesized according to the examples of the present invention has mechanical properties suitable for use as a protective coating film, an indentation test was performed.

[0137] Referring to Figures 10a and 10b, it was confirmed that as the anthracene content increased, the hardness and reduced elastic modulus had higher values. Additionally, it was confirmed that the values ​​of hardness and reduced elastic modulus increased as the supramolecular polymer network (ExAy) was converted to a chemically cross-linked polymer network (c-ExAy). Referring to Figure 10c, which corresponds to the Ashby plot, it was confirmed that among the chemically cross-linked polymer networks, c-E1A1, c-E1A3, and c-E0A1 exhibited superior mechanical properties compared to other plastic materials.

[0138] Figures 11a and 11b are photographs showing the self-repair ability of polymer materials with different copolymerization ratios prepared according to the example in response to external stimulation.

[0139] Referring to Fig. 11a, when a chemically cross-linked polymer network (c-ExAy) coated on a substrate is damaged using a razor blade, it was confirmed that distinct fluorescence was emitted from all polymers depending on the damaged area.

[0140] In addition, photodimerized molecules can return to their original molecular structure by breaking covalent bonds through heat. Referring to Fig. 11b, it was confirmed that damaged areas self-repaired when heat of approximately 130 degrees or higher was applied to a chemically cross-linked polymer network (c-ExAy) followed by irradiation with ultraviolet light. At this time, it was confirmed that the supramolecular polymer network exhibited superior self-repair ability as the anthracene content decreased.

[0141] Figures 12a and 12b illustrate the dual-shape memory properties of a polymer material prepared according to the example. In addition to the damage detection and self-repair properties of the polymer material prepared according to the example, it was confirmed whether the supramolecular polymer network exhibits excellent dual-shape memory properties.

[0142] Referring to Fig. 12a, through a cyclic shape memory test, the anthracene-containing polymer material exhibits a high transient shape fixation ability (R) of approximately 98% or higher. f ) exhibited, and the polymer material showed a high shape recovery ability (R) of over 90%. r It was possible to confirm that it has ).

[0143] Additionally, it was confirmed that among polymer materials, E1A1 can be fixed in a new form by locally irradiating ultraviolet light to enhance thermal and mechanical properties in addition to its existing shape memory properties. Referring to Fig. 12b, it was confirmed that when E1A1 is heated above the glass transition temperature (ii), the region consisting solely of supramolecular polymer networks is restored to its original shape, thereby realizing a new temporary shape. Furthermore, it was confirmed that the supramolecular polymer network can return to its original shape by applying heat to the chemically cross-linked polymer network (iii), which restored it to its original structure.

[0144] Figure 13 is a figure showing the recycling process through depolymerization of a polymer material manufactured according to an example.

[0145] Referring to Fig. 13, it was confirmed that the polymer material prepared according to the example was depolymerized within 2 hours at a relatively mild temperature of 40°C under the same catalyst used during polymerization and restored to monomers. The polymer networks in the initially swollen state were completely dissolved after depolymerization, and it was confirmed through NMR analysis that they were converted into monomers with a purity of over 99%. Subsequently, the monomers constituting the polymer material could be separated and recovered through column purification. Through this, it was confirmed that the polymer material can be selectively applied to a recycling process even when mixed with most general-purpose polymers that lack carbon-carbon double bonds within the polymer chain.

[0146] The foregoing description is merely illustrative, and various modifications may be made by those skilled in the art without departing from the scope and technical spirit of the described embodiments. The foregoing embodiments may be implemented individually or in any combination.

[0147] The present invention can be used in related fields requiring protective coating materials, such as displays, optical devices, and vehicles.

Claims

1. A novel monomer formed by combining Chemical Formula 1 below and any one of Chemical Formulas 2 to 4 below. [Chemical Formula 1] C5H4R1R2 Here, the above chemical formula 1 is cyclic, R1 is a hydroxyl group, a carboxyl group, an amine group, chlorine (Cl), bromine (Br), or iodine (I), and R2 is a hydroxyl group or hydrogen. [Chemical Formula 2] C 13 H9R3 Here, R3 is a carboxyl group, an isocyanate group, a halogen group, a methyl halide group, an amine group, a hydroxymethyl group, a boronic acid group, an aldehyde group, a phenylmethanimine group, or an ethylene group, and the halogen element is chlorine, bromine, or iodine. [Chemical Formula 3] C6H3R4R5R6C2H2Y Here, R4 is hydrogen, a methoxy group, an acetoxy group, a trifluoromethyl group, a methylseleno group, a hydroxyl group, bromine, chlorine, or an amine group, R5 is a hydroxyl group or hydrogen, R6 is a methoxy group or hydrogen, and Y is a carboxyl group, an acyl chloride, or chlorine. [Chemical Formula 4] C6H2R7R8C3HR9O2 Here, R7 is a hydroxyl group, amine group, bromine, or chlorine, R8 is hydrogen, methoxy group, acetyl group, methyl group, hydroxyl group, or chlorine, and R9 is a trifluoromethyl group, methyl group, or hydrogen.

2. In Paragraph 1, The above chemical formula 1 is a novel monomer represented by any one of the following chemical formulas 1-1 to 1-5. [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] [Chemical Formula 1-4] [Chemical Formula 1-5] 3. In Paragraph 1, The above chemical formula 2 is a novel monomer represented by any one of the following chemical formulas 2-1 to 2-10. [Chemical Formula 2-1] [Chemical Formula 2-2] [Chemical Formula 2-3] [Chemical Formula 2-4] [Chemical Formula 2-5] [Chemical Formula 2-6] [Chemical Formula 2-7] [Chemical Formula 2-8] [Chemical Formula 2-9] [Chemical Formula 2-10] 4. In Paragraph 1, The above chemical formula 3 is a novel monomer represented by any one of the following chemical formulas 3-1 to 3-14. [Chemical Formula 3-1] [Chemical Formula 3-2] [Chemical Formula 3-3] [Chemical Formula 3-4] [Chemical Formula 3-5] [Chemical Formula 3-6] [Chemical Formula 3-7] [Chemical Formula 3-8] [Chemical Formula 3-9] [Chemical Formula 3-10] [Chemical Formula 3-11] [Chemical Formula 3-12] [Chemical Formula 3-13] [Chemical Formula 3-14] 5. In Paragraph 1, The above chemical formula 4 is a novel monomer represented by any one of the following chemical formulas 4-1 to 4-11. [Chemical Formula 4-1] [Chemical Formula 4-2] [Chemical Formula 4-3] [Chemical Formula 4-4] [Chemical Formula 4-5] [Chemical Formula 4-6] [Chemical Formula 4-7] [Chemical Formula 4-8] [Chemical Formula 4-9] [Chemical Formula 4-10] [Chemical Formula 4-11] 6. In Paragraph 2 or 3, The above novel monomer is a novel monomer represented by any one of the following chemical formulas 5-1 to 5-20. [Chemical Formula 5-1] [Chemical Formula 5-2] [Chemical Formula 5-3] [Chemical Formula 5-4] [Chemical Formula 5-5] [Chemical Formula 5-6] [Chemical Formula 5-7] [Chemical Formula 5-8] [Chemical Formula 5-9] [Chemical Formula 5-10] [Chemical Formula 5-11] [Chemical Formula 5-12] [Chemical Formula 5-13] [Chemical Formula 5-14] [Chemical Formula 5-15] [Chemical Formula 5-16] [Chemical Formula 5-17] [Chemical Formula 5-18] [Chemical Formula 5-19] [Chemical Formula 5-20] 7. In Paragraph 2 or 4, The above novel monomer is a novel monomer represented by any one of the following chemical formulas 6-1 to 6-65. [Chemical Formula 6-1] [Chemical Formula 6-2] [Chemical Formula 6-3] [Chemical Formula 6-4] [Chemical Formula 6-5] [Chemical Formula 6-6] [Chemical Formula 6-7] [Chemical Formula 6-8] [Chemical Formula 6-9] [Chemical Formula 6-10] [Chemical Formula 6-11] [Chemical Formula 6-12] [Chemical Formula 6-13] [Chemical Formula 6-14] [Chemical Formula 6-15] [Chemical Formula 6-16] [Chemical Formula 6-17] [Chemical Formula 6-18] [Chemical Formula 6-19] [Chemical Formula 6-20] [Chemical Formula 6-21] [Chemical Formula 6-22] [Chemical Formula 6-23] [Chemical Formula 6-24] [Chemical Formula 6-25] [Chemical Formula 6-26] [Chemical Formula 6-27] [Chemical Formula 6-28] [Chemical Formula 6-29] [Chemical Formula 6-30] [Chemical Formula 6-31] [Chemical Formula 6-32] [Chemical Formula 6-33] [Chemical Formula 6-34] [Chemical Formula 6-35] [Chemical Formula 6-36] [Chemical Formula 6-37] [Chemical Formula 6-38] [Chemical Formula 6-39] [Chemical Formula 6-40] [Chemical Formula 6-41] [Chemical Formula 6-42] [Chemical Formula 6-43] [Chemical Formula 6-44] [Chemical Formula 6-45] [Chemical Formula 6-46] [Chemical Formula 6-47] [Chemical Formula 6-48] [Chemical Formula 6-49] [Chemical Formula 6-50] [Chemical Formula 6-51] [Chemical Formula 6-52] [Chemical Formula 6-53] [Chemical Formula 6-54] [Chemical Formula 6-55] [Chemical Formula 6-56] [Chemical Formula 6-57] [Chemical Formula 6-58] [Chemical Formula 6-59] [Chemical Formula 6-60] [Chemical Formula 6-61] [Chemical Formula 6-62] [Chemical Formula 6-63] [Chemical Formula 6-64] [Chemical Formula 6-65] 8. In Paragraph 2 or 5, The above novel monomer is a novel monomer represented by any one of the following chemical formulas 7-1 to 7-27. [Chemical Formula 7-1] [Chemical Formula 7-2] [Chemical Formula 7-3] [Chemical Formula 7-4] [Chemical Formula 7-5] [Chemical Formula 7-6] [Chemical Formula 7-7] [Chemical Formula 7-8] [Chemical Formula 7-9] [Chemical Formula 7-10] [Chemical Formula 7-11] [Chemical Formula 7-12] [Chemical Formula 7-13] [Chemical Formula 7-14] [Chemical Formula 7-15] [Chemical Formula 7-16] [Chemical Formula 7-17] [Chemical Formula 7-18] [Chemical Formula 7-19] [Chemical Formula 7-20] [Chemical Formula 7-21] [Chemical Formula 7-22] [Chemical Formula 7-23] [Chemical Formula 7-24] [Chemical Formula 7-25] [Chemical Formula 7-26] [Chemical Formula 7-27] 9. In any one of paragraphs 6 through 8, A novel monomer having a ring strain greater than 2 kcal / mol and less than 8 kcal / mol.

10. A polymer material capable of maintaining chemical properties, comprising the novel monomer described in any one of claims 1 to 5.

11. In Paragraph 10, A polymer material capable of maintaining chemical properties, wherein the molar ratio of the novel monomer in the polymer material is 1 mol% or more.

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