Monomer having functional group, heat-resistant polymer having rigid main chain using same, and manufacturing method therefor

Abstract

The present invention relates to a monomer having a functional group, a heat-resistant polymer having a rigid main chain using same, and a manufacturing method therefor. Particularly, the present invention relates to a monomer having a pentafluorophenyl group of chemical formula 1, a heat-resistant polymer of chemical formulas 2 and 3 having the monomer of the present invention, and a manufacturing method therefor. According to the present invention, a novel polymer obtained by polymerizing a novel monomer of the present invention has a reactive group of reactive pentafluorophenyl, and thus may exhibit excellent reactivity and enable synthesis of polymers having an excellent polymerization degree by using a polyhydroxyalkylation polymerization method without a protective group. Due to such excellent reactivity, the polymer of the present invention can cause a nucleophilic substitution reaction under mild conditions, and thus an ion-exchange group, such as sulfonic acid or phosphonic acid, can be introduced under mild conditions through such a reaction. In addition, the novel polymer of the present invention has high heat resistance and chemical resistance and good tensile strength, and thus can be used as an engineering plastic. In addition, the novel polymer of the present invention can be imparted with ionic conductivity or other functionalities by introducing a phosphonic acid group or a sulfonic acid group into any one of fluoro positions of pentafluorophenyl of the polymer, and accordingly, may be used as an electrolyte membrane for a fuel cell or water electrolysis. [Chemical formula 1] [Chemical formula 2] [Chemical formula 3]

Description

Monomer having functional groups, heat-resistant polymer having a rigid main chain using the same, and method for manufacturing the same

[0001] The present invention relates to a polymer having high heat resistance and chemical resistance while being endowed with ion conductivity or other functionalities, and a method for manufacturing the same.

[0002] Project ID: 271001960

[0003] Project Number: KN24-54

[0004] Ministry Name: Ministry of Science and ICT

[0005] Project Management (Specialized) Agency Name: National Research Foundation of Korea

[0006] Research Project Name: Nanomaterial Technology Development

[0007] Research Project Title: Development of Carbon-Carbon Structure-Based Binder Materials for High-Temperature PEMFCs

[0008] Project Executing Organization Name: Korea Research Institute of Chemical Technology

[0009] Research Period: 2024.01.01.–2024.12.31

[0010] Project ID: 24110

[0011] Project Number: KN24-110

[0012] Ministry Name: Ministry of Science and ICT

[0013] Project Management (Specialized) Agency Name: National Research Foundation of Korea

[0014] Research Project Name: Green Hydrogen Technology Self-Reliance

[0015] Research Project Title: Development of Next-Generation Materials and Reliability Technology for PEM Water Electrolysis

[0016] Project Executing Organization Name: Korea Research Institute of Chemical Technology

[0017] Research Period: July 1, 2024 – December 31, 2024

[0018] Project ID: 2410003993

[0019] Project No.: TS247-04R

[0020] Ministry Name: Ministry of Trade, Industry and Energy

[0021] Project Management (Specialized) Agency Name: Korea Institute of Industrial Technology Planning and Evaluation

[0022] Research Project Name: Development of Materials and Components Technology

[0023] Research Project Title: Development of Membrane Electrode Assemblies and Stack Element Technologies for PEM Water Electrolysis

[0024] Project Executing Organization Name: Korea Research Institute of Chemical Technology

[0025] Research Period: 2024.01.01.–2024.12.31

[0026] Engineering plastics are high-performance materials that meet specific mechanical, thermal, and chemical requirements beyond everyday use. These plastics possess properties that allow them to replace conventional metals or other traditional materials, enabling weight reduction, cost savings, and simplification of manufacturing processes.

[0027] In addition, reactive engineering plastics that can cause chemical reactions with other molecules or atoms by introducing specific functional groups into polymer chains are being actively researched. These reactive engineering plastics can be used to improve the functions or physical properties of existing polymers or to create new polymer materials. Specifically, they can be used to create composite materials with new functions by combining with other polymers, nanomaterials, fibers, etc., or they can be used to combine with other materials or change surface properties by introducing reactive groups to the polymer surface, or they can be used to create new polymer structures using the introduced reactive groups or to develop polymer materials with new physical properties by introducing functional groups.

[0028] Representative polymers used in engineering plastics include polyamide (PA), polycarbonate (PC), polybutylene terephthalate (PBT), modified polyphenylene oxide (PPO), polyimide (PI), polyethersulfone (PES), polyetheretherketone (PEEK), and polybenzimidazole (PBI). Due to their excellent performance, these polymers are widely utilized in various industrial fields, such as the medical sector, consumer goods, aerospace, automotive, electronics and electrical industries, environmental sector, energy sector, and architecture and construction.

[0029] Recently, polymers possessing high heat and chemical resistance while being endowed with ion conductivity or other functionalities are being utilized in fuel cells, water electrolysis, and secondary batteries. Representative examples include sulfonated polymers developed as electrolyte membranes for fuel cells or water electrolysis, such as Nafion, sulfonated polyetheretherketone, sulfonated polyimide, sulfonated polystyrene, and sulfonated polybenzimidazole, as well as phosphorylated polymers such as phosphoric acid-doped polybenzimidazole. Additionally, there are sulfonated polyaryleneethersulfones in which sulfonic acid groups are introduced into the main chain of the enpla.

[0030] However, engineering polymers such as PAES, PEEK, PI, PA, and PBI are mainly produced by condensation polymerization, but when monomers containing reactive functional groups, such as pentafluorophenyl groups, are introduced, there is a risk that the reactive group may participate in the polymerization reaction, causing side reactions or interfering with the polymerization reaction, thereby causing problems with the polymerization itself.

[0031] In addition, to improve this, polymerization is carried out by substituting a protecting group for a conventional reactive functional group, but this requires an additional process of deprotecting the protecting group after polymerization, which complicates the reaction and risks causing side reactions.

[0032] In particular, when applied to polymer electrolyte membranes, it may be difficult to obtain a high degree of polymerization because the monomer reactivity is low when polymerizing engineering plastics by synthesizing monomers having ion exchange groups such as sulfonic acid groups. In cases where the polymer is formed first and ion exchange groups are introduced (sulfonic acid groups are introduced via post-sulfonation), the ion exchange capacity (degree of sulfonation) is controlled by the reaction time with sulfonating agents such as sulfuric acid, fuming sulfuric acid, and chlorosulfonic acid. However, this may result in problems such as unclear location of the ion exchange group introduction within the chemical structure and poor reproducibility (reproducing the same degree of sulfonation every time).

[0033] Recently, various studies, including the development of new polymer materials, are actively underway to overcome the shortcomings of existing electrolyte membranes and improve their performance.

[0034] The prior art related to this is as follows.

[0035] Korean Patent Registration No. 10-2003719 (Applicant: Korea Research Institute of Chemical Technology; Registration Date: July 19, 2019) relates to a polyamide resin produced from amino acids and dimer acid derivatives derived from vegetable oils. It states that the polyamide resin produced by reacting an 11-aminoundecanoic acid derivative derived from animal or vegetable oils or waste oil with a dimer acid derivative and a diamine exhibits superior physical properties and easy melt molding characteristics compared to conventional technology, and thus can be usefully utilized in fields such as clothing materials, industrial material fibers, engineering plastics, electrical / electronic components, and automotive parts.

[0036] Korean Patent Publication No. 10-2022-0021121 (Applicant: Korea Research Institute of Chemical Technology; Date of Publication: February 22, 2022) relates to an amorphous super engineering plastic fiber and a method for manufacturing the same. More specifically, it describes an amorphous super engineering plastic fiber characterized by excellent high strength, a high glass transition temperature, and a low coefficient of thermal expansion by manufacturing a polyarylene ether copolymer containing isohexade units, which is a type of amorphous super engineering plastic, and introducing a wet spinning method thereon.

[0037] Korean Patent Publication No. 10-2021-0021716 (Applicant: LG Chem Co., Ltd.; Date of Publication: March 2, 2021) relates to a polyamide-imide polymer and an engineering plastic containing the same, and describes a polyamide-imide polymer and an engineering plastic containing the same comprising a first unit represented by the following Chemical Formula 1; and a second unit represented by the following Chemical Formula 2:

[0038] [Chemical Formula 1]

[0039]

[0040] [Chemical Formula 2]

[0041]

[0042] Korean Patent Publication No. 2012-0092055 (Applicant: Elchemtech Co., Ltd.; Date of Publication: August 20, 2012) relates to a polymer electrolyte membrane, a water electrolysis device, a fuel cell, and a fuel cell system including the same, characterized by comprising a polymer having repeating units of the following chemical formula and an inorganic acid substituted with a macromolecule, wherein the macromolecule is one or more mixtures selected from the group consisting of cesium, ammonium, rubidium, sodium, and potassium, and relates to a polymer electrolyte membrane and a method for manufacturing the same, a water electrolysis device including the polymer electrolyte, a fuel cell, and a fuel cell system including the same:

[0043]

[0044] In the present invention, a novel monomer containing a pentafluorophenyl group as a reactive group was used to carry out a nucleophilic aromatic substitution reaction, and a reactive polymer was developed that can introduce various functionalities through a polymer analogous reaction. It was discovered that this polymer can be used as an electrolyte membrane for fuel cells or water electrolysis, which has high heat resistance and chemical resistance and is endowed with ion conductivity or other functionalities.

[0045] The objective of the present invention is to solve the problems of the prior art by providing a monomer having reactive functional groups capable of exhibiting excellent reactivity and enabling the synthesis of a polymer with an excellent degree of polymerization using a polyhydroxyalkylation polymerization method even without a protecting group, a polymer imparted with ion conductivity or other functionalities while possessing high heat resistance and chemical resistance, and a method for manufacturing the same.

[0046] Meanwhile, the technical problems to be solved by the present invention are not limited to those mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art to which the present invention belongs from the description below.

[0047] To achieve the above objective,

[0048] One aspect of the present invention provides a monomer having a pentafluorophenyl group of the following formula 1:

[0049] [Chemical Formula 1]

[0050]

[0051] In addition, another aspect of the present invention is a method for producing the monomer of the present invention,

[0052] A method is provided comprising the steps of: adding a potassium tert-butoxide alcohol solution dropwise to a pentafluorobenzoic acid alcohol solution (Step 1); post-treating the reaction product obtained in Step 1 to obtain potassium 2,3,4,5,6-pentafluorobenzoate (Step 2); mixing the potassium 2,3,4,5,6-pentafluorobenzoate obtained in Step 2 with 5-bromo-m-terphenyl and purging with Ar (Step 3); adding and stirring the mixture obtained in Step 3 with Diglim and raising the temperature to react (Step 4); and post-treating the reaction product obtained in Step 4 to obtain the monomer of claim 1 (Step 5).

[0053] A preferred embodiment of another aspect of the present invention is that in step 1, the alcohol is ethanol, and

[0054] The post-treatment of Step 2 evaporates the alcohol, adds diethyl ether to the residual liquid to precipitate a white solid, filters and dries the solid, and

[0055] Step 3 comprises mixing the potassium 2,3,4,5,6-pentafluorobenzoate and 5-bromo-m-terphenyl obtained in Step 2 with CuI and 1,10-phenanthroline, and purging with Ar.

[0056] In step 4, the temperature is raised to 130℃, and

[0057] The post-treatment of step 5 is characterized by evaporating the deglim and adding methylene chloride to obtain a residual liquid, adding water to it, evaporating the methylene chloride from the methylene chloride layer, filtering, dissolving the residue in methanol to obtain an undissolved solid, and drying.

[0058] In addition, another aspect of the present invention provides a reactive heat-resistant polymer obtained by polymerizing a monomer of the present invention and a compound containing a carbonyl group by polyhydroxyalkylation (Friedel-Crafts aromatic electrophilic substitution reaction), or by copolymerizing a monomer of the present invention with an aromatic ring.

[0059] A preferred embodiment of another aspect of the present invention is characterized in that the heat-resistant polymer is a reactive heat-resistant polymer of the following formula 2 comprising a monomer of the present invention:

[0060] [Chemical Formula 2]

[0061]

[0062] [In the above formula, A' is a residue formed by a condensation reaction from structure A, which has a carbonyl group (-C(=O)-) capable of protonation under superacid conditions and can be combined with an aromatic monomer containing a pentafluorophenyl group through a Friedel-Crafts type condensation reaction, wherein the carbonyl oxygen of A is removed and the residue has a structure in which it is bonded to an aromatic ring via carbon-carbon bonding, and

[0063] Structure A is

[0064]

[0065] [A device selected from a group consisting of].

[0066] Here, 'superacid conditions' refer to a strong acid environment capable of inducing electrophilic activation through the protonation of carbonyl groups during the polymerization process, and specifically include trifluoromethanesulfonic acid (TFSA) or conditions having an acidity equivalent to or greater than that, i.e., an acid environment corresponding to a pKa range of approximately -5 or lower.

[0067] A preferred embodiment of another aspect of the present invention is characterized in that the heat-resistant polymer is a reactive heat-resistant polymer of the following formula 3 comprising a monomer of the present invention:

[0068] [Chemical Formula 3]

[0069]

[0070] [In the above formula, A' is a residue formed by a condensation reaction from structure A, which has a carbonyl group (-C(=O)-) capable of protonation under superacid conditions and can be combined with an aromatic monomer containing a pentafluorophenyl group through a Friedel-Crafts type condensation reaction, wherein the carbonyl oxygen of A is removed and the residue has a structure in which it is bonded to an aromatic ring via a carbon-carbon bond, and

[0071] B' is a residue formed by a condensation reaction from structure B, which comprises two or more single, polycyclic, or heterocyclic aromatic rings, and is a residue having a structure in which two hydrogen atoms are removed, formed by two carbons of the aromatic rings of B each bonding to a carbon of A'.

[0072] Structure A is

[0073]

[0074] It is a group selected from the group consisting of, and

[0075] Structure B is a structure comprising two or more single, polycyclic, or heterocyclic aromatic rings capable of polymerizing under superacid conditions, and preferably a structure comprising two or more single, polycyclic, or heterocyclic aromatic rings capable of polymerizing with protonated compound A under superacid conditions, and specifically

[0076]

[0077] [A device selected from a group consisting of].

[0078] In addition, another aspect of the present invention is a method for producing the polymer of the present invention by reaction formula 1, wherein

[0079] A step of dissolving a monomer having a pentafluorophenyl group of Chemical Formula 1 and compound A of Reaction Scheme 1 below in a solvent (Step 1');

[0080] A step of adding trifluoromethanesulfonic acid dropwise to the mixture obtained in step 1' in an ice bath (step 2');

[0081] Step of removing the ice bath and stirring and reacting the mixture at room temperature (Step 3'); and

[0082] A method is provided comprising the step (step 4') of preparing a polymer of Formula 2 by post-processing after the reaction is completed.

[0083] [Reaction Equation 1]

[0084]

[0085] [In the above formula, A' is a residue formed by a condensation reaction from structure A, which has a carbonyl group (-C(=O)-) capable of protonation under superacid conditions and can be combined with an aromatic monomer containing a pentafluorophenyl group through a Friedel-Crafts type condensation reaction, wherein the carbonyl oxygen of A is removed and the residue has a structure in which it is bonded to an aromatic ring via carbon-carbon bonding, and

[0086] The above A is

[0087]

[0088] [A device selected from a group consisting of].

[0089] A preferred embodiment of another aspect of the present invention is characterized in that the solvent of step 1' is dichloromethane, and the post-treatment of step 4' includes precipitating the reaction mixture in methanol to obtain a precipitate, washing it with methanol, filtering, and drying it.

[0090] Another aspect of the present invention is a method for producing the polymer of the present invention by the following reaction scheme 2, wherein

[0091] A step of dissolving a monomer having a pentafluorophenyl group of Formula 1 and compounds A and B of Reaction Formula 2 in a solvent (Step 1);

[0092] A step of dissolving a monomer having a pentafluorophenyl group of Formula 1 and compounds A and B of Reaction Formula 2 in a solvent (Step 1);

[0093] A step of adding trifluoromethanesulfonic acid dropwise to the mixture obtained in Step 1 in an ice bath (Step 2);

[0094] Step of removing the ice bath and stirring and reacting the mixture (Step 3);

[0095] A method is provided comprising the step of preparing a polymer of Formula 3 by post-processing after the reaction is completed (Step 4):

[0096] [Reaction Equation 2]

[0097]

[0098] [In the above formula, A' is a residue formed by a condensation reaction from structure A, which has a carbonyl group (-C(=O)-) capable of protonation under superacid conditions and can be combined with an aromatic monomer containing a pentafluorophenyl group through a Friedel-Crafts type condensation reaction, wherein the carbonyl oxygen of A is removed and the residue has a structure in which it is bonded to an aromatic ring via carbon-carbon bonding, and

[0099] The above A is,

[0100]

[0101] It is a group selected from the group consisting of, and

[0102] B' is a residue formed by a condensation reaction from structure B, which comprises two or more single, polycyclic, or heterocyclic aromatic rings, and is a residue having a structure in which two hydrogen atoms are removed, formed by two carbons of the aromatic rings of B each bonding to a carbon of A'.

[0103] The above B is

[0104]

[0105] [A device selected from a group consisting of].

[0106] A preferred embodiment of another aspect of the present invention is characterized in that the solvent of step 1" is dichloromethane, and the post-treatment of step 4" comprises precipitating the reaction mixture in methanol to obtain a precipitate, washing it with methanol, filtering, and drying it.

[0107] Another aspect of the present invention provides a heat-resistant polymer in which a phosphonic acid group or a sulfonic acid group is introduced into either the fluoro position of the pentafluorophenyl group of the heat-resistant polymer of Formula 2 or Formula 3 of the present invention.

[0108] Another aspect of the present invention is a method for producing a heat-resistant polymer having phosphonic acid groups introduced according to the present invention, wherein

[0109] A heat-resistant polymer of Formula 2 or Formula 3 of the present invention is dissolved in N,N-dimethylacetamide, and

[0110] Tris(trimethylsilyl)phosphite is added to the above solution and stirred to react;

[0111] A method is provided comprising obtaining a heat-resistant polymer with introduced phosphonic acid groups by post-treatment after the reaction.

[0112] Another aspect of the present invention is a method for producing a heat-resistant polymer having a sulfonic acid group introduced according to the present invention, wherein

[0113] A heat-resistant polymer of Formula 2 or Formula 3 of the present invention is dissolved in N,N-dimethylacetamide, and

[0114] Sodium hydrosulfide hydrate is added to the above solution and stirred to react;

[0115] After the reaction, an aqueous hydrochloric acid solution is added to obtain a precipitate, and the precipitate is filtered and dried to obtain a thiolized polymer;

[0116] The above thiolized polymer is added to acetic anhydride, hydrogen peroxide, and sulfuric acid to disperse it, stirred at a temperature of 50°C to 100°C, and reacted;

[0117] A method is provided comprising obtaining a heat-resistant polymer with introduced sulfonic acid groups by post-treatment after the reaction.

[0118] According to the present invention, a novel polymer obtained by polymerizing the novel monomer of the present invention has a reactive group of pentafluorophenyl, so it can exhibit excellent reactivity, and it is possible to synthesize a polymer with an excellent degree of polymerization using a polyhydroxyalkylation polymerization method even without a protecting group, and due to this excellent reactivity, the polymer of the present invention can undergo a nucleophilic substitution reaction under mild conditions, and through this reaction, it is possible to introduce ion exchange groups such as sulfonic acid or phosphonic acid under mild conditions.

[0119] In addition, the novel polymer of the present invention has high heat resistance, chemical resistance, and good tensile strength, making it suitable for use as an engineering plastic. Furthermore, the novel polymer of the present invention can be imparted ion conductivity or other functionalities by introducing a phosphonic acid group or a sulfonic acid group to any one of the fluoro positions of the pentafluorophenyl group of the polymer, and accordingly, can be used as an electrolyte membrane for fuel cells or water electrolysis.

[0120] However, the effects obtainable from the present invention are not limited to those mentioned above, and other unmentioned effects will be clearly understood by those skilled in the art from the description below.

[0121] Figure 1 is a graph showing the NMR results of the monomer prepared by reaction scheme 1 of the present invention.

[0122] Figure 2 is a graph showing the NMR results of a polymer polymerized according to Example 1 of the present invention.

[0123] Figure 3 is a graph showing the NMR results of a polymer polymerized according to Example 2 of the present invention.

[0124] Figure 4 is a graph showing the NMR results of the polymer polymerized according to Example 3 of the present invention.

[0125] Figure 5 is a graph showing the NMR results of the polymer polymerized according to Example 4 of the present invention.

[0126] Figure 6 is a graph showing the NMR results of the polymer polymerized according to Example 5 of the present invention.

[0127] Figure 7 is a graph showing the NMR results of the polymer polymerized according to Example 6 of the present invention.

[0128] FIG. 8 is a graph showing the ATR-FTIR results of polymers polymerized according to Examples 1 to 6 of the present invention.

[0129] Figure 9 is a table showing the GPC results of polymers polymerized according to Examples 1 to 6 of the present invention.

[0130] FIG. 10 is a graph and table showing the TGA results of polymers polymerized according to Examples 1 to 5 of the present invention.

[0131] FIG. 11 is a graph and table showing the DSC results of polymers polymerized according to Examples 1 to 5 of the present invention.

[0132] FIG. 12 is a table showing the solubility results of polymers polymerized according to Examples 1 to 6 of the present invention.

[0133] FIG. 13 is a table showing the physical properties of the polymers polymerized according to Examples 1 and 5 of the present invention.

[0134] Figure 14 is a graph showing the NMR results of a polymer into which a phosphonic acid group was introduced according to Example 7 of the present invention.

[0135] Figure 15 is a graph showing the NMR results of a polymer into which a sulfonic acid group was introduced according to Example 8 of the present invention.

[0136] Figure 16 is a graph showing the NMR results of a polymer into which a phosphonic acid group was introduced according to Example 9 of the present invention.

[0137] Figure 17 is a graph showing the NMR results of a polymer into which a sulfonic acid group was introduced according to Example 10 of the present invention.

[0138] Technical and scientific terms used in this invention are used in the same sense as generally understood by a person of ordinary knowledge in the relevant technical field. Terms defined in ordinary dictionaries are interpreted in a sense consistent with the descriptions in relevant technical literature and this specification, and are not interpreted in an overly ideal or formal sense unless otherwise defined.

[0139] Embodiments of the present invention are described below with reference to the attached drawings so that those skilled in the art can easily understand and practice them. However, the present invention may be implemented in various ways and is not limited to this description. Furthermore, specific descriptions of known technologies or components are omitted during the description of the present invention if there is a risk that such detailed descriptions would overcomplicate the core content of the invention.

[0140] The following is a detailed description of the present invention.

[0141] One aspect of the present invention provides a monomer having a pentafluorophenyl group of the following formula 1:

[0142] [Chemical Formula 1]

[0143]

[0144] The monomer of Chemical Formula 1 above is a novel compound for obtaining a reactive heat-resistant polymer prepared below by polymerization.

[0145] These monomers are characterized by containing functional groups, particularly pentafluorophenyl groups, which can exhibit excellent reactivity and enable the synthesis of polymers with excellent degree of polymerization using polyhydroxyalkylation polymerization even without protecting groups, and allow nucleophilic aromatic substitution reactions to proceed after the formation of the polymer, thereby enabling the formation of reactive polymers capable of introducing various functionalities through polymer reactions.

[0146] The monomer of the present invention can be manufactured in two stages as shown in the following reaction scheme 0.

[0147] The first step involves reacting pentafluorobenzoic acid with potassium tertiary-butoxide to produce potassium 2,3,4,5,6-pentafluorobenzoate.

[0148] Subsequently, the second stage involves reacting potassium 2,3,4,5,6-pentafluorobenzoate with 5'-bromo-m-terphenyl to produce the monomer of the present invention.

[0149] [Reaction Equation 0]

[0150]

[0151] More specifically, it can be manufactured through the following steps:

[0152] A step of adding a potassium tert-butoxide alcohol solution dropwise to a pentafluorobenzoate alcohol solution; and post-treating the obtained reaction product to obtain potassium 2,3,4,5,6-pentafluorobenzoate (Step 1); and

[0153] Step 2: mixing potassium 2,3,4,5,6-pentafluorobenzoate and 5-bromo-m-terphenyl obtained in Step 1, purging with Ar, adding and stirring the obtained mixture, raising the temperature to react, and post-treating the obtained reaction product to obtain the monomer of the present invention.

[0154] Each step is described in detail below.

[0155] Step 1 involves adding potassium tert-butoxide alcohol solution dropwise to a pentafluorobenzoic acid alcohol solution.

[0156] A pentafluorobenzoic acid alcohol solution is obtained, as an example, as an ethanol solution by dissolving pentafluorobenzoic acid in ethanol.

[0157] Potassium tertiary-butoxide alcohol solution is obtained as an example of an ethanol solution by dissolving potassium tertiary-butoxide in ethanol.

[0158] The above-mentioned addition can be carried out by any one of the methods known in the field, and as an example, a potassium tert-butoxide alcohol solution can be added dropwise to a pentafluorobenzoic acid alcohol solution using a dropping funnel.

[0159] It is preferable to perform such price drops at room temperature.

[0160] After completing the dropwise addition, the reaction is carried out by stirring at room temperature, preferably, stirring can be performed at room temperature for 1 to 4 hours.

[0161] Subsequently, the reaction product obtained above is post-treated to obtain potassium 2,3,4,5,6-pentafluorobenzoate.

[0162] As a post-treatment, the solvent is first removed from the reactant obtained in Step 1 by evaporation. Evaporation can be carried out by conventional evaporation methods known in the art.

[0163] A non-polar solvent, for example, diethyl ether, is added to the residual liquid obtained through this process. At this time, a white solid is precipitated. The precipitated white solid is potassium 2,3,4,5,6-pentafluorobenzoate, which is obtained by filtering and drying, for example, by vacuum drying.

[0164] Step 2 involves mixing the potassium 2,3,4,5,6-pentafluorobenzoate and 5-bromo-m-terphenyl obtained in Step 1, and purging with Ar.

[0165] The reactant 5-bromo-m-terphenyl can be mixed in a slightly excess amount compared to potassium 2,3,4,5,6-pentafluorobenzoate, and as an example, potassium 2,3,4,5,6-pentafluorobenzoate and 5-bromo-m-terphenyl are preferably in a molar ratio of 1:1.5 to 2.

[0166] Catalysts, etc., may be added to such reaction mixtures, and as an example, CuI and 1,10-phenanthroline may be added.

[0167] Then, a solvent, e.g., diglyme, is added to the obtained mixture, and the temperature is raised while stirring, e.g., to 130°C. The mixture is reacted at this temperature for several hours, e.g., 24 to 48 hours.

[0168] The obtained reaction product is then post-treated to obtain the monomer of the present invention.

[0169] The reaction product obtained above is cooled, and the solvent, e.g., deglim, is removed by evaporation. Evaporation can be carried out by conventional evaporation methods known in the art.

[0170] The residual liquid obtained through this process is dissolved in a non-polar solvent, e.g., methylene chloride, and filtered to obtain a filtrate. Extraction is performed on the obtained filtrate using water, methylene chloride is evaporated from the obtained methylene chloride layer, filtered, e.g., using a silica gel filter, the solvent of the obtained organic layer is removed, the residue is dissolved in methanol to obtain an undissolved solid, and dried, e.g., vacuum dried.

[0171] Finally, the monomer of claim 1 is obtained.

[0172] It was confirmed that this was synthesized from the NMR results shown in Fig. 1.

[0173] In addition, another aspect of the present invention provides a reactive heat-resistant polymer obtained by polymerizing a monomer of the present invention and a compound containing a carbonyl group by polyhydroxyalkylation (Friedel-Crafts aromatic electrophilic substitution reaction), or by copolymerizing the monomer of claim 1 with an aromatic ring.

[0174] Specifically, the reactive heat-resistant polymer of the present invention provides a reactive heat-resistant polymer of Formula 2 or Formula 3 below, comprising a monomer of the present invention:

[0175] [Chemical Formula 2]

[0176]

[0177] [In the above formula,

[0178] A' is a residue formed by a condensation reaction from structure A, which has a carbonyl group (-C(=O)-) capable of protonation under superacid conditions and can be combined with an aromatic monomer containing a pentafluorophenyl group through a Friedel-Crafts type condensation reaction, wherein the carbonyl oxygen of A is removed and the residue has a structure in which it is bonded to an aromatic ring via carbon-carbon bonding.

[0179] The above structure A is

[0180]

[0181] [A device selected from a group consisting of].

[0182] Here, 'superacid conditions' refer to a strong acid environment capable of inducing electrophilic activation through the protonation of carbonyl groups during the polymerization process, and specifically include trifluoromethanesulfonic acid (TFSA) or conditions having an acidity equivalent to or greater than that, i.e., an acid environment corresponding to a pKa range of approximately -5 or lower.

[0183] [Chemical Formula 3]

[0184]

[0185] [In the above formula, A' is a residue formed by a condensation reaction from structure A, which has a carbonyl group (-C(=O)-) capable of protonation under superacid conditions and can be combined with an aromatic monomer containing a pentafluorophenyl group through a Friedel-Crafts type condensation reaction, wherein the carbonyl oxygen of A is removed and the residue has a structure in which it is bonded to an aromatic ring via a carbon-carbon bond, and

[0186] B' is a residue formed by a condensation reaction from structure B, which comprises two or more single, polycyclic, or heterocyclic aromatic rings, and is a residue having a structure in which two hydrogen atoms are removed, formed by two carbons of the aromatic rings of B each bonding to a carbon of A'.

[0187] Structure A is

[0188]

[0189] It is a group selected from the group consisting of, and

[0190] B is a structure comprising two or more single, polycyclic, or heterocyclic aromatic rings capable of polymerizing under superacid conditions, and preferably a structure comprising two or more single, polycyclic, or heterocyclic aromatic rings capable of polymerizing with protonated compound A under superacid conditions, and specifically,

[0191]

[0192] [A device selected from a group consisting of].

[0193] These polymers were obtained through the polymerization of novel monomers and specific compound A or compounds A and B.

[0194] Specific compounds A and B are carbon-carbon linked main chains, and in particular, compound A can be any compound having a carbonyl group, preferably the compound described in Formula 2.

[0195] As can be seen in FIGS. 8 to 13, the polymer of the present invention has high heat resistance, chemical resistance, and good tensile strength, so it can be used as an engineering plastic.

[0196] Figure 8 shows the thermal decomposition temperature of the polymer sample, confirming the weight loss according to temperature. The temperature at which the weight decreased by 5% ranged from 422°C to 525°C, with two major weight losss. When examining the differential values, the first weight loss was distributed between 467°C and 533°C, and the second weight loss was distributed between 543°C and 647°C. After heating to 800°C, the final remaining char yield maintained a high value of 58 to 72%. These results indicate that the polymerized polymer exhibits sufficient heat resistance as an engineering polymer.

[0197] Figure 9 shows DSC data obtained using a DSC device for the polymerized polymers. It can be seen that the glass transition temperatures of the polymers in Examples 1 to 4 are distributed from 219°C to 222°C. In addition, the glass transition temperature of the polymer in Example 5 was observed at approximately 250°C. As shown in the above results, it was confirmed that all polymerized polymers can maintain their mechanical and thermal properties up to 200°C or higher.

[0198] Figure 10 shows the solubility results of the polymerized polymers in various organic solvents. It was confirmed that all polymerized polymers are well soluble in commercial organic solvents such as NMP, DMAc, THF, chloroform, and dichloromethane. As the polymerized reactive polymers exhibit excellent solubility, it was confirmed that they can be utilized in polymer analogous reactions in various solvent environments.

[0199] Figure 11 shows the stress and strain that occur when the membrane is pulled in a direction parallel to the plane through a tensile test of the polymer membrane. It was confirmed that the polymers of Example 1 and Example 5 each exhibited excellent tensile properties, with fracture stresses of 41.6 MPa and 35.9 MPa, fracture strains of 7.4% and 17.7%, stiffness of 28927 N / m and 21965 N / m, and Young's modulus of 3063 MPa and 1441 MPa. It was indicated that Example 5, containing methyl groups, possessed more flexible mechanical properties compared to Example 1, which contains phenyl groups.

[0200] As described above, the polymer of the present invention has a reactive group of pentafluorophenyl, so it can exhibit excellent reactivity, and it is possible to synthesize a polymer with an excellent degree of polymerization using a polyhydroxyalkylation polymerization method even without a protecting group. Due to this excellent reactivity, the polymer of the present invention can undergo a nucleophilic substitution reaction under mild conditions, and through this reaction, it is possible to introduce ion exchange groups such as sulfonic acid or phosphonic acid under mild conditions.

[0201] Specifically, the polymer of Formula 2 among the polymers of the present invention can be prepared by the following steps as indicated by Reaction Scheme 1:

[0202] A step of dissolving a monomer having a pentafluorophenyl group of Chemical Formula 1 and compound A of Reaction Scheme 1 below in a solvent (Step 1');

[0203] A step of adding trifluoromethanesulfonic acid dropwise to the mixture obtained in step 1' in an ice bath (step 2');

[0204] Step of removing the ice bath and stirring and reacting the mixture at room temperature (Step 3'); and

[0205] Step of preparing the polymer of Chemical Formula 2 by post-processing after the reaction is complete (Step 4'):

[0206] [Reaction Equation 1]

[0207]

[0208] [In the above formula, A' is a residue formed by a condensation reaction from structure A, which has a carbonyl group (-C(=O)-) capable of protonation under superacid conditions and can be combined with an aromatic monomer containing a pentafluorophenyl group through a Friedel-Crafts type condensation reaction, wherein the carbonyl oxygen of A is removed and the residue has a structure in which it is bonded to an aromatic ring via carbon-carbon bonding, and

[0209] The above A is

[0210]

[0211] [A device selected from a group consisting of].

[0212] Here, 'superacid conditions' refer to a strong acid environment capable of inducing electrophilic activation through the protonation of carbonyl groups during the polymerization process, and specifically include trifluoromethanesulfonic acid (TFSA) or conditions having an acidity equivalent to or greater than that, i.e., an acid environment corresponding to a pKa range of approximately -5 or lower.

[0213] Each step is described in detail below.

[0214] Step 1' involves dissolving a monomer having a pentafluorophenyl group of Formula 1 and compound A of Reaction Scheme 1 below in a solvent.

[0215] The above compound A has a structure having a carbonyl group (-CO-) capable of protonation under superacid conditions, and specifically,

[0216]

[0217] It is selected from the group consisting of. Preferably, compound A is trifluoroacetophenone or N-methyl-4-piperidone. The amount of compound A may be a slight excess relative to the monomer, for example, 1.1 to 1.5 equivalents.

[0218] The solvent is a non-polar solvent, and as an example, dichloromethane can be used.

[0219] Step 2' involves adding trifluoromethanesulfonic acid dropwise to the mixture obtained in Step 1' in an ice bath.

[0220] In the above step, the reaction mixture is cooled to 0°C using an ice bath. Afterwards, trifluoromethanesulfonic acid is slowly added dropwise to the reaction mixture.

[0221] Step 3' removes the ice bath after addition and stirs and reacts the mixture at room temperature.

[0222] Step 4' involves post-processing after the reaction is complete to produce the polymer of Chemical Formula 2.

[0223] Post-treatment involves precipitating the reaction mixture in an alcohol, e.g., methanol, washing the obtained precipitate with an alcohol, e.g., methanol, and then filtering and drying it.

[0224] In addition, the polymer of Formula 3 among the polymers of the present invention can be prepared by the following steps as shown by Reaction Formula 2.

[0225] A step of dissolving a monomer having a pentafluorophenyl group of Formula 1 and compounds A and B of Reaction Formula 2 in a solvent (Step 1);

[0226] A step of adding trifluoromethanesulfonic acid dropwise to the mixture obtained in Step 1 in an ice bath (Step 2);

[0227] Step of removing the ice bath and stirring and reacting the mixture (Step 3);

[0228] A method is provided comprising the step of preparing a polymer of Formula 3 by post-processing after the reaction is completed (Step 4):

[0229] [Reaction Equation 2]

[0230]

[0231] [In the above formula, A' is a residue formed by a condensation reaction from structure A, which has a carbonyl group (-C(=O)-) capable of protonation under superacid conditions and can be combined with an aromatic monomer containing a pentafluorophenyl group through a Friedel-Crafts type condensation reaction, wherein the carbonyl oxygen of A is removed and the residue has a structure in which it is bonded to an aromatic ring via carbon-carbon bonding, and

[0232] The above A is,

[0233]

[0234] It is a group selected from the group consisting of, and

[0235] B' is a residue formed by a condensation reaction from structure B, which comprises two or more single, polycyclic, or heterocyclic aromatic rings, and is a residue having a structure in which two hydrogen atoms are removed, formed by two carbons of the aromatic rings of B each bonding to a carbon of A'.

[0236] The above B is

[0237]

[0238] [A device selected from a group consisting of].

[0239] Each step is described in detail below.

[0240] Step 1 involves dissolving the monomer having a pentafluorophenyl group of Formula 1 and compounds A and B of Formula 2 in a solvent.

[0241] Here, compound B is a structure comprising two or more aromatic rings comprising single, polycyclic, or heterocyclic groups, preferably a structure comprising two or more aromatic rings comprising single, polycyclic, or heterocyclic groups capable of polymerization under superacid conditions, and more preferably a structure comprising two or more aromatic rings comprising single, polycyclic, or heterocyclic groups capable of polymerization with protonated compound A under superacid conditions, and specifically

[0242]

[0243] It is selected from the group consisting of. The amount added may be about 2 equivalents relative to the monomer.

[0244] Except for that, it is the same as Step 1' above.

[0245] Step 2" involves adding trifluoromethanesulfonic acid dropwise to the mixture obtained in Step 1" in an ice bath, Step 3" involves removing the ice bath, stirring and reacting the mixture, and Step 4" involves post-treatment after the reaction is complete to produce a polymer of Formula 3, the detailed description thereof is the same as Steps 2', 3', and 4' above.

[0246] In addition, another aspect of the present invention provides a heat-resistant polymer in which a phosphonic acid group or a sulfonic acid group is introduced to either the fluoro position of the pentafluorophenyl of the heat-resistant polymer of Formula 2 or Formula 3 of the present invention.

[0247] Phosphonic acid groups or sulfonic acid groups are known as ion exchange groups with excellent ion conductivity. A heat-resistant polymer of the present invention, in which a phosphonic acid group or a sulfonic acid group is introduced to any one of the fluoro positions of a pentafluorophenyl, has a phosphonic acid group or a sulfonic acid group, and thus possesses high heat resistance and chemical resistance, while also having excellent ion conductivity and other functionalities, and can be utilized in fuel cells, water electrolysis, secondary batteries, etc.

[0248] The heat-resistant polymer of Formula 2 or Formula 3 of the present invention has a reactive group of pentafluorophenyl with excellent reactivity, so it can undergo a nucleophilic substitution reaction under mild conditions, and through this reaction, ion exchangers such as sulfonic acid or phosphonic acid can be introduced under mild conditions.

[0249] A heat-resistant polymer of Formula 2 or Formula 3 of the present invention, wherein a phosphonic acid group or a sulfonic acid group is introduced into any one of the fluoro positions of the pentafluorophenyl, can be prepared through the following steps:

[0250] In the case of manufacturing a heat-resistant polymer having a phosphonic acid group introduced according to the present invention,

[0251] A step of dissolving a heat-resistant polymer of Formula 2 or Formula 3 of the present invention in N,N-dimethylacetamide;

[0252] A step of adding tris(trimethylsilyl)phosphite to the above solution and stirring to react; and

[0253] A step of obtaining a heat-resistant polymer with introduced phosphonic acid groups by post-processing after the reaction.

[0254] In the case of manufacturing a heat-resistant polymer having a sulfonic acid group introduced according to the present invention,

[0255] A step of dissolving a heat-resistant polymer of Formula 2 or Formula 3 of the present invention in N,N-dimethylacetamide,

[0256] A step of adding sodium hydrosulfide hydrate to the above solution and stirring to react;

[0257] A step of obtaining a precipitate by adding an aqueous hydrochloric acid solution after the reaction, and obtaining a thiolized polymer by filtering and drying;

[0258] A step of adding the above thiolized polymer to acetic anhydride, hydrogen peroxide, and sulfuric acid to disperse it, stirring at a temperature of 50°C to 100°C, and reacting;

[0259] A step of obtaining a heat-resistant polymer with introduced sulfonic acid groups by post-treatment after the reaction.

[0260] The post-treatment described above involves cooling the mixture to room temperature, slowly pouring the cooled reaction solution into deionized water to precipitate the product, washing the precipitate under reflux with deionized water, and then filtering and drying.

[0261] The details of the process of the present invention will be explained below through examples and experimental examples. These are representative examples related to the present invention, and it should be noted that the scope of application of the present invention cannot be limited solely by these examples.

[0262] <Example 0> Synthesis of a monomer containing the functional group of the present invention

[0263] A monomer having a reactive group was synthesized according to the following reaction scheme 0.

[0264] [Reaction Equation 0]

[0265]

[0266] Pentafluorobenzoic acid (5 g, 23.576 mmol) was dissolved in 25 ml of ethanol in a reactor, and potassium tertiary-butoxide (2.645 g, 23.576 mmol) was slowly added dropwise to the solution using a dropping funnel at room temperature. After reacting for about 3 hours at room temperature, about 2 / 3 of the ethanol was removed by evaporation. 200 ml of diethyl ether was added to the residual liquid to precipitate a white solid, the precipitated solid was filtered, and vacuum dried to obtain potassium 2,3,4,5,6-pentafluorobenzoate.

[0267] Potassium 2,3,4,5,6-pentafluorobenzoate (1.214 g, 4.851 mmol), 5'-bromo-m-terphenyl (1 g, 3.234 mmol), CuI (0.123 g, 0.647 mmol), and 1,10-phenanthroline (0.117 g, 0.647 mmol) obtained above were added to a reactor and purged with Ar gas. Solvent Diglyme (11 ml) was added to the reaction mixture and heated to 130°C while stirring. After reacting at 130°C for 48 hours, the reactor was cooled and the solvent Diglyme was removed by evaporation. The residue was dissolved in methylene chloride (MC) and filtered to obtain a filtrate. Extraction was performed on the obtained filtrate using water, and MC was removed from the obtained MC layer by evaporation. The obtained residue was filtered using a silica gel filter, and the solvent of the obtained organic layer was removed. The residue was dissolved in methanol, and only the undissolved solid was filtered and vacuum dried to obtain the monomer.

[0268] The NMR results for the prepared monomer are shown in Figure 1.

[0269] As can be seen from Figure 1, the synthesis of the monomer prepared above could be confirmed.

[0270] <Example 1> Polymerization of the present invention

[0271] A polymer was synthesized according to the following reaction scheme 4.

[0272] [Reaction Equation 4]

[0273]

[0274] The monomer (2.0 g, 1.0 eq) prepared in Preparation Example 1 above and trifluoroacetophenone (0.97 g, 1.1 eq) were completely dissolved in dichloromethane (DCM, 20 mL). The reaction mixture was cooled to 0°C using an ice bath. Subsequently, trifluoromethanesulfonic acid (11.37 g, 10 eq) was slowly added dropwise to the reaction mixture. After addition, the ice bath was removed, and the reaction mixture was stirred at room temperature to proceed with the reaction. After the reaction was complete, the reaction mixture was precipitated in methanol. The precipitate was washed with methanol, filtered, and dried to obtain a polymer (yield 95%).

[0275] The NMR results for the manufactured polymer are shown in Figure 2.

[0276] As can be seen from Figure 2, the synthesis of the above-mentioned polymer was confirmed.

[0277] <Example 2> Polymerization of the present invention

[0278] A polymer was synthesized according to the following reaction scheme 5.

[0279] [Reaction Equation 5]

[0280]

[0281] 1.0 g (0.5 eq) of the monomer prepared in Preparation Example 1, 0.58 g (0.5 eq) of meta-phenyl, and 0.97 g (1.1 eq) of trifluoroacetophenone were completely dissolved in 10.9 mL of DCM. The reaction mixture was cooled to 0°C using an ice bath. Subsequently, 7.58 g (10 eq) of trifluoromethanesulfonic acid was slowly added dropwise to the reaction mixture. After addition, the ice bath was removed, and the reaction mixture was stirred at room temperature to proceed with the reaction. After the reaction was complete, the reaction mixture was precipitated in methanol. The precipitate was washed with methanol, filtered, and dried to obtain a polymer (yield 90%).

[0282] The NMR results for the manufactured polymer are shown in Figure 3.

[0283] As can be seen from Figure 3, the synthesis of the above-mentioned polymer was confirmed.

[0284] <Example 3> Polymerization of the present invention

[0285] A polymer was synthesized according to the following reaction scheme 6.

[0286] [Reaction Equation 6]

[0287]

[0288] 1.0 g (0.5 eq) of the monomer prepared in Preparation Example 1, 0.39 g (0.5 eq) of biphenyl, and 0.97 g (1.1 eq) of trifluoroacetophenone were completely dissolved in 10.0 mL of DCM. The reaction mixture was cooled to 0°C using an ice bath. Subsequently, 7.58 g (10 eq) of trifluoromethanesulfonic acid was slowly added dropwise to the reaction mixture. After addition, the ice bath was removed, and the reaction mixture was stirred at room temperature to proceed with the reaction. After the reaction was complete, the reaction mixture was precipitated in methanol. The precipitate was washed with methanol, filtered, and dried to obtain a polymer (yield 90%).

[0289] The NMR results for the manufactured polymer are shown in Figure 4.

[0290] As can be seen from Figure 4, the synthesis of the above-mentioned polymer was confirmed.

[0291] <Example 4> Polymerization of the present invention

[0292] A polymer was synthesized according to the following reaction scheme 7.

[0293] [Reaction Equation 7]

[0294]

[0295] 1.0 g (0.5 eq) of the monomer prepared in Preparation Example 1 and 0.3 g (0.5 eq) of N-methyl-4-piperidone were completely dissolved in 11.7 mL of DCM. The reaction mixture was cooled to 0°C using an ice bath. Subsequently, 0.17 g (0.9 eq) of trifluoroacetic acid was added to the reaction mixture. 2.23 mL (10 eq) of trifluoromethanesulfonic acid was added dropwise to the reaction mixture. After addition, the reaction was carried out by slowly stirring while raising the temperature of the reaction mixture to room temperature without removing the ice bath. After the reaction was complete, the reaction mixture was precipitated in isopropanol. The precipitate was washed with isopropanol, filtered, and dried (yield 90%). 1.11 g of the precipitate was completely dissolved in 7.4 mL of NMP and then added dropwise to a 1M aqueous K2CO3 solution to remove the acid. The precipitate was filtered, washed with distilled water during filtration, and then dried to obtain a polymer.

[0296] The NMR results for the manufactured polymer are shown in Figure 5.

[0297] As can be seen from Figure 5, the synthesis of the above-mentioned polymer was confirmed.

[0298] <Example 5> Polymerization of the present invention

[0299] A polymer was synthesized according to the following reaction scheme 8.

[0300] [Reaction Equation 8]

[0301]

[0302] 2.0 g (1.0 eq) of the monomer prepared in Preparation Example 1 above was completely dissolved in 20.9 mL of DCM. The reaction mixture was cooled to 0°C using an ice bath. Subsequently, 0.7355 g (1.3 eq) of 1,1,1-trifluoroacetic acid was added to the reaction mixture. 2.22 mL (5 eq) of trifluoromethanesulfonic acid was added dropwise to the reaction mixture. After addition, the reaction was carried out by slowly stirring while raising the temperature of the reaction mixture to room temperature without removing the ice bath. After the reaction was complete, the reaction mixture was precipitated in methanol. The precipitate was washed with methanol, filtered, and dried (yield 95%).

[0303] The NMR results for the prepared polymer are shown in Fig. 6.

[0304] As can be seen from Figure 6, the synthesis of the polymer manufactured above could be confirmed.

[0305] <Example 6> Polymerization of the present invention

[0306] A polymer was synthesized according to the following reaction scheme 9.

[0307] [Reaction Equation 9]

[0308]

[0309] 1.20 g (1.0 eq) of the monomer prepared in Preparation Example 1 and 2.10 g (4.5 eq) of biphenyl were completely dissolved in 39.0 mL of DCM. Subsequently, 2.43 g (7.15 eq) of 1,1,1-trifluoroacetic acid was added to the reaction mixture. The reaction mixture was cooled to 0°C using an ice bath. Then, 7.31 mL (27.5 eq) of trifluoromethanesulfonic acid was added dropwise to the reaction mixture. After addition, the reaction was carried out by slowly stirring while raising the temperature of the reaction mixture to room temperature without removing the ice bath. After the reaction was complete, the reaction mixture was precipitated in methanol. The precipitate was washed with methanol, filtered, and dried (yield 90%).

[0310] The NMR results for the manufactured polymer are shown in Fig. 7.

[0311] As can be seen from Fig. 7, the synthesis of the polymer manufactured above could be confirmed.

[0312] <Example 7> Synthesis of a polymer substituted with phosphonic acid functional groups

[0313] A polymer was synthesized according to the following reaction scheme 10.

[0314] [Reaction Equation 10]

[0315]

[0316] The polymer of Example 1 (2.0 g) with introduced pentafluorophenyl groups was completely dissolved in N,N-dimethylacetamide (DMAc, 6.38 mL). Tris(trimethylsilyl)phosphite (4.33 g, 4 eq) was added to the polymer solution, and the reaction mixture was purged with nitrogen to create an inert atmosphere, and an outlet was installed. The reaction temperature was raised to 180°C, and the reaction was carried out by reflux for 8 hours. After the reaction was complete, the reaction mixture was cooled to room temperature. The cooled reaction mixture was slowly poured into deionized water (100 mL) to precipitate the product. The precipitate was refluxed with deionized water and washed. It was separated by filtration and dried (yield 90%).

[0317] The NMR results for the manufactured polymer are shown in Fig. 14.

[0318] As can be seen from Fig. 14, the synthesis of the polymer manufactured above could be confirmed.

[0319] <Example 8> Synthesis of a polymer substituted with sulfonic acid functional groups

[0320] A polymer was synthesized according to the following reaction scheme 11.

[0321] [Reaction Equation 11]

[0322]

[0323] The polymer of Example 1 (1.0 g) with introduced pentafluorophenyl groups was completely dissolved in N,N-dimethylacetamide (DMAc, 10 mL). Sodium hydrosulfide hydrate (0.30 g, 3 eq) was slowly added in small amounts to the polymer solution, and the mixture was stirred at room temperature for 24 hours. After the reaction was complete, the reaction mixture was poured into a 1 M aqueous HCl solution (50 mL) to precipitate. The precipitate was washed with deionized water, filtered, and dried. The previously prepared thiolized polymer (1.0 g) was added to acetic anhydride (10.0 mL), hydrogen peroxide (30 wt%, 7.0 mL), and sulfuric acid (H2SO4, 99%, 1.0 mL) and dispersed in the reaction solution. The mixture was stirred at 50°C for 24 hours, and then the temperature was raised to 100°C and stirred for an additional 1 hour. Once the reaction was complete, the reaction solution was concentrated using a rotovap, and the residue was dialyzed with deionized water. Dialysis was performed in a 0.05 M NaCl aqueous solution for 24 hours, followed by an additional 48 hours with deionized water. The dialyzed product was dried after removing residual moisture with a rotovap (yield 85%).

[0324] The NMR results for the manufactured polymer are shown in Fig. 15.

[0325] As can be seen from Fig. 15, the synthesis of the polymer manufactured above could be confirmed.

[0326] <Example 9> Synthesis of a Polymer Substituted with Phosphonic Acid Functional Groups

[0327] A polymer was synthesized according to the following reaction scheme 12.

[0328] [Reaction Equation 12]

[0329]

[0330] The polymer of Example 5 (2.0 g) with introduced pentafluorophenyl groups was completely dissolved in N,N-dimethylacetamide (DMAc, 21.5 mL). Tris(trimethylsilyl)phosphite (4.33 g, 4 eq) was added to the polymer solution, and the reaction mixture was purged with nitrogen to create an inert atmosphere, and an outlet was installed. The reaction temperature was raised to 180°C, and the reaction was carried out by reflux for 8 hours. After the reaction was complete, the reaction mixture was cooled to room temperature. The cooled reaction mixture was slowly poured into deionized water (100 mL) to precipitate the product. The precipitate was refluxed with deionized water and washed. It was separated by filtration and dried (yield 90%).

[0331] The NMR results for the manufactured polymer are shown in Fig. 16.

[0332] As can be seen from Fig. 16, the synthesis of the polymer manufactured above could be confirmed.

[0333] <Example 10> Synthesis of a polymer substituted with sulfonic acid functional groups

[0334] A polymer was synthesized according to the following reaction scheme 13.

[0335] [Reaction Equation 13]

[0336]

[0337] The polymer of Example 5 (2.0 g) with introduced pentafluorophenyl groups was completely dissolved in N,N-dimethylacetamide (DMAc, 20 mL). Sodium hydrosulfide hydrate (0.70 g, 3 eq) was slowly added in small amounts to the polymer solution, and the mixture was stirred at room temperature for 24 hours. After the reaction was complete, the reaction mixture was poured into a 1 M aqueous HCl solution (100 mL) to precipitate. The precipitate was washed with deionized water, filtered, and dried. The previously prepared thiolized polymer (2.0 g) was added to acetic anhydride (10.0 mL), hydrogen peroxide (30 wt%, 7.0 mL), and sulfuric acid (H2SO4, 99%, 2.0 mL) and dispersed in the reaction solution. The mixture was stirred at 50°C for 24 hours, and then the temperature was raised to 100°C and stirred for an additional 1 hour. Once the reaction was complete, the reaction solution was concentrated using a rotovap, and the residue was dialyzed with deionized water. Dialysis was performed in a 0.05 M NaCl aqueous solution for 24 hours, followed by an additional 48 hours with deionized water. The dialyzed product was dried after removing residual moisture with a rotovap (yield 85%).

[0338] The NMR results for the manufactured polymer are shown in Fig. 17.

[0339] As can be seen from Fig. 17, the synthesis of the polymer manufactured above could be confirmed.

[0340] <Experimental Example 1> Chemical Structure of Polymerized Polymer - ATR-FTIR

[0341] ATR-FTIR data was obtained for the polymers polymerized in Examples 1 to 6 using an ATR-FTIR device.

[0342] The results are shown in Fig. 8.

[0343] The important peak is as follows: 3000–3100 cm⁻¹ -1 At CH stretch (aromatic), 2900-3000 cm -1At CH stretch (aliphatic), 1500 cm -1 Near CC stretch (aromatic), 1150 cm -1 , 1230 cm -1 Near CF stretch, 1000 cm -1 In-plain CH bending (aromatic) in the vicinity, 750 cm -1 Out-of-plain CH bending (aromatic) can be observed in the vicinity.

[0344] <Experimental Example 2> Physical Properties of Polymerized Polymer - GPC

[0345] GPC data was obtained for the polymers polymerized in Examples 1 to 6 using a GPC device.

[0346] The results are shown in Fig. 9.

[0347] As can be seen from Figure 9, the number average molecular weight is distributed from 18,000 to 27,000, the weight average molecular weight is distributed from 37,000 to 53,000, and the PDI was measured to be 2.1 or less. This means that the monomer of Formula 1 can be polymerized into a high molecular weight polymer.

[0348] <Experimental Example 3> Physical Properties of Polymerized Polymer - TGA

[0349] TGA data was obtained for the polymers polymerized in Examples 1 to 5 using a TGA device.

[0350] The results are shown in Fig. 10.

[0351] As can be seen from Figure 10, the temperature at which the weight was reduced by 5% was distributed between 422°C and 525°C, with two major weight reductions. When the differential values ​​were checked, the first weight reduction was distributed between 467°C and 533°C, and the second weight reduction was distributed between 543°C and 647°C. After raising the temperature to 800°C, the final remaining char yield maintained a high value of 58 to 72%. These results indicate that the polymerized polymer exhibits sufficient heat resistance as an engineering polymer.

[0352] <Experimental Example 4> Physical Properties of Polymerized Polymer - DSC

[0353] DSC data was obtained for the polymers polymerized in Examples 1 to 5 using a DSC device.

[0354] The results are shown in Fig. 11.

[0355] As can be seen from Fig. 11, DSC measurement results show that the glass transition temperatures of the polymers in Examples 1 to 4 range from 219°C to 222°C. In addition, the glass transition temperature of the polymer in Example 5 was observed at approximately 250°C. As shown in the above results, it was confirmed that all polymerized polymers can maintain their mechanical and thermal properties up to 200°C or higher.

[0356] <Experimental Example 5> Physical Properties of Polymerized Polymer - Solubility

[0357] Solubility data was obtained by measuring the solubility of the polymers polymerized in Examples 1 to 3, 5 and 6 in NMP, DMAC, THF, chloroform, and dichloromethane.

[0358] The results are shown in Fig. 12.

[0359] As can be seen from Figure 12, when the solubility of the polymer in various organic solvents was checked, it was confirmed that it dissolves well in commercial organic solvents such as NMP, DMAc, THF, chloroform, and dichloromethane. Since all of the polymerized reactive polymers exhibited excellent solubility, it was confirmed that they can be utilized in polymer analogous reactions in various solvent environments.

[0360] <Experimental Example 6> Physical properties of polymerized polymer - Tensile strength

[0361] Tensile strength data was obtained for the polymers polymerized in Examples 1 and 5 using a tensile strength measuring device.

[0362] The results are shown in Fig. 13.

[0363] As can be seen from Figure 13, in the tensile test of the polymers, it was confirmed that the polymers of Example 1 and Example 5 each exhibited excellent tensile properties, with fracture stresses of 41.6 MPa and 35.9 MPa, fracture strains of 7.4% and 17.7%, stiffness of 28927 N / m and 21965 N / m, and Young's modulus of 3063 MPa and 1441 MPa. This indicated that Example 5, containing methyl groups, possessed more flexible mechanical properties compared to Example 1, which contains phenyl groups.

Claims

1. A monomer having a pentafluorophenyl group of the following chemical formula 1: [Chemical Formula 1] 2. A method for manufacturing the monomer of claim 1, Step of adding potassium tert-butoxide alcohol solution dropwise to a pentafluorobenzoic acid alcohol solution (Step 1); A step of post-treating the reaction product obtained in Step 1 above to obtain potassium 2,3,4,5,6-pentafluorobenzoate (Step 2); Mixing the potassium 2,3,4,5,6-pentafluorobenzoate and 5-bromo-m-terphenyl obtained in Step 2, and Ar purging (Step 3); Step 4: adding and stirring deglim to the mixture obtained in Step 3, and raising the temperature to react; and A method comprising the step (step 5) of post-treating the reaction product obtained in step 4 above to obtain the monomer of claim 1.

3. In paragraph 2, the alcohol in step 1 is ethanol, and The post-treatment of Step 2 evaporates the alcohol, adds diethyl ether to the residual liquid to precipitate a white solid, filters and dries the solid, and Step 3 comprises mixing the potassium 2,3,4,5,6-pentafluorobenzoate and 5-bromo-m-terphenyl obtained in Step 2 with CuI and 1,10-phenanthroline, and purging with Ar. In step 4, the temperature is raised to 130℃, and A method characterized by the post-treatment of step 5, which involves evaporating the deglim and adding methylene chloride to obtain a residual liquid, adding water to the liquid, evaporating the methylene chloride from the methylene chloride layer, filtering, dissolving the residue in methanol to obtain an undissolved solid, and drying.

4. A compound containing a carbonyl group and the monomer of claim 1 obtained by polymerizing by polyhydroxyalkylation (Friedel-Crafts aromatic electrophilic substitution reaction), or A reactive heat-resistant polymer obtained by copolymerizing the monomer of claim 1 with an aromatic ring.

5. A heat-resistant polymer according to claim 4, characterized in that the heat-resistant polymer is a reactive heat-resistant polymer of the following chemical formula 2 comprising the monomer of claim 1: [Chemical Formula 2] [In the above formula, A' is a residue formed by a condensation reaction from structure A, which has a carbonyl group (-C(=O)-) capable of protonation under superacid conditions and can be combined with an aromatic monomer containing a pentafluorophenyl group through a Friedel-Crafts type condensation reaction, wherein the carbonyl oxygen of A is removed and the residue has a structure in which it is bonded to an aromatic ring via carbon-carbon bonds.

6. In paragraph 5, the above structure A A heat-resistant polymer characterized by being selected from the group consisting of 7. A heat-resistant polymer according to claim 4, characterized in that the heat-resistant polymer is a reactive heat-resistant polymer of the following chemical formula 3 comprising the monomer of claim 1: [Chemical Formula 3] [In the above formula, A' is a residue formed by a condensation reaction from structure A, which has a carbonyl group (-C(=O)-) capable of protonation under superacid conditions and can be combined with an aromatic monomer containing a pentafluorophenyl group through a Friedel-Crafts type condensation reaction, wherein the carbonyl oxygen of A is removed and the residue has a structure in which it is bonded to an aromatic ring via a carbon-carbon bond, and B' is a residue formed by a condensation reaction from structure B, which comprises two or more single, polycyclic, or heterocyclic aromatic rings, and is a residue having a structure with two hydrogen atoms removed, formed by two carbons of the aromatic rings of B each bonding to a carbon of A'.

8. In paragraph 7, the above structure A A heat-resistant polymer characterized by being selected from the group consisting of 9. A heat-resistant polymer according to claim 7, characterized in that the structure B comprises two or more aromatic rings comprising a single ring, a polycyclic or heterocyclic ring, which is capable of polymerization under superacid conditions.

10. A heat-resistant polymer according to claim 7, characterized in that the structure B comprises two or more single, polycyclic, or heterocyclic aromatic rings capable of polymerizing with compound A protonated under superacid conditions.

11. In Clause 7, the above structure B A heat-resistant polymer characterized by being selected from the group consisting of 12. A method for producing the polymer of claim 6 according to the following reaction scheme 1, A step of dissolving a monomer having a pentafluorophenyl group of Chemical Formula 1 and compound A of Reaction Scheme 1 below in a solvent (Step 1'); A step of adding trifluoromethanesulfonic acid dropwise to the mixture obtained in step 1' in an ice bath (step 2'); Step of removing the ice bath and stirring and reacting the mixture at room temperature (Step 3'); and A method comprising the step (step 4') of preparing a polymer of Formula 2 by post-processing after the reaction is completed. [Reaction Equation 1] [In the above formula, A' is a residue formed by a condensation reaction from structure A, which has a carbonyl group (-C(=O)-) capable of protonation under superacid conditions and can be combined with an aromatic monomer containing a pentafluorophenyl group through a Friedel-Crafts type condensation reaction, wherein the carbonyl oxygen of A is removed and the residue has a structure in which it is bonded to an aromatic ring via carbon-carbon bonding, and The above A is [A device selected from a group consisting of].

13. In paragraph 12, the solvent of step 1' is dichloromethane, and A method characterized by the post-treatment of step 4' comprising precipitating the reaction mixture in methanol to obtain a precipitate, washing it with methanol, filtering, and drying it.

14. A method for preparing the polymer of claim 7 by the following reaction scheme 2, A step of dissolving a monomer having a pentafluorophenyl group of Formula 1 and compounds A and B of Reaction Formula 2 in a solvent (Step 1); A step of adding trifluoromethanesulfonic acid dropwise to the mixture obtained in Step 1 in an ice bath (Step 2); Step of removing the ice bath and stirring and reacting the mixture (Step 3); A method comprising the step of preparing a polymer of Formula 3 by post-processing after the reaction is completed (Step 4). [Reaction Equation 2] [In the above formula, A' is a residue formed by a condensation reaction from structure A, which has a carbonyl group (-C(=O)-) capable of protonation under superacid conditions and can be combined with an aromatic monomer containing a pentafluorophenyl group through a Friedel-Crafts type condensation reaction, wherein the carbonyl oxygen of A is removed and the residue has a structure in which it is bonded to an aromatic ring via carbon-carbon bonding, and The above A is, It is a group selected from the group consisting of, and B' is a residue formed by a condensation reaction from structure B, which comprises two or more single, polycyclic, or heterocyclic aromatic rings, and is a residue having a structure in which two hydrogen atoms are removed, formed by two carbons of the aromatic rings of B each bonding to a carbon of A'. The above B is [A device selected from a group consisting of].

15. In paragraph 14, the solvent of step 1" is dichloromethane, and A method characterized by the post-treatment of step 4 including precipitating the reaction mixture in methanol to obtain a precipitate, washing it with methanol, filtering, and drying it.

16. A heat-resistant polymer in which a phosphonic acid group or a sulfonic acid group is introduced into any one of the fluoro positions of the pentafluorophenyl group of the heat-resistant polymer of Formula 2 of Claim 5 or Formula 3 of Claim 7.

17. A method for manufacturing a heat-resistant polymer having a phosphonic acid group introduced according to claim 16, A heat-resistant polymer of Formula 2 of Claim 5 or Formula 3 of Claim 7 is dissolved in N,N-dimethylacetamide, and Tris(trimethylsilyl)phosphite is added to the above solution and stirred to react; A method comprising obtaining a heat-resistant polymer with introduced phosphonic acid groups by post-treatment after the reaction.

18. A method for manufacturing a heat-resistant polymer having a sulfonic acid group introduced according to claim 11, A heat-resistant polymer of Formula 2 of Claim 5 or Formula 3 of Claim 7 is dissolved in N,N-dimethylacetamide, and Sodium hydrosulfide hydrate is added to the above solution and stirred to react; After the reaction, an aqueous hydrochloric acid solution is added to obtain a precipitate, and the precipitate is filtered and dried to obtain a thiolized polymer; The above thiolized polymer is added to acetic anhydride, hydrogen peroxide, and sulfuric acid to disperse it, stirred at a temperature of 50°C to 100°C, and reacted; A method comprising obtaining a heat-resistant polymer with introduced sulfonic acid groups by post-treatment after the reaction.

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