Polymer compound and method for producing the same, polymer, and adhesive composition
A novel polymer compound with 1,2-dithiolane in the side chain, produced via a Passerini reaction, addresses inefficiencies in conventional methods by enabling efficient synthesis and adjustable properties, offering self-healing and recyclability.
Patent Information
- Application Number
- JP2024005661
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2024-01-17
- Publication Date
- 2025-07-30
AI Technical Summary
Conventional methods for producing polymers with 1,2-dithiolane in the side chain are inefficient, require multiple synthesis steps, and do not easily allow adjustment of structural and physical properties such as glass transition temperature and elastic modulus.
A novel polymer compound with 1,2-dithiolane in the side chain is produced through a Passerini reaction using α-lipoic acid, an aldehyde, and a diisocyanide, allowing direct use of starting materials without conversion to monomers, thereby reducing synthesis steps and enabling adjustment of molecular weight and physical properties.
The polymer compound exhibits self-healing, remoldability, and recyclability, with adjustable properties like glass transition temperature and elastic modulus, and can be regenerated by de-crosslinking.
Smart Images
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Abstract
Description
Technical Field
[0001] The present invention relates to a polymer compound, a method for producing the same, a multimer, and an adhesive composition.
Background Art
[0002] Conventionally, polymers having excellent mechanical properties and material properties such as adhesive strength as crosslinked polymers and having recyclable characteristics have attracted attention. In general, in a crosslinked polymer, polymer chains are linked by strong chemical bonds, so once a crosslinked structure is formed, it is difficult to remold or recycle the material. However, in recent years, by introducing dynamic bonds (reversible chemical bonds) into the crosslinked polymer, a method has been developed that allows recombination or decomposition of the crosslinked structure by external stimuli such as heat, enabling self-healing, remoldability, recyclability, etc. of the polymer material.
[0003] In polymers having dynamic bonds, it is possible to produce a variety of materials by combining functional groups that give recyclability and responsiveness with a main chain that gives basic physical properties. Among dynamic bonds, the disulfide bond is excellent because it has a good balance between bond stability and reactivity and can be easily and selectively activated by light irradiation, chemicals, and other external stimuli. For this reason, there are many reports on crosslinked polymers having disulfide bonds (S-S bonds). Among them, polymers having dynamic properties based on ring-opening polymerization - bond recombination - depolymerization of 5-membered cyclic disulfide (1,2-dithiolane) have rapidly attracted attention.
[0004] Among the crosslinked polymers derived from compounds containing 1,2 - dithiolane, many of the polymers proposed so far are polymers containing S - S bonds formed by the ring - opening of dithiolane in the main chain (for example, Non - Patent Document 1). However, in polymers whose main chain is formed by the ring - opening polymerization reaction of 1,2 - dithiolane, many physical properties such as mechanical properties (such as elastic modulus), adhesiveness, water resistance, and glass transition temperature are based on the main chain formed by the ring - opening of 1,2 - dithiolane. Therefore, it is difficult to synthesize polymers having physical properties significantly different from those of this main chain.
[0005] On the other hand, polymers having 1,2 - dithiolane in the side chain have also been proposed. However, many of the examples of such polymers are obtained by a method of reacting a compound containing 1,2 - dithiolane with an existing polymer to obtain the target polymer (for example, Non - Patent Document 2), and there are few reported examples of methods for obtaining polymers having 1,2 - dithiolane in the side chain by the polymerization of raw materials (monomers) containing 1,2 - dithiolane. For example, as such an example, a polycarbonate having 1,2 - dithiolane in the side chain by ring - opening polymerization of a cyclic carbonate compound derived from lipoic acid, a natural compound (Non - Patent Document 3), and polymers by radical polymerization of (meth) acrylate compounds also derived from lipoic acid have been reported (Non - Patent Documents 4 and 5).
Prior Art Documents
Non - Patent Documents
[0006]
Non - Patent Document 1
Non - Patent Document 2
[0007] However, conventional methods such as those in Non-Patent Documents 3-5 convert starting materials such as lipoic acid into monomers through one-step or multi-step synthesis reactions and then carry out polymerization reactions. Therefore, from the viewpoints of the number of synthesis steps and atom economy, a more efficient method for producing polymers has been demanded.
[0008] Furthermore, conventional methods such as Non-Patent Documents 3-5 have not always made it easy to adjust the structure such as the polymer main chain and molecular weight, physical properties such as glass transition temperature and elastic modulus, and material properties such as adhesiveness due to the high reactivity of 1,2-dithiolane with radicals and nucleophiles.
[0009] The present invention has been made in view of the above circumstances, and an object thereof is to provide a novel polymer compound having 1,2-dithiolane in a side chain, a method for producing the polymer compound excellent in production efficiency and easy to adjust material properties, a multimer in which a plurality of the polymer compounds are bonded, and an adhesive composition containing the polymer compound or the multimer.
Means for Solving the Problems
[0010] In order to solve the above problems, the following polymer compound, a method for producing the same, a multimer, and an adhesive composition are provided. [1] A polymer compound containing a repeating unit represented by the following general formula (1A).
Chemical formula
[10] An adhesive composition containing the polymer compound according to any one of [1] to [5] or the multimer according to [9]. [Advantages of the Invention]
[0011] The polymer compound of the present invention is a novel polymer compound having 1,2-dithiolane in its side chain, and has self-healing properties, reshaping properties, and reusability. The polymer compound and multimer of the present invention can be adjusted in terms of structure such as the molecular weight of the polymer compound, physical properties such as glass transition temperature and elastic modulus, and material properties such as adhesiveness according to the compound constituting the monomer (repeating unit).
[0012] The polymer compound (polymer) of the present invention produces a crosslinked polymer that exhibits elastomer-like properties by heating or the like. Further, this crosslinked polymer can be regenerated into the polymer before crosslinking by means of de-crosslinking by reacting a catalytic amount of a thiol compound and a base compound.
[0013] According to the production method of the polymer compound of the present invention, the above novel polymer compound is provided. Further, according to the production method of the polymer compound of the present invention, the number of synthesis steps can be suppressed, the atom economy is excellent, and the above novel polymer compound can be efficiently produced. Further, according to the production method of the polymer compound of the present invention, the structure such as the main chain and molecular weight of the polymer, physical properties such as glass transition temperature and elastic modulus, and material properties such as adhesiveness can be easily adjusted.
[0014] The adhesive composition of the present invention can maintain the adhesive force even when the adhesion and detachment to the adherend are repeated. [Brief Description of the Drawings]
[0015]
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Mode for Carrying Out the Invention
[0016] Hereinafter, an embodiment of the polymer compound of the present invention and its production method will be described. In this specification, the numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value.
[0017] <Polymer Compound> The polymer compound of the present invention contains a repeating unit represented by the following general formula (1A).
[0018] [Chemical formula]
[0019] In formula 1A, n represents the number of repeating units and is an integer of 1 or more. Further, in the polymer compound of this embodiment, n is preferably 2 or more, for example, 2 to 20 or 21 or more. Typically, the polymer compound of this embodiment is a polymer.
[0020] In formula 1A, X1 and X2 are each independent, and at least one of X1 and X2 is 1,2-dithiolane or an organic group having 1,2-dithiolane at its end. In other words, in the polymer compound of this embodiment, both X1 and X2 may be 1,2-dithiolane or an organic group having 1,2-dithiolane at its end, and either one of X1 and X2 may be 1,2-dithiolane or an organic group having 1,2-dithiolane at its end.
[0021] In the present invention, the term "organic group" means, unless otherwise specified, an atomic group obtained by removing one or more hydrogen atoms from an organic compound.
[0022] Furthermore, in formula 1A, X1 and X2 may be the same as or different from each other. For example, when both X1 and X2 are organic groups having 1,2-dithiolane at their ends, X1 and X2 may be the same organic group or different organic groups. Also, when n is 2 or more, the plurality of X1 may be the same as or different from each other, and the plurality of X2 may be the same as or different from each other. In other words, when n is 2 or more, the plurality of X1 may be the same or a plurality of types of organic groups, and the plurality of X2 may be the same or a plurality of types of organic groups.
[0023] In one embodiment of the polymer compound of the present invention, in Formula 1A, at least one of X1 and X2 is preferably a group represented by the following Formula (1B) or Formula (1C).
[0024]
Chemical formula
Chemical formula
[0025] In Formula 1B, * indicates the bonding position, and R1 represents an organic group. The organic group constituting R1 may have a substituent on any carbon atom.
[0026] Preferably, R1 is an organic group having 1 to 32 carbon atoms, for example.
[0027] The organic group constituting R1 is not particularly limited, and examples thereof include an aliphatic group, an aromatic group, and a carbon group containing a hetero element. Specifically, in one form of the polymer compound of the present invention, for example, the organic group constituting R1 can be exemplified by an alkylene group, a phenylene group, a naphthylene group, etc., which may have a substituent. Examples of the hetero element include nitrogen (N), oxygen (O), sulfur (S), phosphorus (P), chlorine (Cl), iodine (I), bromine (Br), etc.
[0028] The alkylene group is not particularly limited, but is preferably a linear or branched alkylene group having 1 to 8 carbon atoms, for example. Specifically, examples thereof include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, etc. These alkylene groups may contain a nitrogen atom, an oxygen atom, a sulfur atom, etc., or may be via a phenylene group.
[0029] Furthermore, in one embodiment of the polymer compound of the present invention, the organic group constituting R1 may include, for example, a structure in which two phenylene groups are bonded via an alkylene group (which may have a substituent). Specifically, for example, the organic group constituting R1 may include a structure represented by -Ph-C m H 2m -Ph- (where m is an integer of 1 or more).
[0030] Furthermore, the organic group constituting R1 may have a substituent on any carbon. Examples of the substituent include a halogen atom, a hydroxyl group, a primary to tertiary amino group, a quaternary ammonium group, an ether group, a polyalkylene glycol group having 2 to 4 carbon atoms, a carbonyl group, a carboxyl group, an amide group, a cyano group, a carbamate group, an epoxy group, an isocyanate group, an acrylate group, a methacrylate group, and the like.
[0031] Furthermore, in the polymer compound of this embodiment, a form is included in which either one of X1 and X2 is 1,2-dithiolane or an organic group having 1,2-dithiolane at an end, and the other is another organic group R2 not having 1,2-dithiolane at an end. In this case, the other organic group R2 is not particularly limited, but may be, like R1, an aliphatic group, an aromatic group, a carbon group containing a hetero element, or the like.
[0032] In Formula 1A, R3 represents an organic group, and when n is 2 or more, a plurality of R3s may be the same as or different from each other. Similarly, R4 represents an organic group, and when n is 2 or more, a plurality of R4s may be the same as or different from each other.
[0033] In one embodiment of the polymer compound of the present invention, the organic groups constituting R3 and R4 can be exemplified by an aliphatic group, an aromatic group, a carbon group containing a hetero element, etc., similar to R1, and may have a substituent. Specifically, for example, the organic groups constituting R3 and R4 can be exemplified by an alkylene group, a phenylene group, a naphthylene group, etc. that may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, a primary to tertiary amino group, a quaternary ammonium group, an ether group, a polyalkylene glycol group having 2 to 4 carbon atoms, a carbonyl group, a carboxyl group, an amide group, a cyano group, a carbamate group, an epoxy group, an isocyanate group, an acrylate group, a methacrylate group, etc.
[0034] Furthermore, in one form of the polymer compound of the present invention, the organic groups constituting R3 and R4 can include, for example, a structure in which two phenylene groups are bonded via an alkylene group (which may have a substituent). Specifically, for example, the organic groups constituting R3 and R4 can include a structure represented by -Ph-C m H 2m -Ph- (m is an integer of 1 or more).
[0035] The number of carbon atoms of the organic groups represented by R3 and R4 is not particularly limited, but R3 is preferably an organic group having 1 to 16 or 17 to 32 carbon atoms (an organic group having 1 to 32 carbon atoms), and R4 is preferably an organic group having 1 to 16 or 17 to 32 carbon atoms (an organic group having 1 to 32 carbon atoms).
[0036] Furthermore, the polymer compound of this embodiment may have arbitrary groups at both ends of the repeating unit shown in Formula 1A.
[0037] The molecular weight of the polymer compound of this embodiment is not particularly limited and may be appropriately adjusted according to the application. Generally, as the number average molecular weight, it is preferably 2000 or more, and more preferably 6000 or more.
[0038] The polymer compound (polymer) of this embodiment has α-acyloxypolyamide in the main chain and 1,2-dithiolane in the side chain. In the polymer compound of this embodiment, for example, when an external stimulus such as heating is applied, both the ring-opening and ring-closing reactions of 1,2-dithiolane occur, and the positions of the cross-linked portions and the main chain change in the polymer, resulting in moldability and self-healing properties. The polymer compound (polymer) of this embodiment is excellent in self-healing properties, remoldability, recyclability, etc. Specifically, the polymer compound (polymer) of this embodiment produces a cross-linked polymer that exhibits elastomer-like properties by heating or the like. Further, this cross-linked polymer can be regenerated into the polymer before cross-linking by de-cross-linking by, for example, reacting a catalytic amount of a thiol compound and a base compound.
[0039] Furthermore, in one embodiment of the polymer compound of the present invention, the polymer compound of the present invention is represented by, for example, the following general formula (6A).
[0040]
Chemical formula
[0041] The polymer compound of this embodiment contains a repeating unit represented by the above formula 1A. In formula 6A, n, X1, X2, R3 and R4 are the same as those in the above formula 1A.
[0042] In formula 6A, X3 is the same as X1 or X2. That is, X3 is 1,2-dithiolane, or an organic group having 1,2-dithiolane at the end, or another organic group not having 1,2-dithiolane.
[0043] Also in the polymer compound of this embodiment, for example, the groups adjacent to R3 and R4 located at the ends may be substituted with other substituents or may be hydrolyzed or the like.
[0044] Further, in another embodiment of the polymer compound of the present invention, the polymer compound of the present invention is represented by, for example, the following general formula (6B). The polymer compound represented by the general formula (6B) has aldehyde groups at both ends of the main chain.
Chemical formula
[0045] The polymer compound of this embodiment contains a repeating unit represented by the above formula 1A. In formula 6B, n, X1, X2, R3 and R4 are the same as those in the above formula 1A.
[0046] Also in the polymer compound of this embodiment, for example, the groups adjacent to R3 and R4 located at the ends may be substituted with other substituents.
[0047] The polymer compounds (polymers) of these embodiments have α-acyloxypolyamide in the main chain and 1,2-dithiolane in the side chain. In the polymer compound of this embodiment, for example, when an external stimulus such as heating is applied, both the ring-opening and ring-closing reactions of 1,2-dithiolane occur, and the positions of the cross-linked portions and the main chain change in the polymer, thereby exhibiting moldability and self-healing properties. The polymer compounds (polymers) of this embodiment are excellent in self-healing properties, remoldability, reusability, etc. Specifically, the polymer compounds (polymers) of these embodiments generate a cross-linked polymer exhibiting elastomer-like properties by heating or the like. Further, this cross-linked polymer can be regenerated into the polymer before cross-linking by de-cross-linking by acting a catalytic amount of a thiol compound and a base compound or the like.
[0048] Also, since X1, X2, X3 constituting the side chain and R3 and R4 constituting the main chain of the polymer compound (polymer) of this embodiment can be composed of various predetermined groups, they can be adjusted to have desired molecular weight, structure, physical properties such as glass transition temperature and elastic modulus, and material properties such as adhesiveness.
[0049] Specifically, the polymer compound of the present invention can be used for various purposes, such as a recyclable polymer or a self-repairable polymer. In addition, the polymer compound of the present invention can be suitably used for applications such as a soft actuator, a 3D printable polymer, and an electronic circuit sealing material.
[0050] <Method of manufacturing polymer compounds> One embodiment of the method for producing a polymer compound of the present invention includes a step of subjecting at least one of compounds represented by the following general formula (2A) or (2B), a compound represented by the general formula (3), and a compound represented by the general formula (4) to a Passerini reaction.
[0051] [ka]
[0052] [ka]
[0053] [ka]
[0054] [ka]
[0055] R1, R3, and R4 in formula (2A), formula 3, and formula 4 represent the same organic groups as in the polymer compound of the present invention described above.
[0056] The compound (carboxylic acid) represented by formula (2A) is preferably alpha lipoic acid (formula 7) below. Since alpha lipoic acid is a natural compound, its synthesis step can be omitted when it is used.
[0057] [ka]
[0058] Furthermore, examples of the compound (carboxylic acid) represented by Formula 2(A) include the following compounds (Formulas 8 to 10).
[0059] [Chemical Formula]
[0060] [Chemical Formula]
[0061] [Chemical Formula]
[0062] Examples of the compound (dialdehyde) represented by Formula 3 include the following glutaraldehyde (Formula 11) and terephthalaldehyde (Formula 12).
[0063] [Chemical Formula]
[0064] [Chemical Formula]
[0065] Examples of the compound (diisocyanide) represented by Formula 4 include the following 1,6 - diisocyanatohexane (Formula 13) and 1,4 - diisocyanatobenzene (Formula 14).
[0066] [Chemical Formula]
[0067] [Chemical Formula]
[0068] The Passerini Reaction is known as a type of three-component condensation reaction. By simply adding and mixing an aldehyde, an isonitrile, and a carboxylic acid simultaneously, an α-acyl-oxyamide can be efficiently obtained. In the method for producing the polymer compound of the present invention, the reaction conditions of the Passerini Reaction are not particularly limited, and three kinds of compounds represented by formula (2A) or (2B), formula 3, and formula 4 can be reacted under conventionally known conditions and methods. In addition, in the method for producing the polymer compound of the present invention, a compound that promotes the Passerini Reaction can be appropriately added.
[0069] The method for producing the polymer compound of the present invention can obtain a polymer compound containing a repeating unit represented by formula 1A (typically, a polymer represented by formula 6) by subjecting the compounds represented by formula (2A) or (2B), formula 3, and formula 4 to the Passerini Reaction. Since the method for producing the polymer compound of the present invention can directly use starting materials such as α-lipoic acid (formula 7) as they are without converting them into monomers for the Passerini Reaction, the number of synthesis steps is suppressed, and it is also excellent in atom economy.
[0070] In addition, the method for producing the polymer compound of the present invention can obtain various polymer compounds by combining the three kinds of compounds represented by formula (2A) or (2B), formula 3, and formula 4. Therefore, by adjusting the combination of the three kinds of compounds, the method for producing the polymer compound of the present invention can obtain a polymer compound in which the structure such as the molecular weight, the physical properties such as the glass transition temperature and the elastic modulus, and the material properties such as the adhesiveness are adjusted.
[0071] In addition, in one embodiment of the method for producing the polymer compound of the present invention, the material may contain a carboxylic acid (Formula 5) that does not have 1,2-dithiolane. That is, in the method for producing the polymer compound of the present invention, together with the carboxylic acid represented by Formula (2A) or (2B), the carboxylic acid represented by the following Formula (5) can be used.
[0072] [Chemical formula]
[0073] In Formula 5, R2 represents an organic group (excluding those having 1,2-dithiolane at the end). As described above, R2 may be, for example, an aliphatic group (e.g., an alkyl group) having 1 to 12 or 12 or more carbon atoms, an aromatic group (e.g., an aryl group), a carbon group containing a hetero element, and the like.
[0074] In the method for producing the polymer compound of the present invention, by adjusting the ratio (molar ratio) of the carboxylic acid (C1) represented by Formula 2 and the carboxylic acid (C2) represented by Formula 5, the number of 1,2-dithiolanes (crosslinked structure) located in the side chain can be adjusted, and thereby, the physical properties and material properties of the polymer compound can be adjusted.
[0075] In the method for producing the polymer compound of the present invention, the ratio (molar ratio) of the carboxylic acid (C1) represented by Formula 2 and the carboxylic acid (C2) represented by Formula 5 is not particularly limited, but from the viewpoint of the physical properties and material properties of the polymer compound (polymer), a range of C1:C2 = 10:90 to 90:10 can be exemplified.
[0076] <Multimer (crosslinked polymer)> The multimer of the present invention is a multimer in which a plurality of the polymer compounds of the present invention are bonded, and includes an S-S bond formed by the ring opening of 1,2-dithiolane. Specifically, in one embodiment of the multimer of the present invention, for example, the 1,2-dithiolane of the compound represented by Formula 6 is ring-opened, and a crosslinked structure in which a plurality of polymer compounds (Formula 6) are bonded to each other via an S-S bond is present.
[0077] More specifically, in one embodiment of the multimer of the present invention, for example, as a multimer containing a polymer compound represented by Formula 6, one having the following structure (Formula 15) can be exemplified.
[0078]
Chemical formula
[0079] The method for synthesizing the multimer of the present invention is not particularly limited. By applying an external stimulus such as heating or UV light irradiation to the polymer compound of the present invention, the S-S bond of 1,2-dithiolane is ring-opened, and in the adjacent polymer compound of the present invention, a crosslinked structure containing an S-S bond formed by the ring-opened S atoms is formed to synthesize the multimer.
[0080] When the polymer compound (polymer (= raw material polymer)) of the present invention is heated or the like, a crosslinked polymer (multimer) is generated. This crosslinked polymer (multimer) generally has the properties of a polymer material called an elastomer. Also, generally, it is difficult to return the crosslinked polymer (multimer) to the raw material polymer, but the crosslinked polymer (multimer) of the present invention can be returned to the raw material polymer before crosslinking by reacting with an appropriate reactant such as a catalytic amount of a thiol compound and a base compound for de-crosslinking. Note that, as for the method of de-crosslinking, a conventionally known method can be appropriately adopted.
[0081] <Adhesive composition> The adhesive composition of the present invention contains the above-described polymer compound and / or multimer of the present invention.
[0082] When the total mass of the adhesive composition is 100% by mass, the adhesive composition of the present invention can contain 0.0001 to 99.99% by mass of the polymer compound or multimer of the present invention. The adhesive composition may contain one of the above-described polymer compounds or multimers of the present invention alone, or may contain two or more thereof.
[0083] The adhesive composition of the present invention can contain a solvent. The content of the solvent in the adhesive composition is not particularly limited, but generally, 1 to 99% by mass is preferable.
[0084] The solvent is not particularly limited as long as it can disperse, dissolve, or swell the high molecular compound of the present invention, and known solvents can be used. Examples of the solvent include aprotic polar solvents such as N-methylpyrrolidone, dichloromethane, tetrahydrofuran, acetone, DMF, acetonitrile, and dimethyl sulfoxide.
[0085] Furthermore, the adhesive composition of the present invention may contain components other than those described above within the range where the effects of the present invention are exhibited. Examples of the components other than those described above include other high molecular compounds, antioxidants, surfactants, pigments, dyes, various fillers, and the like.
[0086] Since the adhesive composition of the present invention has excellent adhesiveness, it can be used, for example, for bonding the same or different substrates such as metal substrates, resin substrates, and glass substrates.
[0087] In addition, even when the adhesive composition of the present invention repeatedly performs adhesion and detachment to an adherend, the adhesive strength is maintained.
[0088] The high molecular compound of the present invention, its production method, multimer, and adhesive composition are not limited to the above embodiments.
Examples
[0089] Hereinafter, the high molecular compound of the present invention, its production method, multimer, and adhesive composition will be described together with examples, but the present invention is not limited to the following examples at all.
[0090] <1> Measuring device (1) 1 1H NMR measurement 1The 1H (400 MHz) NMR spectrum was measured on a JEOL ECS-400 for a CDCl3 solution of the sample and confirmed in ppm (δ) from internal Me4Si. (2) GPC measurement Gel permeation chromatography (GPC) was performed at 40 °C using OMNISEC manufactured by Malvern Panalytical equipped with a GMHHR-M polystyrene mixed gel column (manufactured by Tosoh Corporation), with a refractive index detector and THF as the eluent. GPC was calibrated with PMMA standards. (3) Infrared spectroscopic measurement (IR) The infrared spectrum was recorded on a JASCO FT / IR-6100 (equipped with an ATR attachment). (4) Rheology measurement Rheology measurements were carried out using an Anton Paar MCR 302 rheometer equipped with an 8 mm parallel plate geometry.
[0091] <2> Reagents · α-Lipoic acid: DL-α-lipoic acid (purity > 99.0%) manufactured by Tokyo Chemical Industry Co., Ltd. · Glutaraldehyde: 5.6 M aqueous solution manufactured by Tokyo Chemical Industry Co., Ltd. · Terephthaldehyde: (purity > 98.0%) manufactured by Tokyo Chemical Industry Co., Ltd. · 1,6-Diaminohexane: (purity > 99.0%) manufactured by Tokyo Chemical Industry Co., Ltd. · 1,4-Phenylenediamine: (purity > 98.0%) manufactured by Tokyo Chemical Industry Co., Ltd. · 1,6-Diisocyanohexane: Synthesized from 1,6-diaminohexane according to the literature procedure. · 1,4-Diisocyanobenzene: Synthesized from 1,4-phenylenediamine according to the literature procedure.
[0092] <3>Synthesis of 1,2 - dithiolane - modified polyamide (Example 1) Synthesis of Polymer Compound 1 To a mixture of lipoic acid (2.73 g, 1.32×10 -2 mol) in THF (4.6 mL) in a glass tube, glutaraldehyde (5.6 M aqueous solution, 1.07 mL, 6.00×10 -3 mol) and 1,6 - diisocyanatohexane (0.91 g, 6.00×10 -3 mol) were sequentially added (Passerini reaction). Then, while stirring with a magnetic stirrer under a nitrogen atmosphere, the reaction mixture was heated to 40 °C using an oil bath. A small amount was taken for 1 1H NMR analysis using JEOL ECS - 400, and the conversion rate of the starting materials was calculated. After 46 hours, the obtained solution was gradually poured into vigorously stirred diethyl ether (30 mL). The precipitate was collected by suction filtration and dried in vacuo at room temperature. The desired product was obtained as a pale yellow powder (3.6 g, 93%). The molecular weight Mn of the reaction product by GPC measurement was 6060.
[0093] Figure 1 is a diagram showing the 1 results of 1H NMR analysis of the reaction product of Example 1. As shown in Figure 1, a repeating structure due to α - acyloxypolyamide characteristic of the Passerini reaction product was confirmed.
[0094] Figure 2 is a diagram showing the results of infrared spectroscopic measurement of the reaction product of Example 1. As shown in Figure 2, instead of the peaks of the starting carboxylic acid (lipoic acid), aldehyde (glutaraldehyde), and isocyanide (1,6 - diisocyanatohexane), characteristic peaks of amide and ester were confirmed in the reaction product.
[0095] Figure 3 is a diagram showing the results of GPC measurement of the reaction product of Example 1. As shown in Figure 3, it was confirmed that the reaction product had Mn = 6060 and PDI = 2.20. It was confirmed that the molecular weight increased with the reaction time and the polymerization reaction was proceeding. It was confirmed that the reaction product had a polymer structure.
[0096] (Example 2) Synthesis of Polymer Compound 2 A reaction product was obtained under the same conditions as in Example 1, except that 1,4-diisocyanobenzene was used instead of the isocyanide (1,6-diisocyanohexane) used in Example 1. The molecular weight Mn of the reaction product by GPC measurement was 2330.
[0097] Of the reaction product 1 By 1H NMR analysis, a repeating structure due to α-acyloxypolyamide characteristic of the Passerini reaction product was confirmed. Also, by infrared spectroscopic measurement, characteristic peaks of amide - ester were confirmed in the reaction product. Furthermore, by GPC measurement, it was confirmed that the molecular weight of the reaction product increased with the reaction time, indicating that the polymerization reaction was proceeding. It was confirmed that the reaction product had a polymer structure.
[0098] (Example 3) Synthesis of Polymer Compound 3 A reaction product was obtained under the same conditions as in Example 1, except that terephthalaldehyde was used instead of the aldehyde (glutaraldehyde) used in Example 1. The molecular weight Mn of the reaction product by GPC measurement was 1650.
[0099] Figure 4 is a diagram showing the results of 1H NMR analysis of the reaction product of Example 3. As shown in Figure 4, a repeating structure due to α-acyloxypolyamide characteristic of the Passerini reaction product was confirmed. 1 Figure 5 is a diagram showing the results of infrared spectroscopic measurement of the reaction product of Example 3. As shown in Figure 5, characteristic peaks of amide - ester were confirmed in the reaction product, replacing the peaks of the raw material carboxylic acid (lipoic acid), aldehyde (terephthalaldehyde), and isocyanide (1,6-diisocyanohexane).
[0100] Figure 5 is a diagram showing the results of infrared spectroscopic measurement of the reaction product of Example 3. As shown in Figure 5, characteristic peaks of amide - ester were confirmed in the reaction product, replacing the peaks of the raw material carboxylic acid (lipoic acid), aldehyde (terephthalaldehyde), and isocyanide (1,6-diisocyanohexane).
[0101] Figure 6 is a diagram showing the results of GPC measurement of the reaction product of Example 3. As shown in Figure 6, it was confirmed that the reaction product had Mn = 1650 and PDI = 1.95. It was confirmed that the molecular weight increased with the reaction time, indicating that the polymerization reaction was proceeding. It was confirmed that the reaction product had a polymer structure.
[0102] (Example 4) Synthesis of Polymer Compound 4 A reaction product was obtained under the same conditions as in Example 1, except that terephthalaldehyde was used instead of the aldehyde (glutaraldehyde) used in Example 1, and 1,4-diisocyanobenzene was used instead of isonitrile (1,6-diisocyanohexane). The molecular weight Mn of the reaction product by GPC measurement was 810.
[0103] of the reaction product 1 By 1H NMR analysis, a repeating structure due to α-acyloxypolyamide characteristic of the Passerini reaction product was confirmed. Also, by infrared spectroscopic measurement, characteristic peaks of amide - ester were confirmed in the reaction product. Furthermore, by GPC measurement, it was confirmed that the molecular weight of the reaction product increased with the reaction time, indicating that the polymerization reaction was proceeding. It was confirmed that the reaction product had a polymer structure.
[0104] (Example 5) Synthesis of Polymer Compound 5 As the carboxylic acid, lipoic acid and C5H 10 COOH (R2 = C5H 10 ) were used in a molar ratio of 1:1, and a reaction product was obtained under the same conditions as in Example 1. The molecular weight Mn of the reaction product by GPC measurement was 8860.
[0105] Figure 7 is a diagram showing the 1 results of 1H NMR analysis of the reaction product of Example 5. As shown in Figure 7, a repeating structure due to α-acyloxypolyamide characteristic of the Passerini reaction product was confirmed.
[0106] Figure 8 is a diagram showing the results of infrared spectroscopic measurement of the reaction product of Example 5. As shown in Figure 8, instead of the peaks of the starting carboxylic acid (lipoic acid / C5H 10 COOH), aldehyde (glutaraldehyde), and isonitrile (1,6 - diisocyanatohexane), characteristic peaks of amide and ester were confirmed in the reaction product.
[0107] Figure 9 is a diagram showing the results of GPC measurement of the reaction product of Example 5. As shown in Figure 9, it was confirmed that the reaction product had Mn = 8860 and PDI = 1.98. It was confirmed that the molecular weight increased with the reaction time, indicating that the polymerization reaction was proceeding. It was confirmed that the reaction product had a polymer structure.
[0108] Figure 10 is a diagram showing the structures and molecular weights of the polymer compounds in Examples 1 - 5.
[0109] <4> Synthesis, Molding, and Repeated Molding of Crosslinked Polyamide (YSH - 2 - 31) The 1,2 - dithiolane - modified polyamide 1 synthesized in Example 1 was heated at 110 °C for 3 hours and then at 170 °C for 6 hours to obtain a crosslinked polymer (multimer). This crosslinked polymer was cut out and filled into a stainless steel mold for disk - shaped samples (diameter = 8 mm, thickness = 1 mm), and heated at 170 °C for 20 minutes under pressure. Rheological measurement was performed on the obtained disk - shaped sample. The molded sample was cut into small pieces and remolded under the same molding conditions as before. This cutting and remolding were repeated 3 times. As a result, it was confirmed that this polymer had remoldability and reprocessability derived from a dynamic crosslinked structure.
[0110] <5> Adhesion Test The polymer compound 1 (1,2-dithiolane-modified polyamide) synthesized in Example 5 was heated at 170 °C for 6 hours to obtain a crosslinked polymer (multimer). This crosslinked polymer was cut out with a cutter or the like, placed on a substrate such as stainless steel or glass, and further, the crosslinked polymer on the substrate was sandwiched from above with another substrate (Fig. 11(A)). This was pressed with a clip (Fig. 11(B)), heated at 180 °C for 30 minutes, and a tensile shear test was performed on the obtained sample.
[0111] After the shear test, the polymer sample was recovered from the substrate (by peeling off, scraping, etc. the polymer). This was used for the adhesion of new substrates similar to the above, and a tensile shear test was performed again. The change in the adhesive force (tensile shear stress) when this was repeated was measured.
[0112] The results are shown in Fig. 12. As shown in Fig. 12, it was confirmed that this crosslinked polymer maintained its adhesive force even when the adhesion to and recovery (desorption) from the adhesion object (substrate) were repeated.
[0113] <6> Crosslinking removal (regeneration) test The 1,2-dithiolane-modified polymer (molecular weight Mn = 8740) synthesized in the same manner as in Example 1 was heated at 170 °C for 6 hours to obtain a crosslinked polymer (multimer). This was immersed in chloroform, and 3 mol% of benzyl mercaptan and 3 mol% of 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) were added with respect to the amount equivalent to the 1,2-dithiolane groups in the polymer, and the mixture was stirred at 40 °C for 2 hours to obtain a polymer solution. It was confirmed by GPC analysis that the polymer synthesized in Example 5 before crosslinking was regenerated by the crosslinking removal of the crosslinked polymer (Fig. 13).
Claims
1. A polymer compound containing a repeating unit represented by the following general formula (1A). 【Chemical 1】 (In the formula, n is an integer of 1 or more, X １ , X ２ are each independent, and at least one of X １ , X ２ is 1,2 - dithiolane or an organic group having 1,2 - dithiolane at its end, X １ and X ２ may be the same as or different from each other. When n is 2 or more, a plurality of X １ may be the same as or different from each other, and a plurality of X ２ may be the same as or different from each other. R ３ represents an organic group, and when n is 2 or more, a plurality of R ３ may be the same as or different from each other, R ４ represents an organic group, and when n is 2 or more, a plurality of R's ４ may be the same as or different from each other)
2. X １ 、 X ２ wherein at least one of them is a group represented by the following general formula (1B) or formula (1C): The polymer compound according to Claim 1. 【Chemical 2】 (In the formula, * indicates the bonding position, and R １ represents an organic group) [Chemical Formula 3] (In the formula, * indicates the bonding position)
3. The polymer compound according to Claim 1 or 2, wherein n is 2 or more.
4. The polymer compound according to any one of Claims 1 to 3. R １ is an organic group having 1 to 32 carbon atoms,
5. The polymer compound according to any one of Claims 1 to 4. R ３ is an organic group having 1 to 32 carbon atoms, and R ４ is an organic group having 1 to 32 carbon atoms,
6. A method for producing a polymer compound according to any one of Claims 1 to 5, comprising subjecting at least one of the compounds represented by the following general formula (2A) or formula (2B), a compound represented by general formula (3), and a compound represented by general formula (4) to a Passerini reaction. A method for producing a polymer compound.
7. 【Chemical Formula 4】 (wherein, R １ represents an organic group) 【Chemical Formula 5】 [Chemical Formula 6] (wherein, R ３ represents an organic group) 【Chemical Formula 7】 (wherein, R ４ represents an organic group) The method for producing a polymer compound according to Claim 6, wherein the compound represented by the general formula (2A) is α-lipoic acid.
8. The method for producing a polymer compound according to Claim 6 or 7, further comprising subjecting a compound represented by the following general formula (5) to a Passerini reaction.
9.
10. A multimer in which a plurality of the polymer compounds according to any one of Claims 1 to 5 are bonded, and which contains an S—S bond formed by ring-opening of the 1,2-dithiolane. 【Chemical 8】 (wherein, R ２ represents an organic group (excluding those having 1,2-dithiolane)) A multimer.
11. An adhesive composition containing the polymer compound according to any one of Claims 1 to 5 or the multimer according to Claim 9. An adhesive composition.