Novel diol compounds with an isocyanurate skeleton

Abstract

To solve the problem in which introducing isocyanurate skeletons into resin systems, such as polyester, polyurethane, polycarbonate, polymerized from diol monomers, is desired for the expression of characteristics such as heat resistance, mechanical strength, moisture resistance, and electrical properties, but there are only a limited number of reports of isocyanurate compounds with hydroxy groups, and to provide novel diol compounds with isocyanurate skeletons.SOLUTION: The foregoing problem is solved by a compound represented by the following formula (1) (where A is a divalent organic group terminated with a carbon atom, and R is a hydrogen atom or a monovalent organic group).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a novel diol compound having an isocyanurate skeleton. [Background technology]

[0002] Isocyanurate compounds have traditionally been used as resin modifiers and crosslinking agents in the field of resin materials. Because they have a rigid, highly stackable central skeleton, their incorporation into resin materials can impart unprecedented physical properties, such as improved mechanical strength, heat resistance, moisture resistance, and hydrolysis resistance.

[0003] Patent Document 1 shows that combining polyphenylene ether with an isocyanurate crosslinking agent exhibits excellent electrical properties. Patent Document 2 discloses an isocyanurate compound having a glycidyl group, and describes that combining it with an epoxy resin can impart good heat resistance and mechanical properties. Furthermore, cases have been reported in which an isocyanurate skeleton is directly introduced into the main skeleton of a resin as a monomer, rather than just as a crosslinking agent or resin modifier.

[0004] The diamine compound having an isocyanurate skeleton described in Patent Document 3 can be used as a raw material (monomer) for polyimide resins, and it is expected that unprecedented physical properties can be achieved by directly introducing an isocyanurate skeleton into a polyimide skeleton. In addition, the diamine compound can also be used as a curing agent for epoxy resins.

[0005] Patent Document 4 also describes a diamine monomer having an isocyanurate skeleton, shows the use of a polyimide obtained using the monomer as a liquid crystal aligning agent, and discloses the unique physical properties of polyimides containing an isocyanurate skeleton. As such, diamine monomers having an isocyanurate skeleton are essential for introducing specific structures into resins such as polyamides, polyimides, and polybenzoxazoles, and various examples have been reported. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] WO2020 / 196718 [Patent Document 2] Patent No. 6513012 [Patent Document 3] Patent Publication No. 2014-58452 [Patent Document 4] Patent No. 4868167 Summary of the Invention [Problem to be solved by the invention]

[0007] On the other hand, diol monomers are also important in introducing specific structures into resins. For example, diol monomers can be used to obtain resins such as polyesters, polyurethanes, and polycarbonates. The introduction of an isocyanurate skeleton into these resin systems is desirable from the viewpoint of expressing properties such as heat resistance, mechanical strength, moisture resistance, and electrical properties. However, there have been limited reports of isocyanurate compounds with hydroxy groups.

[0008] In view of the above circumstances, an object of the present invention is to provide a novel diol compound having an isocyanurate skeleton. [Means for solving the problem]

[0009] The present invention can solve the above problems by providing the following novel diol compound containing an isocyanurate skeleton.

[0010] [1] A compound represented by general formula (1): (wherein, A is a divalent organic group terminated in a carbon atom, and R is a hydrogen atom or a monovalent organic group.) [ka]

[0011] [2] The compound according to [1], wherein A in general formula (1) is a methylene group.

[0012] [3] The compound according to [2], wherein R in general formula (1) is a monovalent hydrocarbon group having 60 or less carbon atoms. [Effects of the Invention]

[0013] The diol compound having an isocyanuric acid skeleton of the present invention can impart the rigidity characteristic of isocyanurates to urethanes, polyesters, polycarbonates, and the like. In addition, the carbon-carbon triple bond allows for further rigidity, and the compound can also be used for thermal crosslinking and function as a reaction site for hydrosilylation and the like. Furthermore, the substituent on the isocyanurate ring (R in general formula (1)) can be varied in various ways, significantly expanding the range of monomer options available when synthesizing resins with various properties. DETAILED DESCRIPTION OF THE INVENTION

[0014] Although the embodiments of the present invention are described below, the present invention is not limited thereto. All academic documents and patent documents described in this specification are incorporated herein by reference. Unless otherwise specified in this specification, "A to B" representing a numerical range means "A or more (including A and greater than A) and B or less (including B and less than B)."

[0015] The diol compound having an isocyanurate skeleton of the present invention has phenyl groups bonded to two of the three nitrogen atoms on the isocyanurate ring, and a substituent having a terminal hydroxyl group bonded to the phenyl group via a carbon-carbon triple bond.Furthermore, a hydrogen atom or a substituent is bonded to the remaining nitrogen atom on the isocyanurate ring, and is a diol compound represented by general formula (1). [ka]

[0016] An example of a synthesis scheme for obtaining the diol compound of the present invention is shown in (Synthesis Scheme). In reaction (A), a solution of an isocyanate compound (1-1) such as 3-bromophenyl isocyanate, 4-bromophenyl isocyanate, or 4-chlorophenyl isocyanate dissolved in a solvent is added dropwise to a cyanate salt dispersed in a solvent. After the reaction, the solvent is distilled off under reduced pressure, and the resulting mixture is separated several times using an appropriate organic solvent and water. The aqueous layer is then recovered, and a Brønsted acid is added to precipitate the isocyanurate compound (1-2). After the product is recovered, it may be further purified, such as by washing or recrystallization.

[0017] Examples of the solvent for this reaction and the solvent for the dropping solution include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dibutylpropanamide, dimethyl sulfoxide, and 1,4-dioxane. Of these, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide are preferably used.

[0018] Examples of cyanate that can be used include potassium cyanate and sodium cyanate. The reaction is carried out at a temperature of 25°C to 150°C, preferably 40°C to 120°C, and more preferably 60°C to 100°C. The reaction takes place over a period of 10 to 120 minutes, preferably 15 to 60 minutes. After the addition, the reaction is continued for a period of 10 minutes to 6 hours, preferably 15 minutes to 3 hours.

[0019] The organic solvent used for separation is not particularly limited, and hexane, toluene, ethyl acetate, diethyl ether, methylene chloride, chloroform, etc. can be used, or a combination of two or more of these can be used. Examples of acids to be added to the aqueous layer after separation include hydrochloric acid, sulfuric acid, acetic acid, etc., with hydrochloric acid being preferred. When recrystallizing the obtained solid, alcohols such as methanol, ethanol, 2-propanol, and esters such as ethyl acetate and butyl acetate can be used, and these can be combined with hydrocarbons such as hexane as a poor solvent, with ethanol being particularly preferred.

[0020] When R is a hydrogen atom, step (B) of introducing the substituent R can be omitted and the process can proceed to step (C) of the cross-coupling reaction. Here, the case where R is other than a hydrogen atom will be described. Any known organic synthesis method can be used to introduce the substituent R. As an example, the substituent R can be introduced by dissolving the isocyanurate compound (1-2) and a base in an appropriate solvent, adding 1.0 to 2.0 equivalents, preferably 1.1 to 1.5 equivalents, of the compound RX, which is the source of the substituent R, relative to the isocyanurate, and carrying out the reaction.

[0021] Here, R is a monovalent organic group, and X is a leaving group of any type, including chloro, bromo, iodo, tosyloxy, mesyloxy, and trifluoromethanesulfonyloxy. The substituent R is a monovalent organic group, and is not particularly limited, including alkyl groups such as methyl, ethyl, n-propyl, n-butyl, s-butyl, and t-butyl, and hydrocarbon groups containing carbon-carbon double or triple bonds such as allyl, homoallyl, cinnamyl, and propargyl. Heteroatom-containing substituents such as glycidyl and oxetanyl are also acceptable.

[0022] The substituent R can be varied widely, and by changing the substituent, it is possible to achieve the desired material properties, resin polymerizability, etc. When the substituent R is a hydrogen atom (when no substituent is substantially introduced), the NH bond of the isocyanurate ring functions as an acid. Therefore, it is also possible to use the diol compound of the present invention as an acid group without actively introducing the substituent R.

[0023] It is also possible to introduce an isocyanurate structure into the main skeleton of the resin as a monomer without introducing the substituent R, and then introduce the substituent R or use it as a crosslinking point. In the present invention, the advantages of using an isocyanurate ring rather than a benzene ring as the central skeleton of the diol are not only the rigidity and strong stacking properties unique to isocyanurates, but also the ease of introducing a substituent and the function as an acid group.

[0024] The base is not particularly limited, but examples thereof include triethylamine, diisopropylethylamine, pyridine, quinoline, isoquinoline, 3,5-lutidine, 2,6-lutidine, and picoline. Inorganic bases such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and sodium hydride can also be used. The base can be used in an amount of 1.0 to 3.0 equivalents relative to the substrate (1-2), preferably 1.1 to 2.0 equivalents.

[0025] The solvent for this reaction is not particularly limited, but examples thereof include tetrahydrofuran, 1,4-dioxane, acetone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dibutylpropanamide, and dimethyl sulfoxide.

[0026] The reaction can be carried out at a temperature of 20° C. to 120° C., preferably 40° C. to 100° C., more preferably 50° C. to 90° C. The reaction time can be 1 hour to 12 hours, preferably 1 hour to 6 hours.

[0027] After the reaction, the solvent may be removed by distillation under reduced pressure, and an appropriate purification procedure may be carried out. For example, purification by separation, recrystallization, or column chromatography may be carried out alone or in combination. Alternatively, the reaction may proceed to the next reaction without purification. In this case, the crude product may be obtained by distillation under reduced pressure, and then charged into the cross-coupling reaction. Alternatively, the solvent may not be removed by distillation under reduced pressure, and the substrates and catalyst required for the cross-coupling reaction may be newly charged into the same reaction vessel.

[0028] Step (C) can be carried out by the Sonogashira cross-coupling reaction. The substrate (1-3) and an alcohol containing a carbon-carbon triple bond are dissolved in a solvent, and the cross-coupling reaction proceeds by adding a palladium catalyst, a copper catalyst, and an amine compound.

[0029] Preferred amine compounds include triethylamine, diisopropylethylamine, and diethylamine, and are generally added in large excess relative to the substrate. Specifically, the amount is 10 or more equivalents relative to the substrate. Palladium catalysts such as tetrakis(triphenylphosphine)palladium and bis(triphenylphosphine)palladium dichloride are suitable. Copper(I) halides can be used as copper catalysts, with copper(I) iodide being particularly preferred. While the solvent is not particularly limited, the amine compounds listed above may be used as solvents. In this case, if the solubility of the substrate is insufficient, a solvent that dissolves the substrate and does not inhibit the reaction may be added as a cosolvent.

[0030] Specific examples include tetrahydrofuran, 1,4-dioxane, acetone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dibutylpropanamide, and dimethyl sulfoxide. The reaction can be carried out at a temperature of 20°C to 150°C for a reaction time of 1 hour to 48 hours, preferably 1 hour to 12 hours. After the reaction, the solvent is distilled off under reduced pressure, and then a separation operation is carried out to remove the remaining metal catalyst and amine components, followed by purification by recrystallization and / or column chromatography.

[0031] The substrate alcohol may be any alcohol compound having a terminal alkyne, such as 2-propyn-1-ol, 3-butyn-1-ol, 3-butyn-2-ol, 4-pentyn-2-ol, 1-pentyn-3-ol, 5-hexyn-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-penten-4-yn-3-ol, 3-methyl-1-pentyn-3-ol, 1-hexyn-3-ol, 1-ethynyl-1-cyclohexanol, 1-octyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, (±)-dehydrolinalool, 4-ethyl-1-octyn-3-ol, ethinylestradiol, and the like. [ka]

[0032] (Application) The diol compound of the present invention can be used as a polymerization monomer to impart unprecedented properties to any resin material, such as thermoplastic resins, thermosetting resins, cation-curable resins, anion-curable resins, radical-curable resins, etc. By introducing the rigid structure of isocyanurate and alkyne into the main chain skeleton of the resin, it is possible to improve mechanical strength, heat resistance, chemical resistance, hydrolysis resistance, etc.

[0033] When the diol compound of the present invention is used as a polymerizable monomer for a resin, the type of resin is not particularly limited, but it is particularly suitable for use in resins that can generally be polymerized using the diol compound as a monomer. Examples of such resins include polyesters, polyurethanes, polycarbonates, and resins containing these as part of the repeating units. Furthermore, since the diol compound of the present invention has a carbon-carbon triple bond, it can also be incorporated into a siloxane resin by a hydrosilylation reaction.

[0034] The diol compound of the present invention or a resin obtained using the compound can be used in various applications, such as adhesives, pressure-sensitive adhesives, electronic materials, insulating materials (including printed circuit boards, electric wire coatings, etc.), high-voltage insulating materials, interlayer insulating films, TFT passivation films, TFT gate insulating films, TFT interlayer insulating films, TFT transparent planarizing films, insulating packings, insulating coating materials, adhesives, highly heat-resistant adhesives, highly heat-dissipating adhesives, optical adhesives, adhesives for LED elements, adhesives for various substrates, adhesives for heat sinks, paints, UV powder paints, inks, colored inks, UV inkjet inks, coating materials (including hard coats, sheets, films, release paper coats, optical disk coats, and optical fiber coats), and molding materials (including sheets, films, FRP, etc.). ), sealing materials, potting materials, encapsulating materials, encapsulating materials for light-emitting diodes, liquid crystal sealants, sealants for display devices, encapsulating materials for electrical materials, encapsulating materials for various solar cells, high-heat-resistant sealants, resist materials, liquid resist materials, colored resists, dry film resist materials, solder resist materials, binder resins for color filters, transparent planarizing materials for color filters, binder resins for black matrices, photospacer materials for liquid crystal cells, transparent encapsulating materials for OLED elements, photolithography, materials for solar cells, materials for fuel cells, display materials, recording materials, vibration-proof materials, waterproof materials, moisture-proof materials, photosensitive drums for copiers, solid electrolytes for batteries, etc. The isocyanuric acid skeleton-containing polymer may also be used as an additive to other resins, etc. Needless to say, the uses are not limited to those listed below. [Example]

[0035] The present invention will be specifically explained below with reference to examples, but the present invention is not limited to these examples.

[0036] Example 1 A reaction vessel was charged with 1 L of N,N-dimethylformamide (DMF) and 48 g of potassium cyanate and heated to 75°C. A solution of 198 g of 4-bromophenyl isocyanate dissolved in 500 mL of DMF was added dropwise over 30 minutes using a dropping funnel. After the addition, the mixture was stirred for 1 hour to complete the reaction. The DMF was removed under reduced pressure, and 1 L of ethyl acetate and 3 L of water were added. Concentrated hydrochloric acid was added to the aqueous layer, and the precipitate was collected and recrystallized from ethanol to yield 178 g of white crystals (2).

[0037] A flask was charged with 21.9 g of the above white crystals (2), 16.6 g of 2-propyn-1-ol, 3.51 g of bis(triphenylphosphine)palladium(II) dichloride, 1.9 g of copper(I) iodide, and 500 mL of triethylamine, and the mixture was stirred under a nitrogen atmosphere at 80°C for 8 hours to react. After completion of the reaction, the triethylamine was removed under reduced pressure, and recrystallization was carried out from ethanol to obtain 30.2 g of diol compound (3) represented by the following formula: [ka] [ka]

[0038] Example 2 A reaction vessel was charged with 1 L of N,N-dimethylformamide (DMF) and 48 g of potassium cyanate and heated to 75°C. A solution of 198 g of 3-bromophenyl isocyanate dissolved in 500 mL of DMF was added dropwise over 30 minutes using a dropping funnel. After the addition, the mixture was stirred for 1 hour to complete the reaction. The DMF was removed under reduced pressure, and 1 L of ethyl acetate and 3 L of water were added. Concentrated hydrochloric acid was added to the aqueous layer, and the precipitate was collected and recrystallized from ethanol to yield 169 g of white crystals (4).

[0039] A flask was charged with 21.9 g of the above white crystals (4), 16.6 g of 2-propyn-1-ol, 3.51 g of bis(triphenylphosphine)palladium(II) dichloride, 1.9 g of copper(I) iodide, and 500 mL of triethylamine, and the mixture was stirred under a nitrogen atmosphere at 80°C for 8 hours to react. After completion of the reaction, the triethylamine was removed under reduced pressure, and recrystallization was carried out from ethanol to obtain 32.4 g of diol compound (5) represented by the following formula: [ka] [ka]

[0040] Example 3 The procedure was carried out in the same manner as in Example 1 up to the point where (2) was obtained. A flask was charged with 43.9 g of white crystals (2), 13.3 g of allyl bromide, 11.1 g of triethylamine, and 500 mL of tetrahydrofuran, and the mixture was heated to 70°C and stirred for 1 hour. After the reaction was completed, the solvent was distilled off under reduced pressure, and the crude product was separated into water and diethyl ether. This separation procedure was repeated twice. The organic layer was concentrated to obtain 45.5 g of compound (6).

[0041] A flask was charged with 23.9 g of compound (6), 6.62 g of 2-propyn-1-ol, 3.51 g of bis(triphenylphosphine)palladium(II) dichloride, 1.90 g of copper(I) iodide, and 500 mL of triethylamine, and the mixture was stirred under a nitrogen atmosphere at 80°C for 8 hours to react. After completion of the reaction, the triethylamine was removed under reduced pressure, and the mixture was purified using a silica column and then recrystallized from ethanol to obtain 18.4 g of diol compound (7) represented by the following formula: [ka] [ka]

[0042] Example 4 The procedure was the same as in Example 2 up to the point where compound (4) was obtained. A flask was charged with 43.9 g of white crystals (5), 8.85 g of chloromethyl methyl ether, 11.1 g of triethylamine, and 500 mL of tetrahydrofuran, and the mixture was heated to 70°C and stirred for 1 hour. After the reaction was completed, the solvent was distilled off under reduced pressure, and the crude product was separated into water and diethyl ether. This separation procedure was repeated twice. The organic layer was concentrated to obtain 47.8 g of compound (8).

[0043] A flask was charged with 24.1 g of the above white crystals (8), 6.72 g of 2-propyn-1-ol, 4.51 g of bis(triphenylphosphine)palladium(II) dichloride, 2.44 g of copper(I) iodide, and 500 mL of triethylamine, and the mixture was stirred under a nitrogen atmosphere at 80°C for 8 hours to react. After completion of the reaction, the triethylamine was removed under reduced pressure, and the mixture was purified using a silica column and then recrystallized from ethanol to obtain 16.7 g of diol compound (9) represented by the following formula: [ka] [ka]

Claims

[Claim 1] A compound represented by general formula (1): In the formula, A is a methylene group, and R is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an s-butyl group, an t-butyl group, an allyl group, a homoallyl group, a cinnamyl group, a propargyl group, or a methoxymethyl group. 【Chemistry 1】

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