JP2023161970A - Novel diol compound with isocyanurate skeleton - Google Patents

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

The present invention relates to a diol compound having a novel isocyanurate skeleton.

Isocyanurate compounds have traditionally been used as resin modifiers and crosslinking agents in the field of resin materials. Because it has a central skeleton that is rigid and has strong stacking properties, it can be incorporated into resin materials to develop unprecedented physical properties, such as mechanical strength, heat resistance, moisture resistance, and hydrolysis resistance. Improvement becomes possible.

Patent Document 1 shows that excellent electrical properties can be exhibited by combining polyphenylene ether with an isocyanurate crosslinking agent. Patent Document 2 discloses an isocyanurate compound having a glycidyl group, and states that it can impart good heat resistance and mechanical properties when combined with an epoxy resin. Furthermore, there have been reports of cases in which isocyanurate skeletons are introduced not only as crosslinking agents and resin modifiers, but also as monomers directly into the main skeleton of resins.

The diamine compound having an isocyanurate skeleton described in Patent Document 3 can be used as a raw material (monomer) for polyimide resin, and it is expected that unprecedented physical properties can be expressed by directly introducing an isocyanurate skeleton into the polyimide skeleton. be done. Further, the diamine compound can also be used as a curing agent for epoxy resin.

Patent Document 4 also describes a diamine monomer having an isocyanurate skeleton, indicates the use of a polyimide made using the monomer as a liquid crystal aligning agent, and discloses the unique physical properties of the isocyanurate skeleton-containing polyimide. ing. As described above, diamine monomers having an isocyanurate skeleton are essential for introducing specific structures into resins such as polyamides, polyimides, and polybenzoxazole, and various examples have been reported.

WO2020/196718 Patent No. 6513012 JP2014-58452 Patent No. 4868167

On the other hand, diol monomers are also important in introducing specific structures into resins. For example, resins such as polyester, polyurethane, and polycarbonate can be obtained from diol monomers. Introduction of isocyanurate skeletons into these resin systems is desirable from the viewpoint of developing properties such as heat resistance, mechanical strength, moisture resistance, and electrical properties, but there are limited reports on isocyanurate compounds with hydroxy groups. It was a target.

In view of the above circumstances, the present invention aims to provide a novel diol compound having an isocyanurate skeleton.

The present invention can solve the above problems with a diol compound containing the following novel isocyanurate skeleton.

[1]. A compound represented by general formula (1). (However, in the formula, A is a divalent organic group whose terminal is a carbon atom, and R is a hydrogen atom or a monovalent organic group.)

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

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

The diol compound having an isocyanuric acid skeleton according to the present invention can impart rigidity peculiar to isocyanurate to urethane, polyester, polycarbonate, and the like. In addition, since it has a carbon-carbon triple bond, it can be further imparted with rigidity, and can also be subjected to thermal crosslinking and can function as a reaction site for hydrosilylation and the like. In addition, the substituent on the isocyanurate ring (R in general formula (1)) can be changed in various ways, which greatly expands the monomer options when trying to synthesize resins with various characteristics than before. be able to.

Embodiments of the present invention will be described below, but the present invention is not limited thereto. Note that all of the academic literature and patent literature described in this specification are incorporated by reference in this specification. In this specification, unless otherwise specified, the numerical range "A to B" means "A or more (including A and larger than A) and B or less (including B and smaller than B)".

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 hydroxyl group at the end of the phenyl group is carbon- Bonded via a carbon triple bond. Furthermore, a hydrogen atom or a substituent is bonded to the remaining nitrogen atom on the isocyanurate ring, and the diol compound is represented by the general formula (1).

An example of a synthesis scheme for obtaining the diol compound of the present invention is shown in (Synthesis Scheme). In the reaction (A), a solution in which an isocyanate compound (1-1) such as 3-bromophenyl isocyanate, 4-bromophenyl isocyanate, or 4-chlorophenylisocyanate is dissolved in a cyanate salt dispersed in a solvent is added dropwise. drip. After the reaction, the solvent was distilled off under reduced pressure, and the water layer was separated several times using an appropriate organic solvent and water. The aqueous layer was collected and Brønsted acid was added to obtain the isocyanurate compound (1-2). is precipitated. After collecting the product, further purification operations such as washing and recrystallization may be performed.

The solvent for this reaction and the solvent for the dripping solution are 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, dimethylsulfoxide, 1,4-dioxane, among others, N,N-dimethylformamide, N,N-dimethylacetamide, N- Methyl-2-pyrrolidone and dimethyl sulfoxide are preferably used.

Potassium cyanate, sodium cyanate, etc. can be used as the cyanate. The reaction temperature is 25°C to 150°C, preferably 40°C to 120°C, more preferably 60°C to 100°C. The reaction time is 10 to 120 minutes for dropwise addition. Preferably it is 15 minutes to 60 minutes. After the dropwise addition, the reaction is continued for a period of 10 minutes to 6 hours, preferably 15 minutes to 3 hours.

The organic solvent used for liquid separation is not particularly limited, but hexane, toluene, ethyl acetate, diethyl ether, methylene chloride, chloroform, etc. can be used, and a plurality of these may be used in combination. Examples of the acid added to the aqueous layer after separation include hydrochloric acid, sulfuric acid, acetic acid, etc., and among them, hydrochloric acid is preferred. When recrystallizing the obtained solid, alcohols such as methanol, ethanol, and 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. However, ethanol is particularly preferred.

The step (B) of introducing the substituent R may be omitted when R is a hydrogen atom, and the step may proceed to the cross-coupling reaction step (C). Here, the case where R is other than a hydrogen atom will be explained. Any known organic synthesis method can be used to introduce the substituent R. For example, an isocyanurate compound (1-2) and a base are dissolved in a suitable solvent, and the substituent R is introduced as a source of the substituent R. The substituent R can be introduced by adding 1.0 to 2.0 equivalents, preferably 1.1 to 1.5 equivalents, of a certain compound RX to the isocyanurate and carrying out the reaction.

Here, R is a monovalent organic group, and X is a leaving group, and the type is not particularly limited, but examples include a chloro group, a bromo group, an iodo group, a tosyloxy group, a mesyloxy group, a trifluoromethanesulfonyloxy group, etc. Can be mentioned. The substituent R is a monovalent organic group, and is not particularly limited, but includes, for example, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a s-butyl group, a t-butyl group, Examples include hydrocarbon groups containing carbon-carbon double bonds and triple bonds, such as allyl group, homoallyl group, cinnamyl group, and propargyl group. A substituent containing a heteroatom such as a glycidyl group or an oxetanyl group may also be used.

There are a wide variety of substituents R, and by changing the substituents variously, it is possible to achieve desired material properties, resin polymerizability, etc. When the substituent R is a hydrogen atom (substantially no substituent is introduced), the NH bond of the isocyanurate ring functions as an acid. Therefore, it is also possible to utilize the diol compound of the present invention as an acid group without actively introducing the substituent R.

It is also possible to introduce the isocyanurate structure into the resin main skeleton 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 advantage of using an isocyanurate ring instead of a benzene ring as the central skeleton of the diol is not only isocyanurate's unique rigidity and strong stacking property, but also the ease of introducing substituents and its function as an acid group. There is also.

The above base is not particularly limited, but triethylamine, diisopropylethylamine, pyridine, quinoline, isoquinoline, 3,5-lutidine, 2,6-lutidine, picoline, etc. can be used. 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, preferably 1.1 to 2.0 equivalents, based on the substrate (1-2).

The solvent used in this reaction is not particularly limited, but includes 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, dimethylsulfoxide and the like.

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

After the reaction, the solvent may be distilled off under reduced pressure and an appropriate purification operation may be carried out. Examples include purification by liquid separation, recrystallization, and column chromatography, and these may be performed alone or in combination. Alternatively, the reaction may proceed to the next reaction without purification. In that case, the crude product may be obtained by distilling off the solvent under reduced pressure and the cross-coupling reaction may be carried out, or the substrates and catalysts required for the cross-coupling reaction may be placed in the same reaction vessel without removing the solvent under reduced pressure. You may also prepare a new one.

Step (C) can be carried out by Sonogashira cross-coupling reaction. A cross-coupling reaction proceeds by dissolving the substrate (1-3) and an alcohol having a carbon-carbon triple bond in a solvent, and adding a palladium catalyst, a copper catalyst, and an amine compound to cause a reaction.

As the amine compound, triethylamine, diisopropylethylamine, diethylamine, etc. can be preferably used, and the amount added is generally in large excess relative to the substrate. Specifically, it is 10 equivalents or more relative to the substrate. As the palladium catalyst, tetrakis(triphenylphosphine)palladium, bis(triphenylphosphine)palladium dichloride, or the like can be suitably used. Copper (I) halide can be used as the copper catalyst, and it is particularly preferable to use copper (I) iodide. There are no particular restrictions on the solvent, but the above amine compound may be used as a solvent, or 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 co-solvent. You may.

Specifically, tetrahydrofuran, 1,4-dioxane, acetone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3- Examples include methoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dibutylpropanamide, and dimethylsulfoxide. The reaction temperature can be carried out at 20° C. to 150° C., and the reaction time is 1 hour to 48 hours, preferably 1 hour to 12 hours. After the reaction, the solvent is distilled off under reduced pressure, a liquid separation operation is performed to remove the remaining metal catalyst and amine components, and the product is purified by recrystallization and/or column chromatography.

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, (±)- Examples include dehydrolinalool, 4-ethyl-1-octin-3-ol, and ethinyl estradiol.

(Application)
The diol compound of the present invention can be polymerized to give unprecedented properties to all resin materials, such as thermoplastic resins, thermosetting resins, cationic curable resins, anionic curable resins, and radical curable resins. It can be used as a monomer for By introducing the rigid structure of isocyanurate and alkyne into the main chain skeleton of the resin, mechanical strength, heat resistance, chemical resistance, hydrolysis resistance, etc. can be improved.

When the diol compound of the present invention is used as a monomer for resin polymerization, the type of resin is not particularly limited, but it can be suitably used for resins that can generally be polymerized using a diol compound as a monomer. Examples of such resins include polyester, polyurethane, polycarbonate, and resins containing these as part of repeating units. Further, 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.

The diol compound of the present invention or a resin made using the compound can be used for various purposes. For example, adhesives, adhesives, electronic materials, insulating materials (including printed circuit boards, wire coatings, etc.), high voltage insulating materials, interlayer insulating films, passivation films for TFTs, gate insulating films for TFTs, interlayer insulating films for TFTs, Transparent flattening film for TFT, insulation packing, insulation coating material, adhesive, high heat resistance adhesive, high heat dissipation adhesive, optical adhesive, LED element adhesive, adhesive for various substrates, heat sink adhesive , paints, UV powder coatings, inks, colored inks, UV inkjet inks, coating materials (including hard coats, sheets, films, release paper coats, optical disk coats, optical fiber coats, etc.), molding materials (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 sealing materials, resist materials, liquid resist materials, colored resists, dry film resist materials, solder resist materials, binder resins for color filters, transparent flattening materials for color filters, binder resins for black matrices, photo spacers for liquid crystal cells Materials, transparent sealing materials for OLED devices, stereolithography, materials for solar cells, materials for fuel cells, display materials, recording materials, anti-vibration materials, waterproof materials, moisture-proof materials, photosensitive drums for copiers, solid electrolytes for batteries, etc. can be mentioned. Further, the isocyanuric acid skeleton-containing polymer may be used as an additive to other resins. Note that it goes without saying that the uses are not limited to the following.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited only to these Examples.

(Example 1)
A reaction vessel was charged with 1 L of N,N-dimethylformamide (hereinafter referred to as DMF) and 48 g of potassium cyanate, and heated to 75°C. A solution prepared by dissolving 198 g of 4-bromophenyl isocyanate in 500 mL of DMF was added dropwise over 30 minutes using a dropping funnel, and after the addition was completed, the reaction was completed by stirring for 1 hour. After removing DMF under reduced pressure and adding 1 L of ethyl acetate and 3 L of water, concentrated hydrochloric acid was added to the aqueous layer, the precipitate was collected, and recrystallized with ethanol to obtain 178 g of white crystals (2). .

In a flask, 21.9 g of the above white crystal (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 were charged, and the mixture was stirred and reacted at 80° C. for 8 hours under a nitrogen atmosphere. After the reaction was completed, triethylamine was removed under reduced pressure, and recrystallization was performed with ethanol to obtain 30.2 g of diol compound (3) represented by the following formula.

(Example 2)
A reaction vessel was charged with 1 L of N,N-dimethylformamide (hereinafter referred to as DMF) and 48 g of potassium cyanate, and heated to 75°C. A solution prepared by dissolving 198 g of 3-bromophenyl isocyanate in 500 mL of DMF was added dropwise over 30 minutes using a dropping funnel, and after the addition was completed, the reaction was completed by stirring for 1 hour. After removing DMF under reduced pressure and adding 1 L of ethyl acetate and 3 L of water, concentrated hydrochloric acid was added to the aqueous layer, the precipitate was collected, and recrystallized with ethanol to obtain 169 g of white crystals (4). .

In a flask, 21.9 g of the above white crystal (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 were charged, and the mixture was stirred and reacted at 80° C. for 8 hours under a nitrogen atmosphere. After the reaction was completed, triethylamine was removed under reduced pressure, and recrystallization was performed with ethanol to obtain 32.4 g of diol compound (5) represented by the following formula.

(Example 3)
The same procedure as in Example 1 was carried out up to the point where (2) was obtained.
43.9 g of white crystals (2), 13.3 g of allyl bromide, 11.1 g of triethylamine, and 500 mL of tetrahydrofuran were placed in a flask, 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 between water and diethyl ether. This liquid separation operation was performed twice in total. The organic layer was concentrated to obtain 45.5 g of compound (6).

In a flask, 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. was charged and reacted by stirring at 80° C. for 8 hours under a nitrogen atmosphere. After the reaction was completed, triethylamine was removed under reduced pressure, the product was purified using a silica column, and then recrystallized with ethanol to obtain 18.4 g of diol compound (7) represented by the following formula.

(Example 4)
The same procedure as in Example 2 was carried out up to the point where compound (4) was obtained.
43.9 g of white crystals (5), 8.85 g of chloromethyl methyl ether, 11.1 g of triethylamine, and 500 mL of tetrahydrofuran were placed in a flask, 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 between water and diethyl ether. This liquid separation operation was performed twice in total. The organic layer was concentrated to obtain 47.8 g of compound (8).

In a flask, 24.1 g of the above white crystal (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 were charged, and the mixture was stirred and reacted at 80° C. for 8 hours under a nitrogen atmosphere. After the reaction was completed, triethylamine was removed under reduced pressure, the product was purified using a silica column, and then recrystallized with ethanol to obtain 16.7 g of diol compound (9) represented by the following formula.

Claims (3)

A compound represented by general formula (1).
However, in the formula, A is a divalent organic group whose terminal is a carbon atom, and R is a hydrogen atom or a monovalent organic group.
2. The compound according to claim 1, wherein A in general formula (1) is a methylene group. Furthermore, the compound according to claim 2, wherein R in the general formula (1) is a monovalent hydrocarbon group having 60 or less carbon atoms.