JP2003073340A - Isophthalic acid compound and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a monomer comprising a one to three (substituted) acryloyl groups-having isophthalic acid compound useful as a raw material for acrylic polymers. SOLUTION: This isophthalic acid compound is represented by the general formula [1] R<5> , R<6> and R<7> are each H or a (substituted) acryloyl of formula [2], provided that at least one of R<4> , R<6> and R<7> is the (substituted) acryloyl; X is a halogen atom; R<1> is H or a 1 to 4C alkyl; R<2> , R<3> and R<4> are each H or a 1 to 10C alkyl}, and the method for producing the isophthalic acid compound is characterized by reacting a bis(2-hydroxyethyl)5-hydroxyisophthalate (BH5HI) represented by the general formula [3] with a (substituted) acrylic acid compound represented by the general formula [4] in the presence of an acid catalyst or reacting the BH5HI with an acrylic halide compound represented by the general formula [5] in the presence of a base, a metal and a metal compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an isophthalic acid compound having a (substituted) acryloyl group and a method for producing the same. The compound of the present invention relates to radical polymerization and ultraviolet curing monomers in the field of materials such as resins for EL (electroluminescence) protective films, adhesives for dentistry and special paints.

[0002]

2. Description of the Related Art Japanese Unexamined Patent Publication (Kokai) No. 5-214045 describes an acryloyl compound of an existing aromatic carboxylic acid such as benzoic acid, phthalic acid, trimellitic acid and pyromellitic acid. I haven't gotten it.

[0003]

An object of the present invention is to provide a monomer having 1 to 3 (substituted) acryloyl groups as a raw material for an acrylic polymer.

[0004]

[Means for Solving the Problems] The present inventor has conducted diligent research in order to solve the above problems. The screw (2) described in Japanese Patent Application No. 2000-206499 filed previously by the present inventors
-Hydroxyethyl) 5-hydroxyisophthalate (abbreviated as BH5HI) as a raw material,
The present invention has been completed by finding that a novel acryloyl compound can be obtained.

That is, the compound of the present invention has the formula [1]

[0006]

[Chemical 11]

(In the formula, R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or a formula [2]

[0008]

[Chemical 12]

(In the formula, R ¹ is a hydrogen atom or a carbon number of 1 to
4 represents an alkyl group, and R ² and R ³ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ) Represents a (substituted) acryloyl group, and at least one or more represents a (substituted) acryloyl group. ) Related to an isophthalic acid compound and a method for producing the same.

The present invention also provides the formula [3].

[0011]

[Chemical 13]

Bis (2-hydroxyethyl) represented by
5-hydroxyisophthalate (BH5HI) and formula [4]

[0013]

[Chemical 14]

(Wherein R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above) and a (substituted) acrylic acid compound is reacted in the presence of an acid catalyst. BH5HI represented by the above formula [3] and the formula [5]

[0015]

[Chemical 15]

In the formula, R ¹ , R ² and R ³ have the same meanings as described above, and X represents a halogen atom. The present invention relates to a method for producing an isophthalic acid compound represented by the above formula [1] by reacting below. Hereinafter, the present invention will be described in detail.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing an isophthalic acid compound represented by the above formula [1] of the present invention is represented by the following two reaction schemes.

[0018]

[Chemical 16]

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ ,
R ⁷ and X have the same meanings as described above. ) First, (1) will be described. B represented by the formula [3] of the raw material
As described in Japanese Patent Application No. 2000-206499, H5HI can be efficiently produced using a 5-hydroxyisophthalic acid compound and ethylene glycol as raw materials and an acid, a metal or a metal compound as a catalyst.

On the other hand, in the acrylic acid compound represented by the general formula [4], R ¹ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or 1 to 2 carbon atoms. Further, R ² , R ³ and R ⁴ have 1 to 10 carbon atoms,
Preferably, it is a hydrogen atom or has 1 to 5 carbon atoms.

Specifically, acrylic acid, methacrylic acid, tiglylic acid, 3,3-dimethylacrylic acid, 2-methyl-2-pentenoic acid, 2-ethyl-2-hexenoic acid, 2-octenoic acid and the like, And their alkyl ester compounds having 1 to 10 carbon atoms, specifically, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl tiglylate, ethyl tiglylate, 3,3-dimethylacryl. Acid methyl, ethyl 3,3-dimethylacrylate, methyl 2-methyl-2-pentenoate, ethyl 2-methyl-2-pentenoate, methyl 2-ethyl-2-hexenoate, 2-ethyl-2-hexenoic acid Examples thereof include ethyl, methyl 2-octenoate and ethyl 2-octenoate.

This reaction requires an acid catalyst, and as the acid catalyst, mineral acids such as sulfuric acid, hydrochloric acid and nitric acid can be used, and sulfuric acid is particularly preferable. In addition, benzenesulfonic acid, p-
Organic acids such as toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid and trifluoroacetic acid can be used, and benzenesulfonic acid and p-toluenesulfonic acid are particularly preferable. The amount of the acrylic acid compound used may be a theoretical amount or a large excess amount.

Further, examples of the acid catalyst include tungstic acid, molybdic acid and heteropolyacids thereof. Specific examples of the heteropolyacid include H ₃ PW ₁₂ O ₄₀ and H ₄ Si.
W ₁₂ O ₄₀ , H ₄ TiW ₁₂ O ₄₀ , H ₅ CoW ₁₂ O ₄₀ , H ₅ F
eW ₁₂ O ₄₀ , H ₆ P ₂ W ₁₈ O ₆₂ , H ₇ PW ₁₁ O ₃₃ , H ₄ T
_{iMo 12 O 40, H 3 PMo} 12 O 40, H 7 PMo 11 O 39, H
₆ P ₂ Mo ₁₈ O ₆₂ , H ₄ PMoW ₁₁ O ₄₀ , H ₄ PVMo ₁₁ O
_{40, H 4 SiMo 12 O 4} 0, H 5 PV 2 Mo 10 O 40, H 3 PM
Representative examples thereof include o ₆ W ₆ O ₄₀ , H _0.5 Cs _2.5 PW ₁₂ O _40, and their hydrates. Further, a catalyst in which these are supported on carbon or silica can be used. Among these _{heteropolyacids, H 3 PW 13 O 4 0} , H 3 PMo 12
O ₄₀ and hydrates thereof are particularly preferable.

Further, a cation exchange resin such as Amberlyst IR120 and an H type zeolite such as H-ZSM-5 can be used.

In particular, as the catalyst for the transesterification method, in addition to the above-mentioned mineral acids, heteropolyacids, organic acids, cation exchange resins and H-type zeolite, 3ZnO-2B ₂
Fatty acid salts of compounds of Group II of the periodic table represented by O ₃ , cadmium acetate, zinc acetate and calcium acetate can be used. The amount of these catalysts used was 0.
1 to 100% by weight can be used, and 1 to 20% by weight is economically preferable.

This reaction can be carried out using a solvent, although the acrylic acid compound can be used in a large excess, and it is usually preferable to use a solvent. Examples of the solvent include 1,2-dichloroethane (EDC) and 1,1,1-
Halogenated hydrocarbons such as trichloroethane, aromatic hydrocarbons such as benzene, toluene and xylene, 1,2
And ethers such as dimethoxyethane and diethylene glycol dimethyl ether.

The amount of the solvent used is 1-2 with respect to BH5HI.
It is 0 times by weight, more preferably 1 to 6 times by weight. The reaction temperature is 50 to 200 ° C, more preferably 70 to 150 ° C.
Is. The reaction can be carried out at normal pressure or under pressure. The reaction time can be 1 to 50 hours, usually 2-1.
It is practical to do it in 2 hours.

Next, the production method of reaction scheme (2) will be described. The acrylic acid halide compound represented by the general formula [5] has the same R ¹ , R ² and R ^{3 as} described above,
Specifically, it is a halide such as acrylic acid, methacrylic acid, tiglylic acid, 3,3-dimethylacrylic acid, 2-methyl-2-pentenoic acid, 2-ethyl-2-hexenoic acid and 2-octenoic acid. . The types of halogen are fluorine, chlorine, bromine and iodine, and economically chlorine. Particularly, acrylic acid chloride and methacrylic acid chloride are used. The amount used is 1 to 2 times, and more preferably 1 to 1.5 times the theoretical amount of BH5HI.

This reaction requires a base, examples of which include inorganic bases such as carbonates and hydroxides of alkali metals and alkaline earth metals, organic bases such as aliphatic and aromatic bases and alkali metals and alkaline earths. Metal fatty acid salts and the like can be used. Specific examples thereof include sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, trimethylamine, triethylamine, tripropylamine,
Examples include pyridine, picoline, aniline, sodium acetate, sodium oxalate and the like. Particularly, sodium carbonate and triethylamine are preferable. The amount used is 1 to 2 mole times, more preferably 1 to 1.5 mole times, relative to the theoretical amount of BH5HI, and the same amount as the acrylic acid halide compound is preferable. It is also possible to use a metal or metal hydride complex.

As the metal, an alkali metal of Group 1 and an alkaline earth metal of Group 2 of the Periodic Table can be applied, and specific examples thereof include lithium, sodium, potassium, magnesium and calcium. Further, as the metal compound, a metal such as lithium hydride, sodium hydride, potassium hydride, lithium aluminum hydride, sodium aluminum hydride, potassium aluminum hydride, lithium borohydride, sodium borohydride, potassium borohydride, etc. Examples thereof include hydrogenated complexes, metal hydroxides such as sodium hydroxide and potassium hydroxide, metal carbonates such as sodium carbonate and potassium carbonate. Particularly, sodium and sodium hydride are preferable. The amount used is the same as above.

In this reaction, it is preferable to use a solvent. Tetrahydrofuran (TH
F), dioxane, ethers such as 1,2-dimethoxyethane and diethylene glycol dimethyl ether, and the like. The amount of the solvent used is 1 to 20 times by weight, and more preferably 1 to 6 times by weight, that of BH5HI. The reaction temperature is preferably -20 to 100 ° C, particularly preferably 0 to 50 ° C.

After the reaction, water is added to hydrolyze the residual acid chloride, the solvent is distilled off, and the mixture is extracted with a poorly water-soluble solvent (ether system or ester system) and then distilled or column chromatographed. The product can be purified to obtain the desired product. The above-mentioned reaction and purification of the present invention can be performed in a batch system or a continuous system. The products obtained by this reaction are listed below.

[0033]

[Chemical 17]

(In the formula, R ¹ , R ² and R ³ have the same meanings as described above.)

[0035]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Example 1

[0036]

[Chemical 18]

BH5HI was added to a 100 ml four-neck reaction flask.
1.35 g (5 mmol) and 17 g of N, N-dimethylacetamide (DMAc) were charged and cooled to 5 ° C. Under this stirring, sodium hydride (purity 60%) 0.72
g (18 mmol) was added and stirred for 1.5 hours. Further, at 5 ° C., 3.14 g of methacryloyl chloride (3
0 mmol) was added dropwise. After continuing stirring at 5 ° C for 1 hour, the mixture was further reacted at 25 ° C for 6 hours. Ice was added to the reaction solution and then concentrated to remove DMAc. Ethyl acetate / water was added to the residue for extraction, and the insoluble solid matter was removed by filtration.
When the organic layer of the filtrate was concentrated and dried, 3.44 g of an oily matter was obtained. This oily matter was added to n-heptane / ethyl acetate = 19 /
When purified by silica gel column chromatography at 1-3 / 1, 0.59 g of 1,3-bis (2-methacryloyloxyethoxycarbonyl) -5-methacryloyloxybenzene (abbreviated as BMMB) (yield 24. 9%) was obtained.

MASS (FAB ⁺ , m / e (%)): 475 ([M + H] ⁺ , 15), 431
(25), 389 (63), 345 (94), 124 (100), 113 (100). ¹ H-NMR (CDCl ₃ , δppm): 1.82 (s, 6H), 1.95 (s, 3H), 4.38
(dd, J ₁ = 3.21Hz, J ₂ = 4.74Hz, 4H), 4.49 (dd, J ₁ = 3.21Hz, J ₂
= 4.74Hz, 4H), 5.48 (t, J = 1.53Hz, 2H), 5.71 (d, J = 1.53Hz, 1
H), 6.03 (s, 2H), 6.28 (s, 1H), 7.89 (dd, J ₁ = 1.53Hz, J ₂ = 3.3
6Hz, 2H), 8.45 (t, J = 1.52Hz, 1H). ¹³ C-NMR (CDCl ₃ , δppm): 17.78 (2), 17.81,61.98 (2), 62.9
3 (2), 125.96 (2), 127.16 (2), 127.68,127.93,131.39 (2), 1
34.84,135.45 (2), 150.66,164.24,164.99,166.87.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // C07B 61/00 300 C07B 61/00 300

Claims (5)

[Claims] 1. A formula [1] (In the formula, R ⁵ , R ⁶ and R ⁷ are hydrogen atoms or a compound of the formula [2] (In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² and R ³ represent a hydrogen atom or 1 to 1 carbon atoms.
Represents an alkyl group of 0. ) Represents a (substituted) acryloyl group, and at least one or more represents a (substituted) acryloyl group. ) An isophthalic acid compound represented by. 2. A formula [3] Bis (2-hydroxyethyl) 5-hydroxyisophthalate represented by the formula [4] (In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² , R ³ and R ⁴ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.). (Replacement)
A compound represented by the formula [1], which is characterized by reacting an acrylic acid compound with an acid catalyst. (In the formula, R ⁵ , R ⁶ and R ⁷ are hydrogen atoms or a compound of the formula [2] (In the formula, R ¹ , R ² and R ³ have the same meanings as described above.) Represents a (substituted) acryloyl group, and at least one or more represents a (substituted) acryloyl group. ) The manufacturing method of the isophthalic acid compound represented by. 3. The method for producing an isophthalic acid compound according to claim 2, wherein the acid catalyst is p-toluenesulfonic acid, benzenesulfonic acid or sulfuric acid. 4. The formula [3]: Bis (2-hydroxyethyl) 5-hydroxyisophthalate represented by the formula [5] (In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² and R ³ represent a hydrogen atom or 1 to 1 carbon atoms.
0 represents an alkyl group, and X represents a halogen atom. )
An acrylic acid halide compound represented by the formula [1] is characterized by reacting in the presence of a base, a metal and a metal compound. (In the formula, R ⁵ , R ⁶ and R ⁷ are hydrogen atoms or a compound represented by the formula [2] (In the formula, R ¹ , R ² and R ³ have the same meanings as described above.) Represents a (substituted) acryloyl group, and at least one or more represents a (substituted) acryloyl group. ) The manufacturing method of the isophthalic acid compound represented by. 5. The base is an alkylamine and the metal compound is a metal hydride complex or a metal carbonate.
A method for producing the described isophthalic acid compound.