JPS63255249A - Diacrylate dicarboxylic acid and production thereof - Google Patents

Abstract

NEW MATERIAL:A diacrylate dicarboxylic acid expressed by formula I [R<1>, R<2>, R<3> and R<4> are H or -CH2-CH2-OCO-CR=CH2 (R is H or CH3); R<1> and R<2> and R<3> and R<4> are not mutually equal)]. EXAMPLE:A compound expressed by formula II. USE:Useful as a monomer for ultraviolet (UV) curing type ink and coating, having extremely high chemical activity and capable of forming tough films similarly to other acrylic compounds by applying alone or together with other fillers, high polymer materials, such as vinyl based polymers, polyesters or polyamides, onto a metal, glass or high polymer material and optically or thermally crosslinking with acrylic double bonds in the compound. PREPARATION:A compound expressed by formula III is reacted with beta- hydroxyethyl acrylate in the presence of a catalyst and polymerization inhibitor to afford the aimed compound expressed by formula I.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to 5-(2,5-dioxotetrahydro-3-
Furanyl)-3-methyl-3-cyclohexene-1,2
- A diacrylate dicarboxylic acid derivative of dicarboxylic acid anhydride and a method for producing the same.

[Prior art and its problems] Acrylate compounds have been widely used in UV inks, UV paints, etc. as photo/thermal crosslinking curing type adhesives. Examples include acrylate derivatives of polyhydric alcohols such as β-hydroxyethyl acrylate (β-HEA) and β-hydroxyethyl methacrylate (β-HEMA), which form an essential component throughout the life of the invented compound. However, all of these have carboxyl groups. Since it does not have a strong polar group such as that of 2, it is necessary to perform operations such as anchor coating or corona discharge treatment on the surface of the substrate in order to improve its adhesion to the substrate.

For this reason, making the acrylic compound with UV curability have the same effect as the anchor coating agent eliminates the need for these pre-treatments, and after curing, the coating film becomes smooth due to bleeding of the anchor coating agent. It is extremely useful without impairing its properties, and the development of a compound having such properties has been desired.

The present inventors took the above points into consideration and, as a result of intensive research, discovered that the reaction between a polyvalent carboxylic acid anhydride and a compound having an acrylic double bond and a terminal hydroxyl group (β-FIEA, β-FIEMA, etc.) It was discovered that a diacrylate dicarboxylic acid compound having two acrylic double bonds and two carboxyl groups in the same molecule can be obtained, and the present invention was completed.

[Means for Solving the Problems] That is, the present invention has the formula: It is a diacrylate dicarboxylic acid represented by (R1 and R2, R3 and R4 are never equal at the same time), and its manufacturing method is a-<2.5-dioxotetrahydro-3 represented by
-furanyl)-3-methyl-3-cyclohexene-1,
Formula (■) characterized in that 2-dicarboxylic anhydride and β-hydroxyethyl acrylate or β-hydroxyethyl methacrylate are reacted in the presence of a catalyst and a polymerization inhibitor: (wherein Rj, R2, R3 and R
4 is a hydrogen atom or -CH2-CH2-0CO-CR=
Arrange the CH2 group (R=H or CH3), R1 and R
2, R3 and R4 are never equal at the same time).

The compound represented by the formula (I>) according to the present invention is a new compound and has both an acrylic double bond and a polar group such as a carboxylic acid group or an ester group in one molecule.
It is useful as a UV-curable ink and a seven-point marker for Il'ff.

5-, which is a raw material for producing the above compound (I>)
(2,5-dioxotetrahydro-3-furanyl)-3
-Methyl-3-cyclohexene-1,2-dicarboxylic anhydride (MCTC) reacts with alcohol to open the ring of the acid anhydride and produce a half ester. MCTC is
It has two acid anhydride groups in its molecule, has no superiority or inferiority in reactivity, and can be easily converted into a ring-opening half-ester. Generally, this reaction can be carried out in an excess of alcohol, with or without a catalyst, at a temperature lower than that required for the ester formation reaction from the free carboxylic acid and alcohol. However, in the present invention, excess β
-The presence of HEA or β-HEMA requires a large amount of polymerization inhibitor, and in the process of removing β-HEA or β-HEMA under reduced pressure after the reaction,
Since the polymerization inhibitor is removed together with these, the resulting diacrylate dicarboxylic acid causes polymerization and gelation within the system. Therefore, in the present invention, unlike the usual reaction between an alcohol and an acid anhydride, it is necessary to match the equivalent weight and to proceed the reaction at a low temperature. For this reason, in the present invention, unlike conventional ring-opening half-esterification reactions that have been well known, strictness is required in the selection of reaction conditions and catalysts.

Examples of catalysts include inorganic and organic protic acids such as sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, and trifluoroacetic acid; Lewis acids such as zinc chloride, boron fluoride, titanium chloride, and tin chloride; and tertiary Amine, pyridine derivatives can be used. Among these, the half-esterification reaction can be most advantageously completed by using 4-dimethylaminopyridine, 4-pyrrolidinoviridine, or triethylamine in combination with pyridine derivatives.

The reaction may be carried out with or without a solvent, but since the diacrylate dicarboxylic acid produced is an extremely viscous oil, it is difficult to carry out the reaction completely without a solvent. Use of a suitable solvent is desirable.

Usable solvents include the acid anhydride of the substrate, β-HEA, β-
The type is not particularly limited as long as it is inert with HEMA and the catalyst, but examples include benzene, toluene,
Aromatic hydrocarbons such as xylene, tetrahydrofuran,
Ether solvents such as dioxane and dimethoxyethane,
Aprotic polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, or dichloroethane, chloroform,
Examples include aliphatic or aromatic halogen compounds such as methylene chloride and 0-dichlorobenzene, and in particular, toluene and tetrahydrofuran are commonly used.

The reaction can be carried out at a temperature ranging from room temperature to a temperature at which esterification of free carboxylic acid occurs, for example, 140° C. or less. However, as mentioned above, since the raw material acrylate and the product are easily polymerized by heat,
The reaction temperature is preferably 60'C to 100C.

Furthermore, a polymerization inhibitor is used in the reaction system to inhibit polymerization. As the polymerization inhibitor, hydroquinone, hydroquinone 7-methyl ether, phenothiazine, etc. are used. The amount to be added may be as much as necessary to inhibit the polymerization of β-HEA, β-HEMA, and the product diacrylate dicarboxylic acid, that is, about 10 ppm to 5%.

According to the method of the present invention, the compounds represented by the formula (I>) are usually obtained in the form of a mixture due to the difference in the esterification site during half-esterification, but all of the compounds have an acrylic diacetate in the molecule. There is no difference in that they have a heavy bond, a carboxylic acid group, and an ester group, so there is no problem in practical use even if they are a mixture.

[Effects of the Invention] The diacrylate dicarboxylic acid of the present invention has two free carboxyl groups, two ester bonds, and two active acrylic double bonds in the same molecule, and is extremely chemically active. It is a compound. For example, this compound can be applied alone like other acrylic compounds or together with fillers, vinyl polymers, polyesters, polyamides, and other polymeric materials onto metal, glass, or polymeric materials. Next, by photo- or thermally cross-linking the acrylic double bonds in the compound, a tough coating film can be produced, and due to the presence of polar groups such as carboxyl groups and ester groups in the molecule, the acrylic double bonds in the compound can be crosslinked. It is expected that the adhesion will be excellent.

The present invention will be explained below using examples.

Example 1 A 1 fJ glass reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 340 Cl of toluene, 0.5 CJ of dimethylaminopyridine, 4.0 g of hydroquinone, and 232 g of β-hydroxyethyl acrylate. 'C
The temperature rises to Here, 5-(2,5-dioxo-tetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (MCTC) 264
Add 10 g in 5 portions over 1 hour. After reacting at this temperature for 2 hours, the mixture is reacted at 80° C. for 2 hours.

The reaction was followed by IR and acid value measurement, and when the IR peak at 1840 cm attributed to acid anhydride was no longer observed and the acid value reached the calculated value,
This marked the end of the reaction. After cooling the internal temperature of the reactor to 50° C. or lower, a target compound represented by the following formula (III) was taken out.

(In the formula, R1 and R2, R3 and R4 are 1 and -C, respectively.
(indicating the combination t12-C112-OCO-CH=CH2) The analysis results were as follows.

Infrared absorption spectrum (measured by coating method 1 on KBr plate): Shown in Figure 1 Non-volatile content: 58.3% (140°C, 1 hour) Acid value:
146 (calculated value 149) From the measurement results of gas chromatograph (GC), residual β-
Hydroxyacrylate is 0.3% based on the preparation
(0.7q) or less, it was found from the measurement results of infrared absorption spectrum (IR) that the amount of unreacted MCTC was 0.3% (0.8a) or less.

Example 2 232 g of β-hydroxyethyl acrylate from Example 1
β-hydroxyethyl methacrylate 260 (
], dimethylaminopyridine 0.5 (replaced 7 with dimethylaminopyridine 0.3g and triethylamine 1
．． The same reaction as in Example 1 was carried out except that 4.0 g of hydroquinone was used instead of 4.0 g of hydroquinone monomethyl ether to obtain the target compound represented by the following formula (IV).

(In the formula, R1 and R2, R3 and R4 are 1 and -C, respectively.
The analysis results were as follows.

Infrared absorption spectrum (measured in the same manner as Example 1)
: Nonvolatile content shown in Figure 2: 59.7% (140°C, 1 hour) Acid value:
127.8 (calculated value 128.8>

[Brief explanation of the drawing]

FIG. 1 shows an infrared absorption spectrum of a compound obtained in one example of the present invention, and FIG. 2 shows an infrared absorption spectrum of a compound obtained in another example.

Claims (4)

[Claims] (1) Formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1, R^2, R^3 and R^4 are hydrogen atoms or -CH_2-CH_2-OCO-CR=CH_
Represents two groups (R-H or CH_3), R^1 and R
A diacrylate dicarboxylic acid represented by ^2, R^3 and R^4 are never equal at the same time). (2) Formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 5-(2,5-dioxotetrahydro-3-
Furanyl)-3-methyl-3-cyclohexene-1,2
- A formula characterized by reacting a dicarboxylic acid anhydride with β-hydroxyethyl acrylate or β-hydroxyethyl methacrylate in the presence of a catalyst and a polymerization inhibitor: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula , R^1, R^2, R^3 and R^4 are hydrogen atoms or -CH_2-CH_2-OCO-CR=CH_
Represents two groups (R=H or CH_3), R^1 and R
^2, R^3 and R^4 are never equal at the same time) A method for producing diacrylate dicarboxylic acid represented by: (3) The method for producing diacrylate dicarboxylic acid according to claim 2, which uses 4-dimethylaminopyridine or 4-pyrrolidinoviridine as a component of the catalyst. (4) The method for producing diacrylate dicarboxylic acid according to claim 2, which uses hydroquinone or a derivative thereof as a polymerization inhibitor.