JPH0543512A - Dicyclopentadiene derivtive - Google Patents

Abstract

PURPOSE:To provide a new dicyclopentadiene derivative expectable as a raw material for an acrylate polymer having excellent transparency, heat-resistance, thermal stability, solvent resistance and dielectric characteristics as well as mechanical strength. CONSTITUTION:The dicyclopentadiene derivative of formula I (R is H or CH3). It can be produced by reacting a diol of formula VI with an acrylic acid derivative and/or methacrylic acid derivative in the presence of an esterification catalyst. The starting compound of formula VI is produced by the deacetalization reaction of a m-dioxane derivative of formula V obtained by the condensation reaction of dicyclopentadiene (IV) and formaldehyde. The compound is a polymerizable monomer expected to solve the problem of poor mechanical strength of known alicyclic acrylate polymer and has high industrial value.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a dicyclopentadiene derivative represented by the general formula (I). This derivative is a very useful compound used as a raw material for a novel acrylate polymer having excellent physical and chemical properties such as transparency, heat resistance, thermal stability, solvent resistance, and dielectric properties. ..

[0002]

BACKGROUND OF THE INVENTION Conventionally, an alicyclic compound used for producing an acrylate polymer excellent in physical and chemical properties such as transparency, heat resistance, thermal stability, solvent resistance, and dielectric properties. Examples of the acrylate-based monomer of general formula (IV) obtained by reacting dicyclopentadiene maleate, polyhydric alcohol and, if necessary, an acid in JP-B-61-34446.

[0003]

[Chemical 4] A compound represented by the formula (wherein R represents hydrogen, a methyl group or an isopropyl group) is disclosed.

[0004]

According to the studies by the present inventors, the acrylate polymer of the alicyclic compound described above is very sterically crowded, so that it has a dicyclopentadiene skeleton against external pressure. There was a problem in mechanical strength because the strain between the ester and the ester was large and the bond was easily broken. However, the novel dicyclopentadiene derivative according to the present invention has a methylene group between the dicyclopentadiene skeleton and the ester, and it is expected that the degree of freedom of the molecule is increased against external pressure, and the mechanical strength Can be expected to be excellent in.

Therefore, the objects of the present invention are transparency, heat resistance,
It is an object of the present invention to provide a novel dicyclopentadiene derivative that can be expected as a raw material for producing a polymer having thermal stability, solvent resistance, and dielectric properties and having excellent mechanical strength.

[0006]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted extensive research to develop a monomer as a raw material for a polymer having the above-mentioned function, and as a result, are represented by the general formula (I). The inventors have developed a dicyclopentadiene derivative and completed the present invention.

That is, the present invention has the general formula (I)

[0008]

[Chemical 5] (In the formula, R represents hydrogen or a methyl group) and relates to a dicyclopentadiene derivative.

The method for producing the dicyclopentadiene derivative represented by the general formula (I) of the present invention is not particularly limited, but for example, it can be produced by the following method.

[0010]

[Chemical 6] The metadioxane derivative represented by the general formula (V) is obtained by a condensation reaction between dicyclopentadiene and formaldehyde. As formaldehyde, paraformaldehyde or formalin aqueous solution can be used. The amount used is appropriately 2.0 to 3.0 equivalents to dicyclopentadiene.

In this condensation reaction, a catalyst can be used, and an acid catalyst is preferable as the catalyst. Specific examples thereof include mineral acids such as concentrated sulfuric acid, nitric acid and phosphoric acid, heteropolyacids and ion exchange resins, but concentrated sulfuric acid is preferable from the viewpoint of selectivity. A suitable amount of the catalyst used is 0.15-0.3 equivalents based on dicyclopentadiene.

Further, a solvent may be used in this reaction. Specifically, tetrahydrofuran (THF),
Examples thereof include ether solvents such as dioxane, aromatic hydrocarbon solvents such as benzene and toluene, and ether solvents are particularly preferable.

By carrying out the reaction at a reaction temperature of 60 to 80 ° C. and a reaction time of 5 to 14 hours, the desired metadioxane derivative represented by the general formula (V) can be obtained.

The diol represented by the general formula (VI) is obtained by deacetalizing the metadioxane derivative represented by the general formula (V). This deacetal reaction may be carried out using a mineral acid such as hydrochloric acid and an alcohol solvent such as methanol or ethanol as a solvent. The amount of the mineral acid used is 1-2 equivalent to the metadioxane derivative, and methanol is particularly preferable as the solvent.

The reaction temperature is 60 to 70 ° C. and the reaction time is 2 to 4 hours, whereby the desired diol represented by the general formula (VI) is obtained. The dicyclopentadiene derivative represented by the general formula (I) of the present invention is a diol and an acrylic acid derivative represented by the general formula (VI) obtained as described above and /
Or in the presence of an esterification catalyst with a methacrylic acid derivative,
Obtained by reacting.

As the acrylic acid derivative, acrylic acid,
Acrylic anhydride and acrylic acid halides such as acrylic acid chloride can be exemplified, and as the methacrylic acid derivative, methacrylic acid halides such as methacrylic acid, methacrylic anhydride, and methacrylic acid chloride can be exemplified. ..

The amount of acrylic acid derivative or methacrylic acid derivative to be used is suitably 2-5 equivalents based on the starting diol. As the esterification catalyst, an acid catalyst such as concentrated sulfuric acid may be used, and the esterification catalyst may be 0.05-
It suffices to use 0.15 equivalent. The reaction temperature is 7
The desired dicyclopentadiene derivative represented by the general formula (I) is obtained by reacting at 0-80 ° C for about 5 hours.

In addition to the above-mentioned production method, a reaction of the metadioxane derivative represented by the general formula (V) with an acrylic acid derivative and / or a methacrylic acid derivative, or dicyclopentadiene, formaldehyde, an acrylic acid derivative and The dicyclopentadiene derivative represented by the general formula (I) can be obtained by the reaction with the methacrylic acid derivative. In addition, when the metadioxane derivative is used as a raw material, the amount thereof is appropriately 0.05 to 0.15 equivalent of sulfuric acid, 2 to 5 equivalents of acrylic acid derivative and / or methacrylic acid derivative with respect to the metadioxane derivative. .. When dicyclopentadiene is used as a raw material, 0.05-0.15 equivalents of sulfuric acid, 1-2 equivalents of aldehyde, 2-5 equivalents of acrylic acid derivative and / or methacrylic acid derivative are used with respect to dicyclopentadiene. Is appropriate. The positional isomers of the dicyclopentadiene derivative represented by the general formula (I) of the present invention include the chemical formula (II) or (III).

[0019]

INDUSTRIAL APPLICABILITY The dicyclopentadiene derivative of the present invention is a polymerizable monomer that is expected to be able to overcome the weak mechanical strength of conventionally known acrylate polymers of alicyclic compounds. And its industrial value is high.

[0020]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 In a 100 ml three-necked flask equipped with a stirrer and a thermometer, 6.6 g (50 mmol) of dicyclopentadiene,
30 ml of 1,4-dioxane, dimethyl sulfoxide 2
ml, paraformaldehyde 4.0 g (2.2 eq.)
And 0.4 g of concentrated sulfuric acid was added, and the reaction was carried out at 80 ° C. for 14 hours. The reaction solution was allowed to cool to room temperature, water was added, and the mixture was extracted with ethyl acetate. The extract was dried over anhydrous sodium carbonate. After removing sodium carbonate by filtration, ethyl acetate and low-boiling compounds were removed under reduced pressure. As a result of gas chromatographic analysis of the obtained oily crude product, a metadioxane derivative represented by the general formula (V) was produced in a yield of 51.1% with respect to the raw material dicyclopentadiene.

10 equipped with stirrer, cooling tube and thermometer
In a 0 ml three-necked flask, 2.88 g (15 mmol) of the metadioxane derivative synthesized above, methanol 15
ml and 2N-HCl aqueous solution 1.7 ml,
The reaction was carried out at ℃ for 4 hours. The reaction solution was allowed to cool to room temperature, water was added, and the mixture was extracted with methylene chloride. The extract was dried over anhydrous sodium carbonate. After filtering off sodium carbonate, methylene chloride and low boiling compounds were removed under reduced pressure. After dissolving the obtained oily crude product in acetone, n
-Hexane was added resulting in a white precipitate. After filtering this precipitate off, the crystals were freed from the solvent under reduced pressure. As a result of analyzing this crystal by NMR and IR, it was confirmed to be a diol represented by the general formula (VI). The yield of this product was 1.54 g, which was 54% with respect to the metadioxane derivative as a raw material.

In a 100 ml three-necked flask equipped with a stirrer and a thermometer, 2.01 g of the diol previously synthesized
(16 mmol), acrylic acid 18 g and concentrated sulfuric acid 0.
4 g was added and the reaction was carried out at 80 ° C. for 5 hours. The reaction solution was allowed to cool to room temperature, water was added, and the mixture was extracted with ethyl acetate. The extract was dried over anhydrous sodium carbonate. After removing sodium carbonate by filtration, ethyl acetate and low-boiling compounds were removed under reduced pressure. The obtained oily crude product was separated by high performance liquid chromatography. The obtained oily product was analyzed by NMR, IR and CHN, and as a result, it was confirmed that the product was a mixture of positional isomers of the diacrylate ester shown below.

[0024]

[Chemical 7] As a result of gas chromatographic analysis, this dicyclopentadiene derivative was found to have 14.1 relative to the starting diol.
It was produced in a yield of%.

Regarding the analysis result of this dicyclopentadiene derivative, the elemental analysis result is shown in Table 1, the infrared absorption spectrum is shown in Table 2, and the nuclear magnetic resonance spectrum is shown in Tables 3 and 4.
Shown in.

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

[Table 3]

[0029]

[Table 4]

Claims (2)

[Claims] 1. A compound represented by the general formula (I): (In the formula, R represents hydrogen or a methyl group) A dicyclopentadiene derivative. 2. A compound represented by the following general formulas (II) and (III): (In the formula, R represents hydrogen or a methyl group.) A dicyclopentadiene derivative mixture (wherein R represents hydrogen or a methyl group).