JPH0629277B2 - Acrylate compound and method for producing the same - Google Patents

Description

Detailed Description of the Invention A. TECHNICAL FIELD The present invention relates to a novel (meth) acrylate compound represented by the following general formula (I) and a method for producing the same.

(In the formula, R represents H or CH ₃ ) The compound represented by the formula (I) is a compound which is easily homopolymerized or contains another unsaturated group in the presence of heat, ultraviolet rays, ionizing radiation, or a radical polymerization initiator. Can be copolymerized with.

B. 2. Description of the Related Art Conventionally, various acrylic acid esters have been known.
For example, monofunctional monomers such as methyl methacrylate, ethyl acrylate, and 2-ethylhexyl acrylate, and polyfunctional monomers such as trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and pentaerythritol triacrylate are generally known.

C. DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention However, among the above-mentioned polyfunctional monomers, when used in printing inks and paints, the odor of the unreacted monomers after curing becomes a serious problem. Further, when the polyfunctional monomer is used as a diluent for paints and printing inks, it needs to be used in a large amount with respect to the resin, and therefore has the drawback that the characteristics possessed by the resin are lost.

D. Means, Actions and Effects for Solving Problems As a result of earnest research, the present inventors have obtained a novel (meth) acrylic acid ester having low viscosity, low odor and solubility in a wide range of resins. It was These are useful as raw materials or modifiers for inks, paints, adhesives, coatings, molding resins.

The compound (I) of the present invention can be produced, for example, by the following method.

Dicyclopentadiene and ethylene glycol with sulfuric acid, p
-An ethylene glycol adduct of dicyclopentadiene is obtained by reacting at 100 to 120 ° C for 5 to 8 hours under an acidic catalyst such as toluenesulfonic acid or boron trifluoride. Dicyclopentenyloxyethyl (meth) acrylate can be obtained by esterifying this adduct with (meth) acrylic acid or a (meth) acrylic acid derivative.

When esterification is performed using (meth) acrylic acid, an acidic catalyst such as sulfuric acid or p-toluenesulfonic acid may be used as a catalyst. The polymerization inhibitor used in the reaction step is preferably one that can be easily removed by washing with an aqueous alkaline solution of hydroquinone, hydroquinone monomethyl ether, cuprous chloride or the like.

As an azeotropic solvent used to take out water generated by the esterification reaction to the outside of the system, an azeotropic mixture with water such as benzene, toluene, xylene, n-hexane and methyl isobutyl ketone is prepared, and substantially It is possible to use organic solvents which are immiscible with one another, alone or in mixtures.

Further, (meth) acrylic acid derivatives such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, n-propyl (meth) acrylate, (meth)
It is also possible to produce dicyclopentenyloxyethyl (meth) acrylate by transesterification using a (meth) acrylic acid ester compound such as isopropyl acrylate.

In this case, as the polymerization inhibitor, when using sulfuric acid or paratoluenesulfonic acid as a catalyst for transesterification reaction, hydroquinone, hydroquinone monomethyl ether, etc. are used, but when an alkaline catalyst such as sodium metal or sodium alcoholate is used, it is alkaline. Polymerization inhibitors such as para-phenylenediamine and phenyl-β-naphthylamine are used. The transesterification reaction is promoted by taking out the produced lower alcohol together with a part of the (meth) acrylic acid ester compound from the system.

In this manner, the obtained dicyclopentenyloxyethyl (meth) acrylate was treated with formic acid, acetic acid, propionic acid, butyric acid, succinic acid, adipic acid, benzoic acid, etc. and an organic peracid prepared using hydrogen peroxide. Compound (I) is obtained by epoxidation.

The mixing ratio of dicyclopentenyloxyethyl (meth) acrylate and organic peracid is 0.2 to 2 times mol, preferably 0.5 to 1 times mol, of dicyclopentenyloxyethyl (meth) acrylate.

In the epoxidation reaction, it is preferable to add 100 to 1,000 ppm of hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, β-naphthol and the like as a polymerization inhibitor.

E. Examples Hereinafter, the present invention will be described with reference to Examples.

[Example 1] Production of dicyclopentenyloxyethanol 124 g of ethylene glycol and 5.7 g of boron trifluoride ethyl ether complex were charged into a reaction vessel, heated to 100 ° C, and 132 g of dicyclopentadiene while maintaining the same temperature.
Was added dropwise over 5 hours. After completion of dropping, the reaction was continued for 2 hours to eliminate dicyclopentadiene. The reaction product was cooled to room temperature, and 2.7 m of a 15 N aqueous ammonia solution was slowly added to neutralize the boron trifluoride ethyl ether complex. The obtained reaction product was extracted with n-hexane and washed with water, and then n- with a rotary evaporator.
Remove hexane and dicyclopentenyloxyethanol
169 g was obtained.

Preparation of dicyclopentenyloxyethyl acrylate 194 g of dicyclopentenyloxyethanol thus obtained, 79.2 g of acrylic acid, 2.7 g of p-toluenesulfonic acid as a catalyst, 0.8 g of hydroquinone monomethyl ether as a polymerization inhibitor and 200 m of toluene A reaction vessel equipped with a reflux condenser, a water separator, and a stirrer was charged and heated at a toluene reflux temperature for 5 hours while stirring.
The distilled toluene-water fraction was subjected to water separation in a water separator, and then toluene was continuously returned to the reactor. The reaction was continued until no water was distilled. The water obtained during this period was 18 g. After the reaction, the mixture was cooled to room temperature, washed twice with a saturated aqueous solution of sodium carbonate (500 m), and then washed with saturated saline until it showed no acrylic property. 2.5g of 1,1'-bi-2-naphthol was added to this,
Distilled under reduced pressure to obtain dicyclopentenyloxyethyl acrylate 17 which has a boiling point of 132-135 ° C / 1 mmHg.
1 g was obtained.

Production of Epoxy Dicyclopentenyloxyethyl Acrylate 248 g of dicyclopentenyloxyethyl acrylate thus obtained, 12 g of acetic acid and 58 g of 35% hydrogen peroxide solution were charged in a reaction vessel and reacted at 60 ° C. for 2 hours.
After the reaction, the mixture was cooled to room temperature and washed with saturated saline solution repeatedly until it showed no acidity. To this product, 3 g of 1,1'-bi-2-naphthol was added and distilled under reduced pressure to give a boiling point of 132-1.
122 g of unreacted dicyclopentenyloxyethyl acrylate, which is a fraction of 35 ° C / 1 mmHg, has a boiling point of 135-140 ° C.
121 g of epoxydicyclopentenyloxyethyl acrylate in compound (I) which is a fraction of 1 mmHg was obtained.
The infrared absorption spectrum and nuclear magnetic resonance spectrum of this product are shown in Table 1 and Table 2, respectively.

Example 2 Dicyclopentenyloxyethanol 194 obtained in the production of dicyclopentenyloxyethanol of Example 1
g, methyl acrylate 258 g, tetrabutyl titanate 10 g as a catalyst, and phenothiazine 0.
3 g of a Vigreux type cooling tube equipped with a fractionating head and a reaction vessel equipped with a capillary tube for blowing nitrogen gas from the bottom are charged, and reflux is continued so that a few drops of distillate are distilled every minute.

After reacting for 8 hours, the reaction solution was distilled under reduced pressure to give a boiling point of 132.
164 g of dicyclopentenyloxyethyl acrylate, which is a fraction of ˜135 ° C./1 mmHg, was obtained.

Hereinafter, the epoxydicyclopentenyloxyethyl acrylate in the compound (I) was obtained in the same manner as in the production of the epoxydicyclopentenyloxyethyl acrylate of Example 1.

[Example 3] The boiling point was 133 to 138 ° C / 1 mmHg in the same manner as in the production of dicyclopentenyloxyethyl acrylate of Example 1 except that 72.9 g of acrylic acid was changed to 94.6 g of methacrylic acid.
As a result, 173 g of dicyclopentenyloxyethyl methacrylate was obtained.

In the same manner as in the production of epoxydicyclopentenyloxyethyl acrylate of Example 1, 262 g of dicyclopentenyloxyethyl methacrylate thus obtained was used as a compound (I) having a boiling point of 135 to 140 ° C./1 mmHg. 142 g of epoxydicyclopentenyloxyethyl methacrylate in). The infrared absorption spectrum and nuclear magnetic resonance spectrum of this product are shown in Table 1 and Table 2, respectively.

[Example 4] The boiling point was 133 to 138 ° C / in the same manner as in Example 2 except that 258 g of methyl acrylate was changed to 300 g of methyl methacrylate.
162 g of dicyclopentenyloxyethyl methacrylate, which was a fraction of 1 mmHg, was obtained.

Then, the compound (I) was prepared in the same manner as in the production of the epoxydicyclopentenyloxyethyl acrylate of Example 1.
The epoxy dicyclopentenyl oxyethyl methacrylate in was obtained.

Claims (2)

[Claims] 1. A (meta) represented by the following general formula (I):
Acrylate compound. (In the formula, R represents H or CH _3. ) 2. An ethylene glycol is added to dicyclopentadiene, the addition product is reacted with (meth) acrylic acid or a (meth) acrylic acid derivative, and then epoxidation is carried out with an organic peracid. A method for producing a (meth) acrylate compound represented by the following general formula (I): (In the formula, R represents H or CH _3. )