JPS6281378A - Acrylate compound and production thereof - Google Patents

Abstract

NEW MATERIAL:A (meth)acrylate compound shown by the formula (R is H or CH3). EXAMPLE:Epoxydicyclopentenyloxyethyl acrylate. USE:Useful as a raw material or improver for ink, coating compounds, adhesives, coating agents and molding resins, showing low viscosity, low smell and solubility in a wide range of resins. PREPARATION:Dicyclopentadiene is reacted with ethylene glycol in the presence of an acidic catalyst such as sulfuric acid, p-toluenesulfonic acid, trifluoroboric acid, etc., at 100-120 deg.C to give an adduct of dicyclopentadiene with ethylene glycol. Then, the adduct is reacted with (meth)acrylic acid or (meth)acrylic acid derivative and epoxidized with an organic peracid, to give a compound shown by the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application 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 CH3) The compound represented by formula (I) is easily homopolymerized or combined with other unsaturated group-containing compounds in the presence of heat, ultraviolet rays, ionizing radiation, or a radical polymerization initiator. Copolymerization can be carried out.

B. Conventional technology Various acrylic esters have been known so far.

For example, monofunctional polymers such as methyl methacrylate, ethyl acrylate, and 12-edylhexyl acrylate, and polyfunctional polymers such as trimedylolpropane triacrylate, trimethylolpropane trimethacrylate, and pentaerythritol triacrylate are generally known. It is being

Problems to be Solved by the C0 Invention However, among the above monofunctional additives, when used in printing inks and paints, the odor of unreacted monomers after curing poses a significant problem. Furthermore, when polyfunctional additives are used as diluents for paints and printing inks, they have to be used in large amounts relative to the resin, and therefore have the disadvantage that the properties of the resin are lost.

Means, action, and effect for solving the D1 problem As a result of intensive research, the present inventors have obtained a novel (meth)acrylic acid ester that has low viscosity, low odor, and solubility in a wide range of resins. Ta. This product is useful as a raw material or modifier for inks, paints, adhesives, coatings, and molding resins.

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

Dicyclopentadiene and ethylene glycol as WL acid,
When the reaction is carried out at 100 to 120'C for 5 to 8 hours under an acidic catalyst such as p-toluenesulfonic acid or boron trifluoride, an ethylene glycol adduct of dicyclopentadiene is obtained. This adduct is (meth)acrylic acid or (meth)
Dicyclopentenyloxyethyl (meth)acrylate can be obtained by esterification with an acrylic acid derivative.

When carrying out esterification using (meth)acrylic acid, it is preferable to use an acidic catalyst such as Iia acid or p-toluenesulfonic acid. The polymerization inhibitor used in the reaction step is preferably one that can be easily removed by washing with an alkaline aqueous solution, such as hydroquinone, hydroquinone monomethyl ether, or cuprous chloride.

Azeotropic solvents used to remove water produced by the esterification reaction from the system include benzene, toluene, xylene, n-hexane, methyl isobutyl ketone, etc., which form an azeotropic mixture with water, and are essentially Single or mixtures of mutually immiscible organic solvents can be used.

Also, (meth)acrylic acid derivatives such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, rhopropyl (meth)acrylate, isopropyl (meth)acrylate, etc. It is also possible to produce dicyclopentenyloxyethyl (meth)acrylate by transesterification using an acid ester compound.

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

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

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

In the epoxidation reaction, 100 to 1,000 ppm of hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, or the like is preferably added as a polymerization inhibitor.

E. Example Hereinafter, the present invention will be explained by examples.

(Example 1) ■ Production of dicyclopentenyloxyethanol Ethylene glycol 1249 and 5.7 g of boron trifluoride ethyl ether complex were charged into a reaction vessel, heated to 100°C, and while maintaining the same temperature, dicyclopentadiene 132
g was added dropwise over 5 hours. After the completion of the dropwise addition, the reaction was continued for 2 hours to eliminate dicyclopentadiene. The reaction mixture was cooled to room temperature, and 2.7 ml of 15N aqueous ammonia solution was slowly added to neutralize the boron trifluoride ethyl ether complex. The obtained reaction product was extracted with n-hexane, washed with water, and then n-hexane was removed using a rotary evaporator to obtain dicyclopentenyloxyethanol 1699.

■Production of dicyclopentenyloxyethyl acrylate-1- Dicyclopentenyloxyethanol 1949 thus obtained and 79.2 SF of acrylic acid, 1)-1 to 2.7 g of luenesulfonic acid as a catalyst, and a polymerization inhibitor. 0.8 g of hydroquinone methyl ether and 200 rr of toluene! ! was charged into a reaction vessel equipped with a reflux condenser, a water separator, and a stirrer, and heated at toluene reflux temperature for 5 hours while stirring. Water was separated from the distilled toluene-water fraction in a water separator, and the toluene was continuously returned to the reactor. The reaction was continued until no water was distilled out. 18 g of water was obtained during this time.

After the reaction, cool to room temperature and add 50% saturated aqueous sodium carbonate solution.
Washing was carried out twice at 0 d, and then washing was repeated with saturated saline until alkalinity was no longer exhibited. This one has 1.
2.59 g of 1'-bi-2-naphthol was added and distilled under reduced pressure to obtain 171 g of pentenyloxyethyl acrylate having a boiling point of 132-b.

(2) Production of epoxy dicyclopentenyloxyethyl acrylate 248 g of dicyclopentenyloxyethyl acrylate thus obtained, 112 g of vinegar, and 58 g of 35% hydrogen peroxide were charged into a reaction vessel and reacted at 60°C for 2 hours. After the reaction, the mixture was cooled to room temperature and washed repeatedly with saturated brine until it no longer showed acidity. Add 3 g of 1.1'-bi-2-naphthol to this and perform vacuum distillation to obtain unreacted dicyclopentenyloxyethyl acrylate 122 with a boiling point of 132-135°C/lmHg.
U and boiling point are 135-140'C/1 rrunt1
121 g of epoxy dicyclopentenyloxyethyl acrylate in compound (1), which is a fraction of No. 9, was obtained. Infrared absorption spectrum and nuclear magnetic resonance spectrum of this product 1~
Tables 1 and 2 show the results, respectively.

(Example 2) Dicyclopentenyloxyethanol 19 obtained in the production of dicyclopentenyloxyethanol in Example 1
4 g and methyl acrylate 2589, tetrabutylditane-1-109 as a catalyst, and 0.3 g of phenothiazine as a polymerization inhibitor in a Vigreux type cooling tube equipped with a fractionating head.
The mixture is placed in a reaction vessel equipped with a capillary tube so that nitrogen gas can be blown into it from the bottom, and reflux is continued so that several drops of distillate are distilled out every minute.

After 8 hours of reaction, the reaction solution was distilled under reduced pressure and the boiling point was 13.
2-b 164 g of cyclopentenyloxyethyl acrylate was obtained.

Thereafter, epoxy dicyclopentenyloxyethyl acrylate in compound (I>) was prepared in the same manner as in Example 1 (1) Production of epoxy dicyclopentenyloxyethyl acrylate.

[Example 3] Cyclopentenyloxyethyl methacrylate 173 with a boiling point of 133-b was prepared in the same manner as in Example 1, except that 194.6 g of methacrylic acid was used instead of 72.99 g of acrylic acid.
G is 2+9.

262 g of dicyclopentenyloxyethyl methacrylate thus obtained was treated in the same manner as in Example 1 (1) for the production of epoxydicyclopentenyloxyethyl acrylate, and the boiling point was 135-b (epoxydicyclopentenyloxy in I> 142 g of ethyl methacrylate was obtained.The infrared absorption spectrum and nuclear magnetic resonance spectrum of this product are shown in Tables 1 and 2, respectively.

[Example 4] 258 g of methyl acrylate was mixed with 30 g of methyl methacrylate.
The boiling point was 13 in the same manner as in Example 2 except that the amount was 0 g.
3-b dicyclopentenyloxyethyl methacrylate 16
2g was obtained.

Hereinafter, the compound (I>
Epoxy dicyclopentenyloxyethyl methacrylate was obtained.

Table 1. Infrared absorption spectrum (liquid film) *1... Epoxy dicyclopene, lentenyloxyethyl acrylate *2... Epoxy dicyclopentenyloxyethyl methacrylate Table 2. Nuclear magnetic resonance spectra 1~ ('3 C-NHR, C
DC, e3) Table 2 continued Procedure Ne City official letter (self-proposal) February 18, 1985 18E1 Commissioner of the Patent Office Ubuya) 100 alK Kamogawa L 1, Indication of fact A 1 1985 Patent application No. 221599 2, De Name of acrylate compound and its manufacturing method 3, relationship with the case of the person making the amendment Patent applicant address: 1-4-5 Marunouchi, Chiyoda-ku, Tokyo
Name (234> Sanyo Kokusaku Pulp Co., Ltd. 4, Agent Address: 16 Kanda Kita Jorimono-cho, Chiyoda-ku, Tokyo)
101 English Hill 3rd floor 5, Detailed description of the invention for the specification to be amended Contents of the amendment (1) The formula in Table 2 on page 13 of the old specification was revised as follows rF
.

)k (2) The formula in Table 2 continued on page 14 of the specification black was corrected as follows.

Claims (2)

[Claims] (1) A (meth)acrylate compound represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R represents H or CH_3) (2) The following method characterized by adding ethylene glycol to dicyclopentadiene, reacting the adduct with (meth)acrylic acid or a (meth)acrylic acid derivative, and then epoxidizing with an organic peracid. The general formula for (
A method for producing a (meth)acrylate compound represented by I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R represents H or CH_3)