JPS61221152A - Methacrylate compound and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (R1 and R2 are -OH, or group shown by the formula II; with the proviso that a case where R1 and R2 are simultaneously OH is omitted). EXAMPLE:1,2-Dimethylmethacryloyloxy-4-vinylcyclohexane. USE:A monomer for a polymer or copolymer. Having low vicosity, low odor, and solubility of resins in a wide range, easily polymerizable alone or copolymerizable with another compound containing an unsaturated group in the presence of heat, ultraviolet rays, or a radical initiator, useful as a raw material for modifier for ink, coating compound, coating agent or molding resin. PREPARATION:1,2-Dihydroxy-4-vinylcyclohexane shown by the formula III or 1( or 2)-methacryloyloxy-2( or 1)-hydroxy-4-vinylcyclohexane shown by the formula IV is reacted with methacrylic acid or its derivative in an azeotropic solventin the presence of an esterifying catalyst and a polymerization inhibitor, to give a compound shown by the formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION A. Industrial Field of Application The present invention relates to a novel methacrylate compound represented by the following general formula and a method for producing the same. However, this excludes the case where R, , R, are OH at the same time. ] The compound represented by formula (1) can be easily homopolymerized or copolymerized with other unsaturated group-containing compounds in the presence of ultraviolet rays, ionizing radiation, and a radical polymerization initiator.

B. Conventional technology Various acrylic esters have been known.

For example, methyl methacrylate, ethyl acrylate, ac+
Monofunctional monomers such as 2-ethylhexyl monoruate and polyfunctional monomers such as trimethylolpropane triacrylate, trimethylolpropane triacrylate, and pentaerythritol triacrylate are generally known.

C8 Problems to be Solved by the Invention However, when monofunctional monomers are used in printing inks and paints, the odor of unreacted monomers after curing poses a significant problem.

Furthermore, when polyfunctional monomers are used as diluents for paints and printing inks, they have to be used in large amounts relative to resins, and therefore have the disadvantage that the properties of the resins are lost.

Means, action, and effect for solving the D0 problem As a result of intensive research, the present inventors have obtained a novel methacrylic acid ester that has low viscosity, low odor, and solubility in a wide range of resins.

This product is useful as a raw material for inks, paints, adhesives, coatings, resins for bottom molds, and as a ridge modifier.

The compound (1) of the present invention can be produced by the following method. That is, 1,2-dihydroxy-4-vinylcyclohexane CH=CH represented by formula (4).

is obtained by esterifying with methacrylic acid or a methacrylic acid derivative. Through this esterification reaction, (
Represented by the Shu formula, 1(mano is 29-methacryloyloxy-2(or 1)-hydroxy-4-vinylcyclohexane CH=CH atmosphere and (1,2-dimethacryloyloxy-4-vinyl represented by the open formula) A mixture of cyclohexane can be obtained.

Also, 1,2-dimethacryloyloxy-4-vinylcyclohexane represented by the formula (IV), 1 (or 2)-methacryloyloxy-2 (mayuha 1)-hydroxy-4-vinyl represented by the It can also be obtained by esterifying cyclohexane with methacrylic acid or methacrylic acid derivatives.

When carrying out esterification using methacrylic acid, either sulfuric acid or para-toluenesulfonic acid may be used as the catalyst. 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. Single or mixtures of mutually immiscible organic solvents can be used.

It is also possible to produce by transesterification reaction between a compound (RIH) methacrylic acid ester and a compound (Ill). A transesterification reaction is carried out by heating the methacrylic acid ester compound (n) in the presence of a polymerization inhibitor and a catalyst, and removing the resulting lower alcohol from the system.

In this case, the polymerization inhibitor used as a catalyst for the transesterification reaction is sulfuric acid, hydroquinone or hydroquinone monomethyl ether is used when para-toluenesulfonic acid is used, and alkali-11-based polymers such as metallic sodium and sodium chlorchlorate are used. When a catalyst is used, an alkali-11 polymerization inhibitor such as phenylenediamine or phenyl-.beta.-naphthylamine is used.

E. Example The present invention will be explained below with reference to Examples.

[Example 1] In nine reaction vessels equipped with a reflux condenser, a water separator, and a stirrer, 142 f of compound (I), 206 f of methacrylic acid, 9 f of paratoluene sulfone, and 400 g of toluene were added to 6 f of hydroquinone monomethyl ether. Add and stir while stirring.
Time heated friend. After water was separated from the distilled toluene-water fraction in a water separator, the toluene was continuously returned to the reaction vessel. During this period, 279 yomizu were obtained.

After the reaction, the reaction mixture was cooled to room temperature, washed twice with a 500% aqueous solution of llium carbonate, and then washed with saturated brine until it no longer showed alkalinity. 1,1'-bi-2-naphthol 72 was added to this and vacuum distillation was performed to obtain compound (IV) 97t having a boiling point of 128-b849 and 133-b. The infrared absorption spectra and nuclear magnetic resonance spectra of these products are shown in Tables 1 and 2, respectively.

[Example 2] Compound in Example 1 (compound (m) instead of phantom)
The compound (P/
), that is, 1,2-dimethacryloyloxy-4-vinylcyclohexane 195f was obtained.

[Example 3] A guiguriyu-type fractionating tube was attached, and a capillary tube was attached so that nitrogen gas could be blown into the reaction vessel.
142 f, methacrylic acid methyl ester 100
0 f, add 9 t of para-toluenesulfonic acid to 251 ml of hydroquinone monomethyl ether. Heat this in an oil bath until boiling and continue to reflux. The generated methanol forms an azeotrope with methacrylic acid methyl ester and is distilled off.

After 10 hours of reaction, excess methyl methacrylate was distilled off and the mixture was cooled to room temperature. This is saturated carbonated)
It was washed twice with 11 um water bath solution 500-ml, then washed with saturated saline until it no longer showed alkalinity, and dried over anhydrous sodium sulfate. Add 1.1'-bi-2-naphthol 14f to this, perform vacuum distillation,
A compound (If) 74f with a boiling point of 128-b and a compound (1M91P) with a boiling point of 133-b were obtained.

Table 1 Infrared absorption spectrum (liquid film) Table 2, Nuclear Magnetic Resonance Spectrum ('', C-NMR.

Contents of the amendment Procedural amendment export) August 15, 1985

Claims (2)

[Claims] (1) A methacrylate compound represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R_1 and R_2 represent -OH or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. However, R_1, R_
Except when 2 are OH at the same time. ) (2) 1,2-dihydroxy-4-vinylcyclohexane or 1 (or 2)-methacryloyloxy-2
(or 1) A methacrylate compound represented by the general formula (I) below, which is characterized by reacting -hydroxy-4-vinylcyclohexane with methacrylic acid or a methacrylic acid derivative ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( I ) (In the formula, R_1 and R_2 represent -OH or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. However, R_1, R_2
except when are OH at the same time. ) manufacturing method.