JPS6245560A - Novel acrylate and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [R is -OH or CH2=CH-C (=O)-O-]. EXAMPLE:1,4-Cyclooctanediyl di-2-propenoate. USE:A raw material for ink, coating material, adhesive, covering agent and molding resin or modifier. PREPARATION:1,4-Cyclooctanediol expressed by formula II is esterified with acrylic acid or acrylic acid ester to afford the aimed compound expressed by formula I. The compound expressed by formula I has a low viscosity and odor and further solvency for a wide range of resins. Furthermore, the compound expressed by formula I can be readily homopolymerized or copolymerized with another compound containing an unsaturated group in the presence of heat, ultraviolet rays, ionizing radiation or radical polymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION A. Industrial Application Field The present invention relates to a novel acrylate compound represented by the following general formula (I) and its dino radical.

(In the formula, R does not represent -01-1 or CH2=CHCO-) <I) The compound represented by the formula can be easily monomerized in the presence of heat, ultraviolet IQ, ionizing radiation, or a radical polymerization initiator.
Polymerization or copolymerization with compounds containing unsaturated groups can be carried out.

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

For example, monofunctional monomers such as methyl acrylate, ethyl acrylate, and 2-ethylhexyl acrylate, and polyfunctional monomers such as trimethylolpropane triacrylate-1- and pentaerythritol triacrylate are generally known.

C1 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 multiple amounts with respect to resins, and therefore have the disadvantage that the properties of the resins are lost.

As a result of intensive research, the present inventors have obtained a novel acrylic ester that has low viscosity, low odor, and has solubility in a wide range of resins. I had potatoes.

This product is useful as a raw material or modifier for inks, paints, adhesives, coatings, and molding resins.

Kibenmei's compound (I> is (II> 1 represented by the formula
11 can be easily obtained by esterifying 4-cyclooctanediol with acrylic butyric acid ester.
1. Compound 1 (II) is commercially available 1,5
- Can be prepared by hydrating cyclooctadiene. When compound (II) is subjected to an esterification reaction, a mixture of 4-hydroxycyclooctyl 2-propenoate represented by (III) and 1,4-cyclooctanediyl di-2-propenoate represented by formula (IV) is obtained. I can do it.

In addition, 1,4-cyclooctanediyl di-2-propenoate represented by formula (IV) can be obtained by esterifying 4-hydroxycyclooctyl 2-propenoate represented by (I[I) with acrylic acid or acrylic acid ester. You can also get it by

When esterification is carried out using acrylic acid, the reaction is promoted by using a catalyst and continuously removing the produced water from the system. The catalyst used here is I acid, p
Any known esterification catalyst can be used, such as -1-luenesulfonic acid and boron trifluoride. Advantageously, an azeotropic solvent, such as toluene, is used to separate off the water produced by the reaction.

The reaction temperature is preferably 75 to 120°C from the viewpoint of 1'J fil of reaction time and prevention of polymerization. A polymerization inhibitor is added to prevent thermal polymerization of acrylic acid. Such polymerization inhibitors include hydroquinone, p-methoxyphenol, 2,4-dimethyl-6-shebutylphenol, 3-hydroxythiophenol, α-nitrosol-β-naph1--, p-benzoquinone, ,5-
Examples include dihydroxy-〇-quinone and copper salts.

Compound (1) can also be produced by a transesterification reaction between an acrylic acid ester and Compound 1 (U). In this case, acrylic acid methyl, ethyl, butyl,
Compounding with known acrylic esters such as n-propyl and 1SO-propyl A transesterification reaction is carried out by heating the mixture at 1°C (II) in the presence of a polymerization inhibitor and catalyst, and taking out the resulting lower alcohol from the system. .

In this case, when using sulfuric acid or p-toluenesulfonic acid as a catalyst for the transesterification reaction, hydroquinone, p-methoxyphenol, etc. are used as the polymerization inhibitor, but metallic sodium, sodium When using alkaline catalysts such as alcolade, aluminum alcolade, and tetrabutoxytitanium, alkaline polymerization inhibitors such as p-phenylenediamine and phenyl-β-naphdylamine are used.

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

[Example 1] De was added to a reaction vessel equipped with a reflux condenser, a water separator, and a stirrer.
Compound (II) 1449 manufactured by Ggusa (Inc.)
, acrylic fl 180g, p-toluenesulfone g1
0g, p-methoxyphenol 5g and toluene 400g
was added and heated for 3 hours while stirring. After water was separated from the distilled 1-luene-water fraction in a water separator, toluene was continuously returned to the reaction vessel. After the reaction, the reactor was cooled to room temperature, washed three times with 500 ml of a saturated aqueous sodium carbonate solution, and then washed repeatedly with saturated sodium chloride water until it no longer showed alkalinity. This one has 1.1′ −
Add B-2-naphthol 53 and perform vacuum distillation to obtain a fraction (III
) 122 g of a fraction CIV) having a boiling point of 140° C./1 trvn Hg were obtained.

[Example 2] 144 g of compound (II) and 258 g of acrylic acid methyl ester were placed in a reaction vessel equipped with a Vigreux-type fractionating tube, a stirrer, and a thermometer. ? , l)-methoxyphenol 5g
, 118 g of p-toluenesulfone are added.

Heat this in an oil bath until it boils and continue to reflux. The generated methanol forms an azeotrope with acrylic acid methyl ester and is distilled off.

After 5 hours of reaction, excess acrylic acid methyl ester was distilled off and the mixture was cooled to room temperature. This product was washed three times with 500 d of saturated aqueous sodium carbonate solution, and then washed with saturated saline until it no longer showed alkalinity. 10 g of 1.1'-bi-2-naphthol was added to this and vacuum distillation was carried out to obtain a fraction (I[
132 g of fraction (IV) with a boiling point of 140°C/1 mar H'J was obtained.

[Example 3] In place of compound (lr) in Example 2, compound (I
Compound (IV), i.e., 1
, 251 g of 4-cyclooctanediyl di-2-propenoate were obtained.

Both liquid compounds (I[l) and ([V 2 ) obtained in the examples have low odor and have the following properties.

Infrared absorption spectrum (K B r, film) Compound Wave number (cm-') Absorption type 3420
Hydroxyl group○H stretching vibration 2960 CH stretching vibration 1720 C-○ stretching vibration of acrylic ester ([[[)1628.1615 C)-12-CH-stretching vibration of acrylic ester 1400 CH2=CH of acrylic ester
- In-plane bending vibration 1180 C of acrylic ester = stretching vibration 2960 CH stretching vibration 1720 C=O stretching vibration of acrylic ester 1628, 1615 (IV
) CH2= CH-Stretching vibration 1400
Acrylic acid ester Cl-12= CH-
In-plane bending vibration 1180 C-〇-stretching vibrational nuclear magnetic resonance spectrum of acrylic acid ester (C-NMR, CDCJ23. JEOL FX-600
) Compound Symbol δ(ppm)a
130.3 e 27.1.26.9 f 22,5 (129,8,29,f3 h 70.5 Compound symbol δ (ppm) a 130.2 b 128.9 c 165,1 d 74.O e 27.1 f 22.4 g30.0 - to

Claims (3)

[Claims] (1) An acrylate compound represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R represents -OH or ▲There are mathematical formulas, chemical formulas, tables, etc.▼) (2) A method for producing an acrylate compound represented by the following general formula (I), which comprises reacting 1,4-cyclooctanediol with acrylic acid or an acrylic ester. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R represents -OH or ▲There are mathematical formulas, chemical formulas, tables, etc.▼) (3) 1,4-cyclooctanediyldi-2 characterized by reacting 4-hydroxycyclooctyl 2-propenoate with acrylic acid or an acrylic acid ester
- A method for producing propenoate.