JPS6087280A - Ethylenic unsaturated compound and its preparation - Google Patents

Abstract

NEW MATERIAL:An ethylenic unsatuated compound shown by the formula I (R1 is H, or CH3). USE:Useful as a vehicle for ultraviolet-curing coating compound and ink composition. PREPARATION:A compound shown by the formula II is esterified with an acrylic acid or methacrylic acid to give a compound shown by the formula I . Usually an amount of acrylic acid or methacrylic acid used is >= stoichiometric amount. The reaction is carried out by the use of a catalyst, and it is promoted by distilling formed water. H2SO4, p-toluenesulfonic acid, etc. may be cited as the catalyst, and 0.1-10mol%, preferably 1-5mol% catalyst is used based on acrylic acid or methacrylic acid. The compound shown by the formula II is obtained by condensing 2,2-dimethyl-3 oxypropanal with pentaerythritol.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel ethylenically unsaturated compound and a method for producing the same.

In recent years, ultraviolet curable printing inks, paints, etc. have become popular. Many types of acrylic esters are used as vehicles in these printing inks and paints.

As a result of intensive research, the present inventors have obtained a novel ethylenically unsaturated compound useful as a vehicle for ultraviolet curable printing inks and paints.

That is, the present invention provides (1) an ethylenically unsaturated compound represented by the general formula (wherein R□ represents I-1 or Cl-13).

(2) A method for producing an ethylenically unsaturated compound represented by the following general formula (IT), which is characterized by esterifying the compound represented by the following formula [■] with acrylic acid or methacrylic acid.

average (However, in formula [II], Ro represents H or CH3.

) To explain in more detail, the formula [
I] was obtained by condensation of 2,2-dimethyl-3-oxypropanal and pentaerythritol.

Further, acrylic acid or methacrylic acid is usually used in an amount greater than the stoichiometric ratio. Generally, the molar ratio of carboxylic acid to alcohol is 1.0 to 2.0, preferably 1.1 to 1.5.

The reaction is accelerated by using a catalyst and by distilling the water produced. Such a catalyst is an acidic catalyst such as sulfuric acid or p-toluenesulfonic acid, and the amount used is 0.1 to 10 mol%, preferably 1 to 5 mol%, based on acrylic acid or methacrylic acid. .

Advantageously, an azeotropic solvent is used to distill the water produced by the reaction. Such azeotropic solvents can be heated between 60°C and 1
Any substance that has a boiling point of 30°C and can be easily separated from water can be used, but aliphatic hydrocarbons such as n-hexane and rhohebutane, aromatic hydrocarbons such as benzene and toluene, and fats such as cyclohexane can be used. Cyclic hydrocarbons are suitable.

The amount used is usually 5 to 70 percent by weight of the reaction mixture. The reaction temperature may be in the range of 60 to 130°C, but from the viewpoint of shortening the reaction time and preventing polymerization, the reaction temperature is 75 to 120°C.
Advantageously, it is carried out at °C.

Usually, a polymerization inhibitor is already added to acrylic acid or methacrylic acid, but the polymerization inhibitor may be added again during the reaction. Such polymerization inhibitors include hydroquinone, p-methoxyphenol, 2,4-dimethyl-6-L-butylphenol, 3-hydroxythiophenol, α-nitrone-β-naphthol, p-benzoquinone, 2,5- Examples include dihydroxy-p-quinone, phenothiazine, N-nitron diphenylamine, copper salt, and the like. The amount used is usually 0.0 based on the reaction mixture.
1 to 1 weight.

The ethylenically unsaturated compound of the present invention can be used for industrial purposes by washing it with water or an aqueous alkali solution or separating it from the solvent by a method such as vacuum distillation, if necessary. This ethylenically unsaturated compound [■] is useful as a vehicle for paints and ink compositions, and they can be prepared by a suitable polymerization initiation method, by irradiation with ultraviolet rays or electron beams, or by using an organic peroxide. Homolimers or copolymers can be produced by addition.

This will be explained below using examples. In the examples, parts indicate parts by weight.

Example 1 Into a two-part reactor equipped with a stirrer, a temperature controller, a thermometer, a condenser and a separator, the following structure, which is a condensate of 2,2-dimethyl-3-oxypropanal and pentaerythritol, was added. 220 parts of the compound, 259.4 parts of acrylic acid, 25 parts of I)-) luenesulfonic acid, 2 parts of hydroquinone
1, 320 parts of benzene, and 80 parts of cyclohexane are charged and heated. The produced water is distilled and condensed together with the solvent, and only the water is removed from the system in a separator, and the solvent is returned to the reactor.

Cooling occurred when 54 parts of water had been produced. Reaction temperature is 80℃
The temperature was ~87°C. The reaction mixture was dissolved in 400 parts of benzene and 100 parts of cyclohexane, neutralized with 6-20% aqueous sodium hydroxide solution, and then dissolved in 204 parts of brine.
Wash 3 times with 00 parts. The solvent was distilled off under reduced pressure to obtain 367 parts of a pale yellow solid having the following structure, which had the following properties.

Melting point 70-76°C Acid value (mgKOTt/g) 0.02 Saponification value (
mg KOTl/g) 438.5 Elemental analysis C(
%) l-1 (%) 59.27 6.82 The absorption frequency of the obtained product was measured by high resolution nuclear magnetic resonance (NMR) and the results are shown below.

Absorption frequency (Hz) 3 1 11281.2 2 11259.2 3 11250.4 4 8945.7 7- Absorption frequency (Hz) 5 8939.1 6 8917.0 7 8906.0 8 8864 , 2 9 8859.7 10 '8732.0 11 8701.1 12 8694.5 13 8681.3 14 8672.5 15 7132.3 16 7121.3 17 5272.7 18 5239.6 19 5206.6 20 4796.7 21 4763.7 22 4 732 -8 23 4710.8 8- N Absorption frequency (Hz) 24 4706.4 25 4702.0 26 4334.9 27 4307.6 28 4252.5 2g 4245.9 30 4217.2 31 4131.3 32 2630-8 33 2533.9 34 1330.8 35 1324.2 36 1313.2 37 0.0 In the above measurements, tetramethylmilan was used as a reference material, and chloroform was used as a solvent.
Finally, the results of identifying the D couple of C10 were shown. Of the above self-absorption, rlh
1.7.18.19 indicates the absorption peak position of the solvent 9
-

Example 2 Into 22 reactors equipped with a stirrer, a temperature controller, a thermometer, a condenser and a separator, the following structure, which is a condensate of 2,2-dimethyl-3-oxypropanal and pentaerythritol, was prepared. 220 parts of compound, 309.6 parts of methacrylic acid
p-) 25 parts of luenesulfonic acid, 2 parts of hydroquinone
1 part and 400 parts of toluene were charged and heated, the produced water was distilled and condensed together with the solvent, and only the water was removed from the system using a separator.
The solvent is returned to the reactor. Cooling occurred when 54 parts of water had been produced. The reaction temperature was 110°C to 117°C. The reaction mixture was dissolved in 500 parts of toluene, neutralized with a 20% aqueous solution of caustic soda, and then washed three times with 200 parts of a 204 saline solution. The solvent was distilled off under reduced pressure to obtain 350 parts of a pale yellow solid having the following structure.

10- 6a3 This material has the following properties.

Melting point 55-60°C Acid value (mgKOH/g) 0.03, Chemical value (m
gKOH/g) 394.7 Elemental analysis C (%)
H (%) 62.10 7.78 The absorption frequency of the obtained product was measured by high resolution nuclear magnetic resonance (NMR) and the results are shown below.

Interval Absorption frequency (Hz) 1 11358.4 2 11336.3 3 11329.7 4 9274.0 5 9243, 1 6 9221.1 7 8582.1 11- N Absorption frequency (Hz) 8 8577.7 9 8573.3 10 85.4.4, 7 118502.8 12 7134, 5 13 5270.5 14 5237.4 IS 5206.6 16 4801.1 17 4768.1 18 .2 22 4706.4 23 4699.8 24 4318.6 25 4272.3 26 4265.7 12- N Absorption frequency (Hz) 27 2635.2 28 2547.1 29 1328.6 30 1319.8 31 1242.7 32 1238.3 Among the above absorption peaks, l'&L13.14. I 5 indicates the position of the absorption peak of the solvent.

Patent applicant: Nippon Kayaku Co., Ltd. Patent applicant: Mitsubishi Gas Chemical Co., Ltd. 13- AQ-

Claims (2)

[Claims] (1) An ethylenically unsaturated compound represented by the general formula (in the formula, R1 represents R2 or CH3). (2) A method for producing an ethylenically unsaturated compound represented by the following general formula (n), which is characterized by esterifying the compound represented by the following formula (Il) with acrylic acid or methacrylic acid. ■ In [], R1 represents Hl or CH3.)