JPH034076B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel unsaturated compound and a method for producing the same. Reactions of caprolactone and various polymerization initiators to produce corresponding derivatives thereof, such as polycaprolactone esters, are described in Japanese Patent Publication No. 34-5292, Japanese Patent Publication No. 5293-1973, and Japanese Patent Publication No. 41-9559. etc. are disclosed. Furthermore, various acrylate esters have been synthesized so far. However, the general formula [] (However, R ₂ represents CH ₃ , C ₂ H ₅ , or C ₃ H _7. ) The (meth)acrylate ester of the caprolactone derivative of diols represented by Nakatsuta. The novel unsaturated compound of the present invention is defined by the following structural formula. (In the formula, R ₁ is H or CH ₃ , R ₂ is CH ₃ , C ₂ H ₅ ,
or C ₃ H ₇ ; the average value of m and n is a number from 0 to 15,
The average total value of m+n is a number from 1 to 30, preferably from 1 to 6. ) This new unsaturated compound [] has the general formula [] (However, R ₂ in formula [] is CH ₃ , C ₂ H ₅ , or
C ₃ H ₇ ; The average value of m and n is a number from 0 to 15, m + n
The average total value of is a number from 1 to 30, preferably from 1 to 6. ), the above general formula []
It is characterized in that it is produced by esterifying a condensate of diols represented by and epsilon caprolactone with acrylic acid or methacrylic acid. To explain in more detail, the condensate of diols represented by the general formula [] and epsilon caprolactone used in the present invention is obtained by adding the diols represented by the general formula [] and epsilon caprolactone. . Therefore,
m and n in the formula are average amounts of epsilon caprolactone added. 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 promoted by using a catalyst and the water produced is distilled.Such catalysts include sulfuric acid, p-
It is an acidic catalyst such as toluenesulfonic acid, and the amount used is relative to acrylic acid or methacrylic acid.
It is used in an amount of 0.1 to 10 mol%, preferably 1 to 5 mol%. Advantageously, an azeotropic solvent is used to distill the water produced by the reaction. Such azeotropic solvents can be used as long as they have a boiling point of 60℃ to 130℃ and can be easily separated from water, but aliphatic hydrocarbons such as n-hexane and n-heptane, benzene, and toluene can be used. Aromatic hydrocarbons and cycloaliphatic hydrocarbons such as cyclohexane 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
75-120℃ from the viewpoint of shortening reaction time and preventing polymerization
Advantageously, it is carried out in Although a polymerization inhibitor is usually already added to acrylic acid or methacrylic acid, the polymerization inhibitor may be added again during the reaction. Such polymerization inhibitors include hydroquinone, p-methoxyphenol, 2,4-dimethyl-6-1-butylphenol, 3-hydroxythiol, α-nitroso-β-naphthol, p-benzoquinone,
Examples include 2,5-dihydroxy-p-quinone, phenothiazine, N-nitrosodiphenylamine, and copper salts. The amount used is usually 0.01 to 1% by weight based on the reaction mixture. The unsaturated compound of the present invention can be used for industrial purposes by washing it with water or an aqueous alkali solution, if necessary, or by separating it from the solvent by a method such as vacuum distillation. The unsaturated compounds are useful as vehicles for coating and ink compositions, which can be cured by radiation or by thermal means. Radiation curing is caused by ionization or particulate radiation such as electron beams.
or by actinic radiation such as ultraviolet radiation. When curing is carried out with actinic radiation, many types of photosensitizers or photoinitiators commonly known in the art are included. Radiation curing techniques and heat curing techniques are well known to those skilled in the art, and curing can be accomplished by each of them. The unsaturated compounds can be used alone or in admixture with other monomers or polymers. The new unsaturated compounds can also be polymerized by addition of organic peroxides. Examples will be described below. In the examples, parts indicate parts by weight. Example 1 A compound having the following structure was placed in two reactors equipped with a stirrer, a temperature controller, a thermometer, a condenser, and a separator. 700 parts of a compound having the following structure, which is an adduct of epsilon caprolactone and 237.4 parts of acrylic acid, 7.8 parts of sulfuric acid, hydroquinone
2.5 parts of benzene, 560 parts of benzene, and 140 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 56.4 parts of water had been produced.
The reaction temperature was 80-85°C. The reaction mixture was dissolved in 1080 parts of benzene and 270 parts of cyclohexane, and 20
% saline after neutralization with aqueous caustic soda solution
Wash 3 times with 500 copies. The solvent was distilled off under reduced pressure to obtain 723 parts of a pale yellow liquid. This material has the following properties. Specific gravity (25℃) 1.0900 Viscosity (25℃) 486.6 CPS Acid number 0.02 Refractive index 1.4730 (20℃) Elemental analysis C(%) H(%) 62.49% 8.49% High-resolution nuclear magnetic resonance of the obtained product The results of absorption frequency measurement by (NMR) are shown below. No. Absorption frequency (Hz) 1 2601.562 2 2597.656 3 2490.234 4 1966.796 5 1955.078 6 1927.734 7 1607.421 8 1568.359 9 1189.453 10 1158.203 11 1 125.000 12 1078.125 13 1066.406 14 1037.109 15 960.937 16 957.031 17 947.265 18 583.984 19 576.171 20 572.265 No. Absorption Frequency (Hz) 21 568.359 22 548.828 23 537.109 24 533.203 25 505.859 26 419.921 27 378.906 28 363.281 29 351.562 30 339.843 31 287.1 09 32 253.906 33 113.281 34 95.703 35 −1.953 However, in the above measurement, tetramethylsilane was used as the reference material and the solvent using chloroform as
A coupled measurement of H ¹ and C ¹³ -H was performed, and the results finally showed the identification of the D couple of C ¹³ . Among the above absorptions, Nos. 9, 10, and 11 indicate the absorption peak positions of the solvent. Example 2 Into the same reactor as in Example 1, 600 parts of a compound having the following structure was added. 134.6 parts of acrylic acid, 4.4 parts of sulfuric acid, hydroquinone
1.0 parts of benzene, 360 parts of benzene, and 90 parts of cyclohexane were charged, and the reaction was carried out in the same manner as in Example 1 until the amount of produced water became 32 parts. The reaction temperature was 78-84°C.
Add 960 parts of benzene and 240 parts of cyclohexane to the reaction mixture.
After neutralizing with 20% caustic soda aqueous solution, the solution was washed three times with 500 parts of 20% NaCl aqueous solution. The solvent was distilled off under reduced pressure to obtain 578 parts of a pale yellow liquid. This material has the following properties. Specific gravity (25℃) 1.0900 Viscosity (25℃) 2373 CPS Acid value 0.03 mgKOH/g Refractive index 1.4735 Elemental analysis C(%) H(%) 62.60% 8.71% NMR measurement result No. Absorption frequency (Hz) 1 2603.515 2 2599.609 3 2454.140 4 1957.031 5 1929.687 6 1609.375 7 1570.312 8 1191.406 9 1160.156 10 1126.953 11 1080.078 12 1070.312 13 1037.109 14 970.703 15 962.890 16 958.984 17 949.218 18 931.640 No. Absorption frequency (Hz) 19 585.937 20 576.171 21 550.781 22 539. 062 23 535.156 24 507.812 25 482.421 26 421.875 27 380.859 28 365.234 29 353.515 30 341.796 31 289.062 32 164.062 33 113.281 34 105.468 35 97.656 36 76.171 37 19.531 38 −3.906 Among the above absorptions, No. 8, 9, and 10 are the absorption of the solvent. Indicates peak position. Example 3 In the same reactor as in Example 1, a compound having the following structure was added. 660 parts, mectaryl acid 87.7 parts, p-toluenesulfonic acid 12.5 parts, hydroquinone 1.2 parts, toluene
750 parts were charged, and the reaction was carried out in the same manner as in Example 1 until the amount of water produced was 17.4 parts. Reaction temperature is 113-117
It was warm at ℃. The reaction mixture was dissolved in 1424 parts of toluene, neutralized with a 20% aqueous solution of caustic soda, and then 20%
Wash three times with 300 parts of NaCl aqueous solution. The solvent was distilled off under reduced pressure to obtain 575 parts of a pale yellow wax-like product at room temperature. This material has the following properties. Specific gravity (50℃) 1.0720 Viscosity (50℃) 514.7 CPS Acid value 0.02 mgKOH/g Refractive index 1.4640 (50℃) Elemental analysis C(%) H(%) 63.10% 8.90% NMR measurement result No. Absorption frequency (Hz) 1 2601.562 2 2597.656 3 2046.875 4 2044.921 5 1876.953 6 1568.359 7 1189.453 8 1158.203 9 1125.000 10 1076.171 11 1066.4 06 12 1035.156 13 962.890 14 957.031 15 947.265 16 929.687 17 574.218 18 537.109 No. Absorption frequency (Hz) 19 531.250 20 505.859 21 480.468 22 419.921 23 378.906 24 363.281 25 351.562 26 287.109 27 269.531 28 95.703 Among the above absorptions, No. 7, 8, and 9 indicate the peak positions of absorption of the solvent. Application examples 1, 2, 3 50 parts of the new unsaturated compound obtained in Examples 1, 2, and 3 were mixed with epoxy acrylate resin (Epicote 828 (bisphenol type epoxy resin manufactured by Ciel Petrochemicals) with acrylic acid. 50 parts of the obtained resin), 5.0 parts of Irgakiure 651 (manufactured by Ciba Geigy) as a photosensitizer were added, and the mixture was coated on a steel plate panel, and a high-pressure mercury lamp (manufactured by Toshiba Corporation,
2KW) was UV-cured. The results are shown in Table 1 below.

[Table] Number of times a mercury lamp passes through the lamp until it is dry to the touch.

Claims (1)

[Claims] 1. General formula (In the formula, R ₁ is H or CH ₃ ; R ₂ is CH ₃ , C ₂ H ₅ ,
or C ₃ H ₇ ; average values of m and n are each 0-15
The average total value of m+n is a number from 1 to 30. )
An unsaturated compound represented by 2 General formula below [] (However, R ₂ in formula [] is CH ₃ , C ₂ H ₅ or
C ₃ H ₇ ; The average values of m and n are each a number from 0 to 15,
The average total value of m+n is a number from 1 to 30. ) A method for producing an unsaturated compound represented by the following general formula [ ], which comprises esterifying the compound represented by acrylic acid or methacrylic acid. (However, each symbol in the formula [] is the same as the above formula [], and R ₁ represents H or CH _3. )