JPS5984844A - Ethylenic unsaturated compound and its preparation - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (R is H, or CH3; n and n are 1-5; p is 1-6; q, r, and s are 0-3; with the proviso that p+q+r+s=6, q+r=0-3; p+s=3-6; mp+nq=3-30). USE:A copolymerizable monomer. Having a lower vicosity than dipentaerythritol hexaacrylate, etc., showing curing properties with the same curing speed, being copolymerized with an unsaturated group-containing resin such as an unsaturated polyester, etc. by heat, ultraviolet light rays, ionizing radiation, or in the presence of a radical initiator, to form a cured film having improved resistance. PROCESS:A compound shown by the formula II, etc. is reacted with a compound shown by the formula III (a is 1-5; X is 3-6; Y is 0-3; with the proviso that X+Y=6; total value of a is 3-30) is reacted with acrylic acid or methacrylic acid in an azeotropic solvent in the presence of an acidic catalyst such as sulfuric acid and a polymerization inhibitor at 75-120 deg.C, and esterified to give a compound shown by the formula I .

Description

Detailed Description of the Invention The present invention relates to a novel ethylenically unsaturated compound that can be easily copolymerized with unsaturated group-containing resins in the presence of heat, ultraviolet light, ionizing radiation, or a radical initiator, and a method for producing the same. It is. In recent years, ultraviolet curable printing inks, paints, etc. have become popular.

Acrylic monomers are used as diluents for printing inks and paints, and dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate are generally known as monomers that have particularly fast curing speeds, and the amount used is It has increased. however,
When dipentaerythritol hexa (or penta) acrylate is used as a diluent, dipentaerythritol hexa (or penta) acrylate has a high viscosity and must be used in large amounts relative to the resin. It has the disadvantage of losing its characteristics.

As a result of extensive research, the present inventors have discovered a novel ethylenically unsaturated compound that has considerably lower viscosity than dipentaerythritol hexa (or penta) acrylate and has similar curing speed. I ended up getting this.

That is, the present invention provides (1) the general formula (wherein R is H2 or CH3; m and D are integers having a value of 1 to 5, preferably 1 to 2; p is 1
an integer having a value of ~6, preferably 3-6; q and r are 0. or an integer having a value of 1 to 5, preferably 0. or 1; S is 0. or 1-6
is an integer having a value of , p+q+r+s is 6,
i q + r is an integer having a value of 0° or 1 to O, preferably 0 or 1; p→-8 is an integer having a value of 3 to 6, preferably 5 or 6 And i
The average total value of mp+nq is a number from 3 to 30, preferably from 6 to 12. ), and (2) an ethylenically unsaturated compound having the general formula (1) (wherein R in formula (1) is H or CHs j a is 1 to
An integer having a value of 5, preferably 1 to 2; X is an integer having a value of 3 to O, and Y is 0 or 1 to
is an integer with a value of 3, X, -1-Y is 6,
The number of balance beams and scales of aX is 3 to 30, preferably 6 to 12. The present invention relates to a method for producing a novel ethylenically unsaturated compound represented by the following general formula (1), which is characterized by esterifying a condensate of dipentaerythritol and alkylene oxide represented by () with acrylic acid or methacrylic acid.

General formula C11) (However, in formula (II), R is H2 or CH!; m and nl-t is an integer having a value of 1 to 5, preferably 1 to 2; p is 1 to 6; an integer having a value,
Preferably 3 to 6; q and r are 0° or integers having a value of 1 to 5, preferably 0. or 1, and 8 is 0. or an integer having a value of 1 to 3, i I'
+(1+ r + 8 is 6 = q4-. r is 0 or an integer having a value of 1 to 3, preferably 0 or 1, and j p+ day is an integer having a value of 3 to 6 and preferably 5 or 6 (i ml) + nq
The average total value of is a number of 5 to 30, preferably 6 to 30.
It is 12. ) To explain in more detail, the condensate of dipentaerythritol and alkylene oxide used in the present invention is obtained by adding dipentaerythritol and ethylene oxide or propylene oxide.

Further, acrylic acid or methacrylic acid is usually used in an amount greater than the stoichiometric ratio. Generally, the molar ratio H 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, 1)-) luenesulfonic acid,
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 have temperatures of 6°C to
Any substance having a boiling point of 130°C and easily separated from water can be used, but n-hexane and n-hebutane are usually used in an amount of 5 to 70% by weight of the reaction mixture.

The reaction temperature may range from 60 to 150°C, but from the viewpoint of shortening the reaction time and preventing polymerization, it is advantageous to carry out the reaction at a temperature of 75 to 120°C.

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 hydric quinone, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 3-human tetraoxythiophenol, α-nitrone-β-11-7)- le, p
-benzoquinone, 2,5-dihydroxy-p-quinone,
Examples include phenothiazine, N-nitron diphenylamine, copper salt, and the like. The amount used is usually 0.01 to 1 weight percent 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.

In the present invention, the number of moles of alkylene oxide added is 2
If the number of moles of added 'alkylene oxide is less than 30 moles, the viscosity of the obtained ethylenically unsaturated compound will not be sufficiently reduced, and if the number of added moles of 'alkylene oxide is 30 moles or more, the degree of unsaturation of the obtained ethylenically unsaturated compound will decrease. This is not preferable because it causes problems such as a decrease in the curing speed and physical properties of the film.

Easily copolymerizes with unsaturated group-containing resins, such as unsaturated polyesters, epoxy acrylates, and urethane acrylates, in the presence of an initiator to produce cured films with excellent resistance. I can do jJ.

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

Example 1 600 parts of a compound having the following structure, which is an adduct of dipentaerythritol and propylene oxide, and 517 parts of acrylic acid were placed in a reactor equipped with a stirrer, a temperature control device, a temperature side, a condenser, and a separator. 1 part of sulfuric acid, 17 parts of hydroquinone, 480 parts of benzene, and 120 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. It was cooled when 53.8 parts of water was produced. The reaction temperature is 85'
The temperature was ~86°C.

The reaction mixture was mixed with 1240 parts of benzene and 3 parts of cyclohexane.
After dissolving in 10 parts and neutralizing with a 20% aqueous solution of caustic soda, the mixture was washed three times with 500 parts of 20-chi chicken brine. The solvent was distilled off under reduced pressure to obtain 750 parts of a pale yellow liquid. This material has the following properties.

Specific gravity (25℃) 1.1050 viscosity
Degree (25℃) 1052CPS Saponification value 323.1 ■KOH/r acid value 0 0 4 ++
+yKQH/f refractive index 14705
(2 parts C) Elemental analysis value ~ c H 59.34 7.25% The absorption frequency of the obtained product was measured by high-resolution egg nuclear nitrile resonance (NMR), and the results are shown below.

Kata Absorption frequency・(Hz) 1 2490, 23 '4 2 2486・328 5 j96D, 937 4 1955.546 5 1929.687 6 1925.781 7 1193.359 8, 1158.203 9 1154.765 (01t2 a・906 11 j107.42'1 12 f 074.218 15 1052.734 14 1042.968 15 1017.578 16 1005.906 17 992.187 18 955.078 19 900+ 3902
0 685.54624
6 7 1.8 7.522
281.25023
257.81224
250.00025
173.82826
13.671 In the above measurements, tetramethylsilane was used as a reference substance and chloroform was used as a solvent.

We conducted coupled measurements of c13-a and finally identified the D couple of 013. Among the above absorptions, Ifa7+ 13+ 9 indicates the peak position of absorption of the solvent.

Example 2 Into the same reactor as in Example 1, 570 parts of a compound having the following structure, which is an adduct of dipentaerythritol and propylene oxide, and 311 parts of acrylic acid were added. ? i part, 9.4 parts of sulfuric acid, 2 parts of hydroquinone, 480 parts of benzene, 1 part of cyclohexane
20 parts were charged, and the reaction was carried out in the same manner as in Example 1 until the amount of water produced was 64.8 parts. The reaction temperature was 83-88°C. The reaction mixture was dissolved in 950 parts of benzene and 237.5 parts of cyclohexane, neutralized with 20% aqueous sodium hydroxide solution, and washed five times with 500 parts of 20% aqueous NaCl solution. The solvent was distilled off under reduced pressure to obtain 650 parts of a pale yellow liquid.

This material has the following properties.

Specific gravity (25℃) '1.077 viscosity
degree (25℃)' 11351 CF3
Acid value 0. 0 6
mgKOH/f saponification value 18
7.4 qKOH/f refractive index 1.
4655 (20℃) Elemental analysis c H 60.15%8.35% Measurement results by NMR Absorption frequency (Hz) 1 2490.234 2 1960.95731 9.
3 7.500 4 1931.6405
1191.40 66
116 (L15 67 1
1 34.7658 1109,
j759 1103.51510
1078.12511
1 0 5 2゜73472
1044.92113
992.18714 9
'86.32815 958.
984f/l 923.82
817 687.50018
675.82B”
279,29620
259.76521 25
1.95322 0.0
00 Of the above absorptions, 45,6. '7 indicates the absorption peak position A of the solvent. 22 indicates the absorption peak position of tetramethylsilane.

Example 3 Into the same reactor as in Example 1, 570 parts of a compound having the following structure, which is an adduct of dipentaerythritol and globylene oxide, and methacrylic a3. y 2 parts, p) 20 parts of luenesulfonic acid, 5 parts of hydroquinone, and 800 parts of toluene were charged, and the reaction was carried out in the same manner as in Example 1 until the amount of produced water became 64.8 parts. The reaction temperature was 113-115°C.

The reaction mixture was dissolved in 1102 parts of toluene and neutralized with 20% aqueous sodium hydroxide solution, followed by 5% 20% NaCl aqueous solution.
Wash 3 times with 00 parts. The solvent was distilled off under reduced pressure to obtain 642 parts of a pale yellow liquid.

This material has the following properties.

Specific gravity (215℃) +, 060 viscosity
Degree (25℃) 773.1 cps Acid value 0.03 ■K
OH/f saponification value 142.5 Misaki KO
H/7 refractive index 1.4655 (20℃
) Elemental analysis c H 61.53% 8.85cm NMR measurement results Absorption frequency (H2) 1 2503.9062
2050.78j- 31878,906 41189,453 51158,203 61150,390 71132,812 j 1126.953 9 1121.093 10 1117.187 11' 1107. ．． 42112
11.01.562 13 1076.171 14 1052.754 15 '1044.921 16 1001.953 17 990.234 18 984.375 19 685.54/1 2'0 671.875 21 277.343 22 273 .43725
2 5 7.8 1 224
25 0.00025
21'6.79626
125.04627'
-1,955 Among the above absorptions, A4+5
+7 indicates the absorption peak position of the solvent.

Application example 1, 2.3. Comparative Application Example 1 To 50 parts of the new ethylenically unsaturated compound obtained in Examples 1 and 2.5, epoxy acrylate resin (Epicote 82B (Shell Stone, bisphenol type epoxy resin manufactured by Yukagaku Co., Ltd.) was added to acrylic acid. (resin obtained by esterification), 50 parts of Irgacure 651 (as a photosensitizer)
1.5 parts of Ciba Geigy Co., Ltd.) was added and applied onto a steel plate panel, followed by ultraviolet curing using a high-pressure mercury lamp (Toshiba Co., Ltd., 2KW). The results are shown in Table 1 below. As a comparative example, with the same composition as above, the new ethylenically unsaturated compound was replaced with dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.,
Table 1 below also shows the curing results of the product changed to DPHA (trade name).

Table 1 The number of times a mercury lamp passes through the lamp until it is dry to the touch.

Patent applicant: Nippon Kayaku Co., Ltd. Procedural amendment November 29, 1980 Director of the Patent Office Kazuo Wakasugi 1, Indication of Gouet Patent Application No. 193437, 1982, 2 Name of the invention: Ethylenically unsaturated compound and its manufacturing method 3, and its relationship to the case of the person making the amendment Patent applicant: 11-2 Fujimi-chome, Chiyoda-ku, Tokyo (408)
Nippon Kayaku Co., Ltd. Representative and President Tsunekazu Sakano 4. Agent 6. No number of inventions will increase due to the amendment 7. Subject of the amendment 8. Contents of the amendment as shown in the attached sheet 1.:'\ Among the amendments 1. The scope of claims in the specification is amended as follows.

(1) General formula (in the formula, R is H9 or CH3; the average value of m and n is p+
q+r-1-, s is 6, q+r is a number from 0 to 5, t' 1) + s is a number from 3 to 6, mp +
The average combined value of nq is a number from 3 to 50. ) is an ethylenic compound.

(2) The following general formula (I) has a number of 1 to 5, the average value of X is a number of 3 to 6, and Y
The average value of aX is a number from 0 to 5, which is x+Y6, and the average total value of aX is a number from 5 to 50. 1. A method for producing an ethylenically unsaturated proboscis represented by the general formula (n), which comprises esterifying a compound represented by the formula (n) with acrylic acid or methacrylic acid.

General formula L10 (However, R in formula CIIJ is H9 or CH3i 111 and n, p+q+r-4-i is 6, q-1-
r is Op -1-n The average combined value of q is a number from 3 to 30. ) Correct lines 13 to 3 from the bottom of page 2, N-, and 5 as follows.

[(In the formula, R is Hl or CH31 The average value of m and n is that J
'LzoJ'L''i is a number from 5 to 5, preferably 1 to 2
the average value of p is a number from 1 to 6, preferably 3 to 6; the average value of q and r is each a number from 0 to 3, preferably 0 or 1; The daily average value is 0
~6, p+q+r+9 is 6 and i (L'
+r is a number from 0 to 3.

Preferably, it is O or 1; p+8 is a number from 3 to 6, preferably 5 or 6, and the average total value of 1mp-1-nq is a number from 6 to 30, preferably "6"・Same oath, 6
Correct lines 11 to 8 from the bottom of the page as follows.

[However, R in the formula [Ij is H or CH3; a (7)
The average value is a number from 1 to 5, preferably 1 to 2; the average value of X is a number from 3 to 6, and the average value of Y is a number from 0 to 3.
X+YJ 4, same book, lines 12 to 2 from the bottom of page 7 are corrected as follows.

Claims (2)

[Claims] (1) General formula (in formula 1, F is H2 or CH3: m and n are integers having a value of 1 to 5, p is an integer having a value of 1 to 6, and q and r are 0. or Cod number with a value of 1 to 3, day must be OI or an integer with a value of 1 to 3, p + q
+r+day is 6 and q0r is 0. or an integer having a value of 1 to 3, p+8 is an integer having a value of 3 to 6, and the average total value of mp-4-nq is a number of 3 to 30. ) is an ethylenically unsaturated compound. (2) The following general formula (1) (However, in formula [,1), R is H2 or CH3; a is 1 to 5
is an integer having a value of , or is an integer having a value of 3 to 6, and Y is 0. or an integer having a value of 1 to 3,
X-1-Y is 6, and the average total value of aX is 5 to 3,0
is the number of A method for producing an ethylenically unsaturated compound represented by the following general formula CII), which comprises esterifying the compound represented by the formula CII) with acrylic acid or methacrylic acid. (However, in the formula (If), R x H9, CHs i m and n are integers having a value of 1 to 5, and p is a value of 1 to 6 to 3
is an integer having a value of ', p + s is an integer having a value of 5 to 6, and the average total value of mp, 4 - nq is 3 to 3.
It is the number of 0. )