JPS63270641A - Di(meth)acrylic acid ester - Google Patents

Abstract

NEW MATERIAL:A di(meth)acrylic acid ester shown by formula I (R is H or CH3; average value of n is 1-50). USE:A readily handleable liquid having relatively low viscosity at normal temperature and useful as a vehicle for ultraviolet-curing type or electron ray curing type printing ink or coating compound having excellent flexibility and improved curing properties. PREPARATION:A carbonate diol shown by formula II is reacted with acrylic acid or methacrylic acid preferably in the presence of a polymerization inhibitor at 50-130 deg.C, preferably 65-90 deg.C to give a compound shown by formula I readily polymerizable in the presence of heat, ultraviolet light, ionization, radiation or radical initiator. The compound shown by formula II is obtained by subjecting 3-methyl-1,5-pentanediol to ester interchange reaction with a diaryl carbonate or dialkyl carbonate.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention provides novel di(meth)acrylic acid esters that can be easily (co)polymerized in the presence of heat, ultraviolet light, ionization, radiation, or radical initiators. It is related to.

(Prior Art) Various polycarbonate acrylic esters have been developed and are being considered as components of adhesives, paints, and the like.

(Problems to be Solved by the Invention) However, polycarbonate acrylic esters that have been studied in the past, for example, JP-A-52-1045
The polycarbonate acrylic ester disclosed in No. 53 is useful as an adhesive, but the problem when using it is that it is solid or a liquid with high viscosity at room temperature, so it is difficult to handle, and adhesives etc. When used for this purpose, it may crystallize before use and must be heated and dissolved before use.

(Means for Solving the Problems) The present invention provides a liquid with relatively low viscosity at room temperature that is useful as a vehicle for ultraviolet curable or electron beam curable printing inks and paints, and has excellent flexibility and curability. An object of the present invention is to provide a novel di(meth)acrylic acid ester. That is, the present invention relates to the following general formula [I] (wherein, R represents H or CR2, and the average value of n is 1 to 5.
The number is 0, preferably 3 to 30. ) It relates to a di(meth)acrylic acid ester represented by

This new di(meth)acrylic acid ester general formula [■]
can be produced by the reaction of a carbonate diol represented by the following general formula [■] (where n has the same meaning as above) and acrylic acid or methacrylic acid at elevated temperature. Regarding this reaction.

This will be discussed in more detail later. The carbonate diol of general formula (n) can be obtained by transesterification of 3-methyl-1,5-bentanediol and diaryl carbonate or dialkyl carbonate. can be obtained. Specific examples of diaryl carbonate or hasialkyl carbonate used as raw materials include:

Side light, diphenyl carbonate, bis-chlorophenyl carbonate, dinaphthyl carbonate.

Examples include phenyl-tolyl carbonate, phenyl-chlorophenyl carbonate, phenyl-chlorophenyl carbonate, dimethyl carbonate, diethyl carbonate, and the like. The transesterification reaction between the diol compound and diaryl carbonate or dialkyl carbonate is carried out under reduced pressure.

The reaction is carried out by distilling off by-product phenol and the like at a reaction temperature of 50 to 200°C. Preference is given to using transesterification catalysts (eg tetrabutyl titanate, sodium phenolate).

The amount used is 0.01 to 1% by weight based on the diaryl carbonate or dialkyl carbonate. The carbonate diol represented by the general formula C1,l] thus obtained is a monocarbonate diol having one carbonate structure in one molecule or a polycarbonate diol having two or more carbonate structures in the molecule.

Preparation of di(meth)acrylic esters (general formula CI) Di(meth)acrylic esters (general formula [I) are prepared by reacting carbonate diols of general formula CID with acrylic acid or methacrylic acid or mixtures thereof. Ru. The amount of acrylic acid or methacrylic acid used is about 1 to 5 moles per 0.5 mole of carbonate diol (general formula [II)] charged. The reaction is preferably carried out in the presence of a polymerization inhibitor to minimize or retard the polymerization of (meth)acrylic double bonds. The polymerization inhibitors mentioned above are well known to those skilled in the art and they are used in concentrations of 0.01 to 5% by weight of the mixture. Examples of these polymerization inhibitors include hydroquinone, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, p-
-benzoquinone, phenothiazine, N-nitron diphenyl, fourea.

Examples include copper salts. The reaction is generally carried out at temperatures between about 50°C and 1
Esters of carbonate diols (general formula [■]) with acrylic acid or methacrylic acid to produce di(meth)acrylic esters (general formula [I]) at a temperature of 30 °C, preferably 65 °C to 9 o °C for a sufficient period of time to ensure completion of the process. This time is
It will vary depending on the batch size, the respective reactants and catalysts and the reaction conditions employed. Acrylic acid still used esterification catalyst still 0.1 to methacrylic acid
It is present in a concentration of 15 mol%, preferably between 1 and 6 mol. Any known esterification catalyst can be used, examples of which include p-)luenesulfonic acid, methanesulfonic acid, phosphoric acid, sulfuric acid, and the like. It is desirable to have an inert solvent such as hexane, cyclohexane, benzene, toluene present to aid in the removal of water produced during the esterification reaction. The di(meth)acrylic esters (general formula [■]) are useful as vehicles for coating and ink compositions;
It can be cured by radiation or by thermal means. Radiation curing can be carried out by particulate radiation, such as ionizing or electron beams, or by actinic radiation, such as ultraviolet radiation. When curing is carried out with actinic radiation C, various photoinitiators commonly known to those skilled in the art are included, such as benzophenone, N,N-dimethylbenzoyl ester, etc. 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 di(meth)acrylic acid ester may be used alone or in combination with other monomers such as trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, or unsaturated group-containing resins such as unsaturated groups. It can be used as a vehicle by mixing with resins such as saturated polyester, polyester acrylate, epoxy acrylate, and urethane acrylate. When used in combination with other monomers or resins.

The mixing ratio can be any desired ratio and is not particularly limited.

This novel di(meth)acrylic acid Nistelha can also be polymerized by adding an organic peroxide (eg, benzoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, etc.).

(Example) In a typical embodiment, S (meth)acrylic acid,
Polycarbonate diol (general formula (II)).

Charge the catalyst, solvent, and polymerization inhibitor into the reactor. This mixture is heated until esterification is substantially complete, and then the di(meth)acrylic ester (general formula [I]) is recovered by conventional methods.

The invention is further illustrated by the following examples. In the following, parts refer to parts by weight unless otherwise specified.

Example 1 A compound of the following structural formula (average molecular weight 58
1. OH value 195.0) 581 parts.

172.8 parts of acrylic acid, 13.4 parts of 1)-toluenesulfonic acid, 1.1 parts of hydroquinone, 400 parts of benzene
100 parts of cyclohexane and heated.

The produced water is distilled together with the solvent, and only the water is removed from the system using a separator, and the solvent is returned to the reactor. It was cooled when 37.8 parts of water was produced. What is the reaction temperature?

The temperature was 82-86°C. The reaction mixture was diluted with benzene 1200
part and 500 parts of cyclohexane.

After neutralizing with a 20% caustic soda aqueous solution, it is washed three times with 500 parts of 20% saline. The solvent was distilled off under reduced pressure to obtain 624 parts of a pale yellow liquid. This product has a viscosity (25℃) 6
It was 60 cps.

The results of 15G nuclear magnetic resonance (NMR) measurement of the obtained product are shown below.

Lagoon Chemical shift (1) [) m) Strength (ch)
1 166, 203
10312 155, 288
1054'5 130
．． 598 19064
428, 518 190
35 79, 268
9766 77, 05
9 10677
74, 980 11498
64, 013 781
0? 62. 634
251010 '55. 475
927 1+1 26
．． 639 596912
19, 181 5106
Note that the above measurements were performed using tetramethylsilane as a reference substance and single-fold chloroform as a solvent.

This was done using the proton decoupling method.

Example 2 Into the same reactor as in Example 1, 504 parts of a compound having the following structural formula (average molecular weight: 1008.08, valence: 111.3), 86.4 parts of acrylic acid, 2.4 parts of sulfuric acid, 0.5 parts of hydroquinone, Prepared 400 parts of benzene, 100 parts of cyclohexane,
The reaction was carried out in the same manner as in Example 1 until the amount of water produced was 19.1 parts. What is the reaction temperature?

The temperature was 83-87°C. The reaction mixture was diluted with benzene 1200
part and 300 parts of cyclohexane.

Neutralization, washing, and solvent removal were performed in the same manner as in Example 1 to obtain 545 parts of a pale yellow liquid.

This has a viscosity (25° C.) of asoocps.

Measurement results by NMR Chemical shift (ppm) Intensity (chi) 1
165.294 3552 +54-3
78 11533 129.687
9114 127.608 6305
78.358 5706 76.
149 5187 74.070
6296 65.103 6535q
61.725 9871Q
34.566 722411 25.72
9 342312 18.192
2402 Example 3 Into the same reactor as in Example 1, 622 parts of a compound having the following structural formula (average molecular weight 2074, OH value 54.1), 43.2 parts of acrylic acid, 1.4 parts of sulfuric acid, and 2 fluoron/Shydrolone were added. , 3 parts, and 600 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 11.8 parts. The reaction temperature was 10
The temperature was 5-116°C. The reaction mixture was diluted with toluene 1800
The solution was neutralized, washed, and desolventized in the same manner as in Example 1 to obtain 642 parts of a pale yellow liquid. This has a viscosity (2
5℃).

It was 48,400 Cp days.

Measurement results by NMR Chemical shift (Illpm) Intensity (CH) 1
155.288 21552 1
30, 598 58 13
128.518 261
4 79, 268
7005 77, 059
6 306 74.980
79 17 67.443
2878 66.013 908
39 62.654
59710 35.475 896
311 26+ 639
504112 19+ 101
529713 0,000
235 Example 4 Into the same reactor as Example 1, the same carbonate diol compound as Example 1 (average molecular weight 581°, valence 195+
0) 581 parts, methacrylic acid 206.4 parts, sulfuric acid 6.8 parts
1.6 parts of /S hydroquinone and 600 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 38.2 parts. What is the reaction temperature?

The temperature was 100-117°C. The reaction mixture was diluted with toluene 18
00 parts and neutralized in the same manner as in Example 1.

After washing and removing the solvent, 5741 parts of a pale yellow liquid was obtained.

This product had a viscosity (25° C.) of 290 cpg.

Measurement results by NMR Chemical shift (ppm) Intensity (chi) 1 1
67.373 7512 455.288
14363 136.445 16
924 125.270 28945
79.268 6206 77.05
9 8017 74.980 8
018 66.013 6165 9 62.764 252110
35, 475 77511
1 26, 898
226712 26, 639
316013 19, 101
248014 18,
522 113715
0, 000 3!50
Comparative Example 1 A compound of the following structural formula (manufactured by Nippon Polyurethane Co., Ltd., DN-981°08 valence 112.2) was placed in the same reactor as Example 1.
m9KOH/7. average molecular weight 1000) 700 parts, 121 parts of acrylic acid, 14 parts of p-toluene aluminum phosphoric acid, 1. o parts, 560 parts of benzene, and 140 parts of cyclohexane.

By heating, 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 25.2 parts of water had been produced. The reaction temperature is 8
The temperature was 0-86°C. The reaction mixture was dissolved in 960 parts of benzene and 240 parts of cyclohexane, neutralized with a 20% caustic Nogoo aqueous solution, and washed three times with 500 parts of 20% brine. The solvent was distilled off under reduced pressure to obtain 667 parts of a pale yellow solid. This thing.

It has the following properties.

Melting point: 43°C Application Examples 1 to 4, Application Comparative Example 1 KAYA was added as a photopolymerization initiator to 100 parts of the di(meth)acrylic acid ester obtained in Examples 1 to 4 and Comparative Example 1.
5 parts of CURK BP (manufactured by Nippon Kayaku Co., Ltd., benzophenone) and KAYACUREEPA as an accelerator
After adding 10 parts of N,N-dimethylbenzoic acid ethyl ester (manufactured by Nippon Kayaku Co., Ltd.) and coating it on a PVC sheet with a film thickness of 25 μm using a roll coater, a high-pressure mercury lamp (manufactured by Toshiba Corporation,
2xw).

In the table ■, the bending of the paint film is 180° with the paint film outside.
It was bent and its condition was visually judged.

Curing time was expressed in seconds until dry to the touch.

Table -■ (Effects of the Invention) The di(meth)acrylic acid ester of the present invention is liquid at room temperature and easy to handle (useful as a vehicle for printing inks and paints. The resulting coating film has excellent flexibility.

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R represents H or CH_3, and the average value of n is 1 to
The number is 50. ) Di(meth)acrylic acid ester represented by