JPS6270341A - Production of glycidol ester unsaturated monomer - Google Patents

Abstract

PURPOSE:To advantageously obtain the titled compound, by reacting a radically polymerizable unsaturated monomer having carboxyl group with glycidol at a specific molar ratio in the presence of a basic catalyst in an atmosphere of a mixed gas of an inert gas and oxygen gas within a specific oxygen gas concentration range. CONSTITUTION:A radically polymerizable unsaturated monomer having carboxyl group is reacted with glycidol at 1.05-1.5molar ratio of the glycidol to the unsaturated monomer in the presence of a basic catalyst, e.g. pyridine, in an atmosphere of a mixed gas of an inert gas and oxygen in >=1% oxygen concentration at <=95 deg.C to afford the aimed glycidol ester unsaturated monomer. Thereby, the aimed glycidol ester unsaturated monomer, having >=2 hydroxyl groups in one molecule and surely containing one radically polymerizable group can be obtained without forming a compound containing no or two or more radically polymerizable groups and requiring any purification step.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to anti-fogging paints having two or more hydroxyl groups in one molecule;
Water-based paint, tJV-FBlii! The present invention relates to a method for producing glycidol ester unsaturated monomers, which are expected to be used in aqueous resins used in chemical coatings and contact lenses.

More specifically, the present invention combines a radically polymerizable unsaturated 111d compound having a carbo-4-syl group and glycidol in the L ratio 1.05-1 () of glycidol/unsaturated monomer in the absence of a base-attaching catalyst. [Hands, inert gas with an oxygen concentration of 1% or more/
The present invention relates to a method for producing a glycidol ester unsaturated monomer having two or more hydroxyl groups in one molecule, which is characterized by a reaction temperature of 95° C. or lower in an oxygen gas atmosphere.

(Prior art) Conventionally, as radically polymerizable unsaturated monomers having a hydroxyl group, 2-hydroxyethyl 7 acrylate, 2-dronyl methacrylate, and 1,4-butanediol monoacrylate have been used. 1-, 1,4-butanediol [nomethacrylate, hydroxib "]] pyl acrylate 1-hydro 4-dipropyl methacrylate, [dylene oxide adduct of acrylic acid, ethylene oxytoy-j adduct of methacrylic acid, 2- ε of hydro4-cyTdelacrylate
-caprolacone adducts, ε-caprolacone adducts of 2-hydro-X-sibutyl methacrylate, and the like are known. These radically polymerizable unsaturated monomers are used in a wide range of applications, including as raw materials or intermediates for thermosetting paints, adhesives, urethane acrylate resins, and the like.

In recent years, there has been active development and research into anti-fog paints, water-based paints, water-based resins, UV/EB curable paints, etc.
There is a need for a highly hydrophilic, radically combinable, unsaturated single fn compound having many hydroxyl groups in its molecule. However, the radically polymerizable unsaturated monomer mentioned above has F! water in one molecule! 1
It has only one, making it unsuitable for these uses.

Therefore, many synthetic studies have been conducted on 2.3-dihydroxypropyl acrylate or 2.3-dihydroxypropyl methacrylate as a radically polymerizable unsaturated monomer having two hydroxyl groups in one molecule that meets the above purpose.
child.

(Problems to be Solved by the Invention) For example, in the reaction of esterification of acrylic acid and glycerin, it is extremely difficult to react only 1% of water fj of glycerin. A mixture of triacrylates is prepared, but it is very difficult to separate 2,3-dihydroxypropyl acrylate from this mixture.

In addition, in the transesterification reaction between Nisder acrylate and glycerin, similar to the case of esterification, the U compound of glycerin's t-no, g-, and 1-helical acrylate-1~ is formed.
Since its purification is difficult, it is very difficult to obtain 243-dihydroxypropyl acrylate-1 by this method as well.

Further, French Patent No. 2,391,988 discloses that acrylic acid is used in excess of 5 to 30% relative to glycidol, and the reaction is carried out at 80 to 120'C.

A method for producing glycerin monoacrylate has been disclosed, but this method requires purification of the culm to remove unreacted acrylic acid, and if the purification step is omitted, only a product with a high acid value can be obtained.

-=75, a selective hydrolysis method for glycidyl acrylate-1 has also been studied, but due to the reaction characteristic that glycidyl acrylate itself polymerizes, even this method has 2.
Obtaining 3-dihydroxypropyl acrylate is very difficult.

I have described the synthesis of 2,3-dihydroxypropyl acrylate that has been researched so far, but in general, acrylic esters, especially acrylic esters with hydroxyl groups, are prone to porous and insoluble "bob cone polymerization", and purification and separation is difficult. This has become a huge problem in terms of operation, operation, and even strikes.

Therefore, the present inventors conducted intensive studies to solve the drawbacks of the above-mentioned known techniques regarding the production method of radically polymerizable unsaturated monomers having two or more hydroxyl groups in one molecule, and as a result, the present invention was developed. completed.

(Means for Solving the Problems) Namely, 1. The present invention is based on [a radically polymerizable unsaturated monomer having a carboxyl group and glycidol in a molar ratio of glycidol/unsaturated monohanging body of 1.05 to 1. In step 5, the reaction is carried out at 95°C or lower in the presence of a basic catalyst in an inert gas/oxygen u gas atmosphere with an oxygen concentration of 1% or more. ”.

According to the present invention, a compound having two or more hydroxyl groups in one molecule without producing a compound containing no radically polymerizable functional group or a compound containing two or more radically polymerizable functional groups, and always having one radically polymerizable functional group The unsaturated monomer containing glycidol ester can be produced without purification.

Examples of the radically polymerizable unsaturated monomer having a carboxyl group used in the present invention include acrylic acid, β-acryloyl primary thiedylsuccinic acid, β-acryloyloxyethylphthalic acid, β-acryloyloxyethylmaleic acid, β-acryloyloxypropionic acid, methacrylic acid, β-methacryloyloxyedylsuccinic acid, β-methacryloyloxyethyl phthalic acid, β-methacryloyloxyethylmaleic acid, itaconic acid, maleic acid,
Examples include maleic acid monoalkyl esters (alkyl group having 1 to 12 carbon atoms), and among these, acrylic acid and methacrylic acid are particularly preferred.

The amount of glycidol used for the radically polymerizable monomer having a carboxyl group is 1.05 moles of I-glycidol per 1 mole of the radically polymerized bamboo monomer, or 1.5 moles. 10j] When the amount is less than the above, a large amount of radically polymerizable monomer with unreacted carboxyl groups remains, and the acid value is 5.
Hard to get smaller.

On the other hand, if the amount is more than 1.5 mol, unreacted glycidol tends to remain.

Basic catalysts that can be used in the present invention include pyridine, triethylamine, triethylamine, benzylamine,
Examples include benzyldimethylamine, r-tramethylan7inium chloride, su]-lium carbonate, sodium hydroxide, and 7J hydroxide. The amount of the basic catalyst used is 0.01 parts per 100 parts of the total amount of the radically polymerizable monomer having a carboxyl group and glycidol.
-.5.00 parts is preferable, and 0.05 to 1.00 parts is more preferable.

The present invention is basically carried out in a solvent-free system, but if solvent distillation is not necessary, reactive solvents such as benzine, i~l, xylene, acetic acid, etc. can be used. It is also possible to carry out the reaction in a solvent system that does not contain any functional groups.

In the present invention, it is necessary to carry out the reaction in a DI atmosphere of an inert gas/acid gas mixture with an oxygen concentration of 1% or more, and the preferred oxygen concentration is 2 to 21%.

Inert gases used in the present invention include helium, nitrogen, carbon dioxide, etc., but air is usually sufficient.

The reason for using an atmospheric gas containing at least 1% of oxygen is that oxygen has an effect on inhibiting the polymerization of acrylic hexamer.

The method for producing the glycidol ester unsaturated monomer of the present invention is to add a predetermined amount of catalyst and optionally a C polymerization inhibitor to a radically polymerizable unsaturated monomer containing a carboxyl group, for example, Hyde L11. -Non, by-aid, 111 amounts of carboxylcarpolymerization of henon, 4-methyl-2,6-di-t-butylphenol (811 units), 1-nobutyl phenol, etc., and 1-1% of glycidol. - Add 0.01 to 500 parts to 100 parts of the tar material, and place in an inert gas/oxygen mixed gas atmosphere with a predetermined oxygen concentration at a reaction temperature of 95°C or less, preferably 50 to -90°C. A fixed amount of glycidol is added all at once or continuously to initiate the reaction.

If the temperature exceeds 95°C, it becomes unstable and may cause gelation. Conversely, below 50℃, the reaction rate decreases.
The structure of the obtained glycidol ester unsaturated monomer is N
Identification can be confirmed by MR, IR, elemental analysis, G I"C, OH value, double bond measurement, etc.

(Effect of the invention) The glycidol ester unsaturated monomer according to the present invention has two or more hydroxyl groups in one molecule without forming a compound containing no radically polymerizable functional group or a compound containing two or more radically polymerizable functional groups, and Since it always contains one radically polymerizable functional group, it is a highly hydrophilic radically polymerizable unsaturated monomer and can be used as a raw material or intermediate for antifogging paints, water-based paints, water-based resins, U and FB curable resins, etc. It is expected that it will be used in a wide range of applications.

The present invention will be explained below with reference to Examples, but the present invention is not limited by these.

In addition, parts in the examples mean parts by weight.

Example 1.

360 parts of acrylic acid, 3.9 parts of triethylamine, and 3,1 parts of hydroquinone 7-methyl-al in a 1.1) 5-layer separable flask equipped with a stirrer, a temperature system, a reflux condenser, a dropping funnel J3, and an air introduction tube. The temperature of the contents was raised to 90°C while blowing air.

Next, while maintaining the temperature of the contents at 90°C, 425.5 parts of glycidol was added at a constant rate for 4 hours, and then about 10
The reaction was continued for several hours, oxirane oxygen 0.15% (glycidol reaction rate 981%), acid value 4.0 (RgKOtl
792.5 parts of glycidol nisal acrylate-1 with a reaction rate of 98.9%) was obtained.

The analysis results of the obtained glycidol ester acrylate are as follows.

Acid value: 4.0 (All
! J ni Kano 10) Oxirane Oxygen: 0.15% Iodine value: 161.6 (Number of grams of El element in 100g of polymer) Hydroxyl value: 803.5 (ttty KOII/
g) GPC analysis; Fig. 1 IR analysis; Fig. 2 NMR analysis; Fig. 3 The specific formula of the obtained glycidol ester acrylate is as shown below.

■ n= 2~4 CI+2= CH-COOCH2C12COO-(C1
12C11CI+20), 1l---(2,)■. -1 to 4 The measurement strip f1 by GPC chromatography is as follows.

lN5TRIIH[N'l':5IIIHADZI
I HI'lCHODEL 1. c-3^C0II
IHN:5HIHAD7U H2C-60
0.5mX7.9mmφ-×1118G-30
-X 1 113G-20-X I H3G-15, -X1 113G-10-X I GADI Co! UHN: H
2O-600, 5mX7.9mmφ -X10ETEC
TOR:5llODEX HODEL RI 5E
-31RANGE: A1T
8 XMOBILE PH^SE:
Tl11FLOW RAT[: 1. Oml/m
1nPRFSS ・80 ko/ctdSAH
P1. E5IZE: 2.0 μm
10x Rare CIIART 5PFIID: 2
．． 5 mm/m1nCOLIIHN TEHP l
The characteristics of the main absorption wavenumbers in the IR absorption spectrum diagram in Figure 2 at 50°C are as follows.

3385,5cm Characteristic absorption band of -OH (O-1"
Stretching vibration) 3036.5cm = C1l, characteristic absorption band (C1
-1, L asymmetric stretching vibration) 2881.0 cm Aromatic-〇 〇 H characteristic absorption band 1720.9 cm -C=C-Coo (C-〇 stretching vibration) 1ρ - Vesicle 1633.2 cm CI-! ! :L=CH-'R(
C=C stretching vibration) Characteristic absorption band of terminal vinyl 1290.5 cm -C=C-Coo -(C-0
(stretching vibration) 1188.7cm Same as above 1115.5cm 2nd grade 0H (stretching vibration of C-0 l7
I) 1058.5 cm 1st class 0N (stretching vibration of C-0) Further, the signals in the NMR spectrum diagram of FIG. 3 are as follows.

4. Pro1-signal of 2ppm Zigpuru COOC1-1-5.7-6
．． Jig pull of 6 ppm CH= CH-COO- Jig pull of ton Example 2 Example 1. 344.4 parts of methacrylic acid in the same apparatus as
- 3.4 parts of Liebulamine and 2.7 parts of Hyde[1-1non[Tumedel ether] were added, and the temperature of the contents was raised to 85° C. while air was flowing. Next, while maintaining the temperature of the contents at 85°C, add 340.4 parts of glycidol to -
Prepare at a constant rate for 4 hours, and continue the reaction for about 9 hours after step 1)
Thus, 690°9 parts of glycidol ester methacrylate with oxirane oxygen 0.18% (reaction rate of glycidol 983%) and acid value 0.78 (reaction rate of #l!? methacrylic acid 99.8%) was obtained. Ta.

The analysis results of the obtained glycidol nistil methacrylate 1~ are as follows d3.

Acid value: 0.78 (IIIgKOJ
+/(1)A xylan oxygen -〇. 18% Iodine value: 148.2 (polymer 100Ω
Number of grams of sagebrush combined with) 01-1 value; 704.5 (011/su to ■) 15 glycidol nispur methacrylate I
The demonstrative formula for is shown below.7, CIl = C−C
00-(C112C11C1120)n-11■ n-1-~4 ″'Kawaishi-1,15

[Brief explanation of drawings]

Figures 1, 2, and 3 are the gel perminiscence (G F) chromatogram, IR spectrum, and NMR spectrum of glycidol nitride acrylate-1 obtained in Example 1, respectively. .

Claims (1)

[Claims] A radically polymerizable unsaturated monomer having a carboxyl group and glycidol are mixed at a glycidol/unsaturated monomer molar ratio of 1.
．． 05 to 1.5 in the presence of a basic catalyst in an inert gas/oxygen mixed gas atmosphere with an oxygen concentration of 1% or more at 95°C or lower. .