JPH0729981B2 - Method for producing composition comprising glycidol ester unsaturated monomer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention relates to an antifogging paint having two or more hydroxyl groups in one molecule,
The present invention relates to a method for producing a composition comprising a glycidol ester unsaturated monomer, which is expected to be applied to water-based paints, UV / EB curable paints, and water-based resins used for contact lenses.

More specifically, the present invention relates to a radically polymerizable unsaturated monomer having a carboxyl group and glycidol as glycidol /
In one molecule characterized by reacting at 95 ° C or less in an inert gas / oxygen mixed gas atmosphere with an oxygen concentration of 1% or more in the presence of a basic acid catalyst with a molar ratio of unsaturated monomers of 1.05 to 1.5 The present invention relates to a method for producing a glycidol ester unsaturated monomer having substantially no free carboxyl group and epoxy group and having two or more hydroxyl groups.

(Prior Art) Conventionally, as a radically polymerizable unsaturated monomer having a hydroxyl group, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1.4-butanediol monoacrylate, 1.4-butanediol monomethacrylate, hydroxypropyl acrylate, Hydroxypropyl methacrylate, ethylene oxide adduct of acrylic acid, ethylene oxide adduct of methacrylic acid, ε-caprolactone adduct of 2-hydroxyethyl acrylate, ε-caprolactone adduct of 2-hydroxyethyl methacrylate, etc. are known. These radically polymerizable unsaturated monomers are widely used as raw materials or intermediates for thermosetting paints, adhesives, urethane acrylate resins and the like.

In recent years, active development and research of antifogging paints, water-based paints, water-based resins, UV / EB curable paints, etc. have been carried out. Saturated monomers are sought. However, the radically polymerizable unsaturated monomer has only one hydroxyl group in one molecule and is not suitable for these applications.

Therefore, many synthetic studies were conducted on 2.3-dihydroxypropyl acrylate or 2.3-dihydroxypropyl methacrylate as a radically polymerizable unsaturated monomer having two hydroxyl groups in one molecule which meets the above object.

(Problems to be Solved by the Invention) For example, it is extremely difficult to react only one hydroxyl group of glycerin in the reaction by esterification of acrylic acid and glycerin, and it is usually a mixture of mono-, di- and triacrylates of glycerin. However, it is very difficult to separate 2.3-dihydroxypropyl acrylate from this mixture.

Also, in the transesterification reaction of acrylic acid ester and glycerin, as in the case of esterification, a mixture of mono-, di-, and triacrylates of glycerin is obtained, and since its purification is difficult, 2.3-dihydroxypropyl acrylate is also obtained by this method. It's very difficult. In addition, in French Patent 2391988, acrylic acid is used in excess of 5 to 30% with respect to glycidol.
Although a method for producing glycerin monoacrylate by carrying out a reaction at ~ 120 ° C is disclosed, this method requires a purification step for removing unreacted acrylic acid,
If the purification step is omitted, only high acid value can be obtained.
On the other hand, although a selective hydrolysis method of glycidyl acrylate has been studied, it is difficult to obtain 2.3-dihydroxypropyl acrylate even by this method because of the reaction characteristic that glycidyl acrylate itself is polymerized.

As mentioned above, the synthesis of 2.3-dihydroxypropyl acrylate, which has been studied so far, is described. Generally, acrylic acid ester, particularly acrylic acid ester having a hydroxyl group is apt to cause porous insoluble "popcorn polymerization",
Purification separation has become a very serious problem in terms of process, operation and cost.

Therefore, the inventors of the present invention have publicly known the above-described method for producing a radically polymerizable unsaturated monomer which does not substantially contain a free carboxyl group and epoxy group and has two or more hydroxyl groups in one molecule. The present invention has been completed as a result of intensive studies to solve the drawbacks of the technology.

(Means for Solving the Problems) That is, the present invention describes that “a radical-polymerizable unsaturated monomer having a carboxyl group and glycidol are present in the presence of a basic catalyst at a glycidol / unsaturated monomer molar ratio of 1.05 to 1.5. under,
Characterized by reacting at 95 ° C or lower in an inert gas / oxygen mixed gas atmosphere having an oxygen concentration of 1% or more, and containing substantially no free carboxyl group and epoxy group, and containing two or more hydroxyl groups The present invention provides a method for producing a composition comprising a glycidol ester unsaturated monomer.

According to the present invention, a compound having no radical-polymerizable functional group or a compound containing two or more radicals has two or more hydroxyl groups in one molecule and must have at least one radical-polymerizable functional group. Compositions comprising glycidol ester unsaturated monomers containing can be prepared without purification steps.

As the radically polymerizable unsaturated monomer having a carboxyl group used in the present invention, acrylic acid, β-acryloyloxyethyl succinic acid, β-acryloyloxyethyl phthalic acid, β-acryloyloxyethyl maleic acid, β-acryloyl Oxypropionic acid, methacrylic acid, β-methacryloyloxyethyl succinic acid, β-methacryloyloxyethyl phthalic acid, β-methacryloyloxyethyl maleic acid, itaconic acid, maleic acid,
Examples thereof include maleic acid monoalkyl esters (having 1 to 12 carbon atoms in the alkyl group), among which acrylic acid and methacrylic acid are particularly preferable. The amount of glycidol used with respect to the radically polymerizable monomer having a carboxyl group is glycidol with respect to 1 mol of the radically polymerizable monomer.
It is 1.05 to 1.5 mol. If it is less than 1.05 mol, a large amount of unreacted radical-polymerizable monomer having a carboxyl group remains, and the acid value is less than 5. On the other hand, if it exceeds 1.5 mol, unreacted glycidol tends to remain.

The basic catalyst that can be used in the present invention includes pyridine, triethylamine, tributylamine, benzylamine,
Examples thereof include benzyldimethylamine, tetramethylammonium chloride, sodium carbonate, sodium hydroxide and potassium hydroxide. The amount of the basic catalyst used is preferably 0.01 to 5.00 parts, more preferably 0.05 to 1.00 part, based on 100 parts of the total amount of the radically polymerizable monomer having a carboxyl group and glycidol.

The present invention is basically carried out in a solventless system, but when the solvent distillation is unnecessary, benzene, toluene, xylene,
It is also possible to carry out the reaction in a solvent system that does not have a reactive functional group such as η-butyl acetate.

In the present invention, it is necessary to carry out the reaction in an inert gas / oxygen mixed gas atmosphere having an oxygen concentration of 1% or more, and the preferable oxygen concentration is 2 to 21%.

Further, as the inert gas used in the present invention, helium, nitrogen, carbon dioxide gas and the like can be used, but air is usually sufficient. The reason for using the atmosphere gas containing at least 1% oxygen is that oxygen has a polymerization inhibiting effect on the acrylic monomer. The method for producing a composition comprising a glycidol ester unsaturated monomer according to the present invention comprises a radically polymerizable unsaturated monomer having a carboxyl group in a predetermined amount of a catalyst and optionally a polymerization inhibitor such as hydroquinone or hydroquinone monomethyl. Add 0.01 to 5.00 parts of ether, 4-methyl-2.6-di-t-butylphenol (BHT), phenothiazine, etc. to 100 parts of the total amount of the radically polymerizable monomer having a carboxyl group and glycidol to obtain a predetermined oxygen concentration. In an inert gas / oxygen mixed gas atmosphere, the reaction temperature is 95 ° C. or lower, preferably 50 to 90 ° C., and a predetermined amount of glycidol is added all at once or continuously for reaction.

It is unstable above 95 ° C and may cause gelation. On the contrary, the reaction rate becomes slower than 50 ° C. The structure of the obtained glycidol ester unsaturated monomer is NMR, IR,
It can be identified and confirmed by elemental analysis, GPC, OH value, double bond measurement, etc.

(Effect of the Invention) The composition comprising the glycidol ester unsaturated monomer according to the present invention does not form a compound containing no radical-polymerizable functional group or a compound containing two or more functional groups, and has two or more hydroxyl groups in one molecule. As a radically polymerizable unsaturated monomer that is highly hydrophilic and has one radically polymerizable functional group, it is an antifogging paint, water-based paint, water-based resin, UV / EB
It is expected to be applied to a wide range of applications as a raw material or an intermediate for curable resins.

The present invention is described below with reference to examples, but the present invention is not limited to these.

In addition, the part in an example means a weight part.

Example 1. Acrylic acid 3 was added to a 1l5 bottle separable flask equipped with a stirrer, a temperature system, a reflux condenser, a dropping funnel and an air introduction tube.
60 parts, triethiamine 3.9 parts and hydroquinone monomethyl ether 3.1 parts were charged and the temperature of the contents was raised to 90 ° C. while flowing air.

Next, while maintaining the temperature of the contents at 90 ° C, glycidol 42
5.5 parts were charged at a constant rate for 4 hours, and the reaction was continued for about 10 hours. Oxilan oxygen 0.15% (glycidol reaction rate 98.7%) acid value 4.0 (mg KoH / g acrylic acid reaction rate 98.9
%) Glycidol ester acrylate 792.5 parts.

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

Acid value; 4.0 (mg KOH / g) Oxirane oxygen; 0.15% Iodine value; 161.6 (grams of iodine combined with 100 g of polymer) Hydroxyl value; 803.5 (mg KOH / g) GPC analysis; Figure 1 IR analysis; Fig. 2 NMR analysis; Fig. 3 The rational formula of the obtained glycidol ester acrylate is as shown below.

(1) and (2) are peaks other than the main peak in Fig. 1 GPC chromatogram. The measurement conditions by GPC chromatograph are as follows.

Fig. 2 The characteristics of the main absorption wave numbers in the IR absorption spectrum are as follows. 3385.5cm characteristic absorption band -OH (O-H stretching vibration) 3036.5cm = CH ₂ of characteristic absorption band (CH ₂ asymmetric stretching vibration) 2881.0Cm aromatic -OCH ₃ characteristic absorption band 1720.9cm -C = C-COO (C = O stretching vibration) α, β-
Of unsaturated ester Of characteristic absorption bands _{1633.2cm CH 2 = CH-R (} C = C stretching vibration) terminal vinyl of the characteristic absorption band 1290.5cm -C = C-COO- (stretching vibration of C-O) 1188.7cm ibid 1115.5Cm 2 primary OH (Stretching vibration of C-O) 1058.5 cm Primary OH (Stretching vibration of C-O) The signals of the NMR spectrum of Fig. 3 are as follows. Signal of 3.4-4.1ppm −CH ₂ OCH ₂ −, Signal -COOCH signal 4.2ppm protons -CH ₂ OH ₂ - Signal embodiment of the signal CH ₂ = CH-COO- proton signals 5.7~6.6ppm proton 2. methacrylic the same apparatus as in Example 1. Acid 344.4 parts, triethylamine 3.4 parts, hydroquinone monomethyl ether 2.7
The temperature of the contents was raised to 85 ° C. while charging a part and flowing air. Next, while keeping the temperature of the contents at 85 ° C, 340.4 parts of glycidol was charged at a constant rate for 4 hours, and then the reaction was continued for about 9 hours, and oxirane oxygen 0.18% (glycidol reaction rate 98.3%), acid value 0.78 ( 690.9 parts of glycidol ester methacrylate having a reaction rate of 99.8% of mg KOH / g methacrylic acid was obtained.

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

Acid value; 0.78 (mg KOH / g) Oxirane oxygen; 0.18% Iodine value; 148.2 (grams of iodine combined with 100 g of polymer) OH value; 704.5 (mg KOH / g) Indication of glycidol ester methacrylate obtained The sex formula is as follows.

[Brief description of drawings]

FIGS. 1, 2, and 3 are gel permeation (GPC) chromatograms, IR spectra, and NMR of the glycidol ester acrylate obtained in Example 1, respectively.
It is a spectrum.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-51-65705 (JP, A) JP-A-56-79641 (JP, A) JP-A-59-14017 (JP, A) JP-A-50- 154205 (JP, A) JP 54-61117 (JP, A) JP 56-36433 (JP, A) JP 38-22858 (JP, B1) French Patent 2391988 (FR, A) "Acrylic" Acid ester and its polymer [II] "(Sho 50-3-30), Shokoido, pp. 15-21

Claims (1)

[Claims] 1. An inert gas having an oxygen concentration of 1% or more in the presence of a basic catalyst at a glycidol / unsaturated monomer molar ratio of 1.05 to 1.5 of a radically polymerizable unsaturated monomer having a carboxyl group and glycidol. / A glycidol ester unsaturated monomer which does not contain a substantially free carboxyl group and epoxy group and which contains two or more hydroxyl groups, which is characterized by reacting at 95 ° C or lower in an oxygen mixed gas atmosphere A method for producing the composition.