JPH06271564A - Sulfurous ester derivative - Google Patents

Abstract

PURPOSE:To obtain the subject new compound useful as a monomer for providing a reactive resin for advancing crosslinking reaction between an amine and a thiol, excellently protecting environment. CONSTITUTION:A compound of formula I [R<1> is H or lower alkyl; R<2> is lower alkyl; (a) and (b) are 1 or 2; (c) is 0 or 1] such as 5-methacryloyloxymethyl-5-1, 3, 2-dioxathian-2-oxide. The compound of formula I is obtained by reacting a compound of formula II [X is halogen] with a compound of formula III in the presence of a base or reacting a compound of formula IV with thionyl chloride.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel sulfite derivative.

[0002]

2. Description of the Related Art Reactive resin particles have been attracting attention as a useful functional material in the fields of paints, adhesives, medicine and the like. Such reactive resin particles are resin particles having a functional group such as a carboxyl group or an epoxy group, and the crosslinking reaction between these functional groups and other functional groups has usually been carried out in an organic solvent. However, as interest in environmental protection has increased in recent years, it is strongly desired to convert the medium of the crosslinking reaction from an organic solvent to an aqueous medium, and research is actively conducted.
For example, a reactive resin particle having a cyclocarbonate group as a functional group has a characteristic that a crosslinking reaction proceeds in an aqueous medium and at a low temperature, and the obtained crosslinked product can be expected to be used as a functional material. (JP-A-3-6235). Such reactive resin particles have the advantage that the crosslinking reaction proceeds at low temperature in an aqueous medium, and the obtained crosslinked product is expected as a useful functional material in the fields of paints, adhesives, medical care and the like. . However, at present, there are still few types of reactive resin particles having such advantages.

[0003]

DISCLOSURE OF THE INVENTION As a result of intensive investigations under these circumstances, the present inventors have found that a novel sulfite ester represented by the following formula (2) can be converted into a polymerizable monomer such as acrylic acid ester. Reactive resin particles obtained by polymerizing with the body,
It was found that a crosslinking reaction proceeds with amines and thiols in an aqueous medium at low temperature, and the present invention has been completed based on this finding.

[0004]

According to the present invention, the following equation (2) is thus obtained.

[Chemical 2] (Wherein R ¹ represents a hydrogen atom or a lower alkyl group, R ² represents a lower alkyl group, a and b represent 1 or 2, and c represents 0 or 1). To be done.

The sulfite derivative of the present invention is represented by the above formula (2) and is a novel compound not described in the literature. In the formula, R ¹ represents a hydrogen atom or a lower alkyl group such as a methyl group, an ethyl group and a propyl group, and among them, a lower alkyl group is preferable. R ² represents the same lower alkyl group as described above.

A and b are 1 or 2, and c is 0 or 1.

Such sulfite derivative is, for example,
It can be obtained by reacting the acid halide represented by the formula (3) with the cyclosulfites represented by the formula (4) in the presence of a base.

[0008]

[Chemical 3] (In the formula, R ¹ is the same as above. X is a halogen atom.) X is a halogen atom such as a chlorine atom, a bromine atom, a fluorine atom or an iodine atom.

[0009]

[Chemical 4] (In the formula, R ² , a, b and c are the same as those described above.)

Bases are tertiary aliphatic amines such as pyridine, trimethylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, diisopropylamine; 2,6-lutidine, N, N-dimethylaniline, N, N. Examples thereof include tertiary aromatic amines such as diethylaniline and 4-dimethylaminopyridine.

The amount of cyclosulfites represented by the formula (4) is usually 0.5 to 2 mol, preferably 0.7 to 1 with respect to 1 mol of the acid halide represented by the formula (3). 0.5 mol is used. The amount of the base used is usually 1 to 5 mol, preferably 1 to 1 mol of the acid halide represented by the formula (3).
~ 2 moles are used.

A diluent may be used in the reaction. Diluents include hydrocarbons such as toluene, benzene and cyclohexane; ethers such as diethyl ether, tetrahydrofuran and dimethoxyethane; nitriles such as acetonitrile; halogenated hydrocarbons such as methylene chloride and chloroform; acetone; Examples thereof include ketones such as methyl ethyl ketone; esters such as ethyl acetate. The total amount of cyclosulfite and acid halide used is 5 to 50% by weight.
Is appropriately selected within the range.

The reaction temperature is -50 to + 30 ° C, preferably -20 to + 10 ° C, and the reaction time is 1 to 10 hours, preferably 2 to 4 hours.

Further, the sulfite derivative of the present invention is
It can be obtained by reacting the unsaturated carboxylic acid ester represented by the formula (5) with thionyl chloride in the presence of a base.

[0015]

[Chemical 5] (In the formula, R ¹ , R ² , a, b and c are the same as described above.)

The amount of thionyl chloride used is represented by the formula (5)
The amount is usually 1 to 5 mol, preferably 1 to 2 mol, based on 1 mol of the unsaturated carboxylic acid ester represented by. The reaction temperature is -50 to + 30 ° C, preferably -20 to +10.
At C, the reaction time is 1 to 10 hours, preferably 2 to 4 hours.

The same bases as described above are used. Further, also in such a reaction, the same diluent as described above can be present.

After completion of the reaction, hydrogen chloride produced is reacted with a base present in the reaction system to remove it from the reaction system, and then the sulfite derivative can be isolated by performing extraction or distillation.

The thus-obtained sulfite ester derivative has a polymerizable unsaturated bond at the terminal and thus has high reactivity, and is useful as various synthetic intermediates. For example, the sulfite derivative of the present invention readily copolymerizes with polymerizable monomers such as acrylic acid and methacrylic acid to give reactive resin particles. Such reactive resin particles have a cyclosulfite group as a functional group, and are easily crosslinked in a water medium with a diacid base such as ethylenediamine at a temperature of about 0 to 100 ° C, preferably 0 to 80 ° C. To do.

[0020]

EXAMPLES The present invention will be described in more detail with reference to the following examples. Parts and% in the examples and comparative examples are based on weight unless otherwise specified. Example 1 6.6 g of 5-hydroxymethyl-5-methyl-1,3,2-dioxathian-2-oxide was dissolved in 80 ml of methylene chloride, and 6.1 g of triethylamine was added at 10 ° C or lower. Next, 5.2 g of methacrylic acid chloride was gradually added dropwise at 5 to 10 ° C, and the mixture was reacted at room temperature for 3 hours. After the reaction is completed, the reaction solution is filtered,
The filtrate was concentrated under reduced pressure. Ethyl acetate was added to the residue, the organic layer was washed with sodium hydrogen carbonate, and concentrated under reduced pressure to obtain a crude product. When this was distilled under reduced pressure, 5-
Methacryloyloxymethyl-5-methyl-1,3,2
-Dioxathian-2-oxide was obtained with a yield of 69.4%.

The physical properties are shown below. Mass: 234 (M ⁺ )

¹ H-NMR (CDCl ₃ ) δ: 6.13
(S, 1H), 5.65 (s, 1H), 4.89 and 4.
68 (2 × d, 2H), 4.37 and 3.95 (2 × s,
2H), 3.70 and 3.55 (2xd, 2H), 2.0
0 (s, 3H), 1.37 and 0.91 (2 x s, 3H)

Example 2 5-Ethyl-5-, instead of 5-hydroxymethyl-5-methyl-1,3,2-dioxathian-2-oxide
Hydroxymethyl-1,3,2-dioxathian-2-
When the reaction was performed in the same manner as in Example 1 except that the oxide was used, 5-ethyl-5-methacryloyloxymethyl-1,3,2-dioxathian-2-oxide was obtained with a yield of 78.2%. .

The physical properties are shown below. Mass: 248 (M ⁺ )

¹ H-NMR (CDCl ₃ ) δ: 6.09
(S, 1H), 5.54 (s, 1H), 4.30 (m,
2H), 4.00 to 3.80 (m, 2H), 1.92
(S, 3H), 2.00 to 1.80 (m, 2H), 1.
42 to 1.37 (m, 2H), 1.35 (s, 3H)

EXAMPLE 3 3.0 g of methacrylic acid-3,5-dihydroxy-3-methylpentane and 5.5 ml of triethylamine were dissolved in 45 ml of methylene chloride, and the mixture was dissolved at 3-5 ° C.
Then, 1.3 ml of thionyl chloride was gradually added dropwise, and the mixture was further reacted at the same temperature for 1 hour. After completion of the reaction, the reaction solution was filtered and the filtrate was concentrated under reduced pressure. Ethyl acetate was added to the residue, the organic layer was washed with sodium hydrogen carbonate, and concentrated under reduced pressure to give 4-methacryloyloxyethyl-4.
-Methyl-1,3,2-dioxathian-2-oxide was obtained with a yield of 91.9%.

The physical properties are shown below. Mass: 248 (M ⁺ )

¹ H-NMR (CDCl ₃ ) δ: 6.09
(S, 1H), 5.54 (s, 1H), 4.30 (m,
2H), 4.00 to 3.80 (m, 2H), 1.92
(S, 3H) 2.00 to 1.80 (m, 2H), 1.4
2-1.37 (m, 2H), 1.35 (s, 3H)

Reference Example 1 96 parts of ethyl acrylate, 2 parts of methacrylic acid and 5-
Methacryloyloxymethyl-5-methyl-1,3,2
A mixture of 2 parts of dioxathiane-2-oxide, 2.4 parts of sodium dodecylbenzene sulfonate and 14 parts of soft water.
It was added to 9 parts and mixed, and 0.07 part of paramenthane hydroperoxide was added to obtain a monomer emulsion.

2.4 parts of sodium dodecylbenzene sulfonate and 149 parts of soft water were added to the reactor purged with nitrogen, and the temperature was lowered to 10 ° C. 10 of the above monomer emulsion
Weight% was added and stirred for 10 minutes. Then 0.04 parts of sodium formaldehyde sulfoxylate,
Ethylenediaminetetraacetic acid ・ Fe ・ Na ・ dihydrate 0.02
Parts, tetrasodium salt of ethylenediaminetetraacetic acid 0.01
2 parts of a 2% aqueous solution of 7 parts and parametric hydroperoxide of 0.07 part were added to initiate the polymerization reaction. A 0.3% aqueous solution of 0.32 part of sodium formaldehyde sulfoxylate and 0.02 part of ethylenediaminetetraacetic acid.Fe.Na.dihydrate was used during the polymerization reaction.
And 6 parts were gradually added to the reaction system over 6 hours.

After 30 minutes from the start of the above polymerization reaction, the remaining monomer emulsion was gradually added to the reaction system over 5 hours.
After the addition, the mixture was further reacted for 1 hour to obtain a polymer emulsion (solid content: 37.8% by weight). The polymer emulsion had a pH of 5.7 and a viscosity of 7.4 centipoise (measured with a BM type viscometer at 60 rotations and rotor No. 1).

A film having a thickness of 0.4 mm (hereinafter referred to as film 1) was obtained by drying the polymer emulsion at room temperature and forming a film. The tetrahydrofuran insoluble matter of the film 1 was 65.7% by weight. The film 1 was subjected to a tensile test, and the elongation and strength at break were measured. The results are shown in Table 1.

The tensile test was carried out using a Tensilon universal testing machine manufactured by Toyo Baldwin Co., Ltd. at room temperature and a chuck distance of 5
cm, pulling speed 30 cm / min, for a film punched with a No. 2 dumbbell.

Reference Example 2 0.2 part of hexamethylenediamine was added to 100 parts of the polymer emulsion of Reference Example 1 and stirred for 10 minutes. Then, it was dried at room temperature and formed into a film to obtain a film having a thickness of 0.4 mm (hereinafter referred to as film 2). The tetrahydrofuran insoluble matter of the film 2 was 82.9% by weight. The film 2 was subjected to a tensile test, and the elongation and strength at break were measured. The results are shown in Table 1.

[0035]

[Table 1]

Claims (1)

[Claims] 1. The following formula (1): (In the formula, R ¹ is a hydrogen atom or a lower alkyl group, R ² is a lower alkyl group, a and b are 1 or 2, and c is 0 or 1.).