JPH0782265A - Cyclosulfite derivative - Google Patents

Abstract

PURPOSE:To provide a new compound capable of easily crosslinking a polymer even at a low temperature without generating toxic substance such as formaldehyde. CONSTITUTION:A compound of the formula I (R<1> and R<2> are H or lower alkyl; R<3> is alkylene, phenylene, etc.; (a) to (d) are 0 or 1; (e) and (f) are 1 or 2), e.g. bis(5-methyl-1,3,2-dioxathian-2-oxid-5-yl)methyl adipate. This compound, e.g. the compound of the formula I wherein (c) and (d) are 0 and (e) and (f) are 1 can be produced by reacting an acid halide of the formula II (X is halogen) with cyclosulfites of the formula III and the formula IV in the presence of a base such as pyridine. The reaction is preferably carried out at -10 to +90 deg.C for 2-4hr by using 0.7-1.5mol of the compound of the formula II and 1.5-3.5mol of the base based on 1mol of the compound of the formula III and the formula IV.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to novel cyclosulfite derivatives.

[0002]

2. Description of the Related Art Crosslinked products obtained by crosslinking polymers are heat resistant,
Because it has excellent water resistance, solvent solubility resistance, oil resistance, etc.,
It can be widely used in fields such as paints, adhesives and fibers. As the cross-linking agent, for example, methylol urea, methylol phenol, etc. are known, but these usually cause problems in terms of operability and economical efficiency because the cross-linking reaction is difficult to proceed unless the temperature is higher than 130 ° C. there were. Furthermore, since formalin is generated under such a high temperature, there is a problem in terms of safety.

[0003]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made extensive studies under such circumstances, and as a result, the novel cyclosulfite derivative represented by the following formula (2) can be easily produced at a temperature of 100 ° C. or lower. It was found that the polymer can be crosslinked and does not generate a toxic substance such as formalin at that time, and the present invention has been completed based on this finding.

[0004]

Thus, according to the present invention,
A cyclosulfite derivative represented by formula (2) is provided.

[Chemical 2] (In the formula, R ¹ and R ² represent a hydrogen atom or a lower alkyl group. R ³ represents an alkylene group, a phenylene group or a xylylene group. A, b, c and d represent 0 or 1, and e and f represent 1
Or 2 is shown. R ¹ and R ² , a, b, c and d, e and f may be the same or different. )

The cyclosulfite 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 and R ² represent a hydrogen atom; a lower alkyl group such as a methyl group, an ethyl group and a propyl group. Of these, a hydrogen atom or a methyl group is preferable. R ³ is a methylene group, an ethylene group, a trimethylene group, a tetramethylene group,
An alkylene group such as a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group and a decamethylene group; a phenylene group; and a xylylene group. Among the alkylene groups, alkylene groups having 1 to 8 carbon atoms are preferable.

Specific examples of the cyclosulfite derivative include bis (5-methyl-1,3,2-adipate).
Dioxathian-2-oxide-5-yl) methyl, bis (1,3,2-dioxothiolane-2-oxide-4-yl) methyl adipate, bis (5-methyl-1,3,2-dioxathiane-terephthalate- 2-oxide-5
-Yl) methyl, bis (1,3,2-dioxothiolane-2-oxide-4-yl) methyl terephthalate, bis (5-methyl-1,3,2-dioxathiane-malonate-
2-Oxido-5-yl) methyl, bis (1,1) malonate
3,2-dioxothiolane-2-oxide-4-yl)
Methyl, N, N'-bis (5-methyl-1,3,2-dioxathian-2-oxide-5-ylmethoxycarbonyl) hexamethylenediamine, N, N'-bis (1,
3,2-dioxothiolane-2-oxide-4-ylmethoxycarbonyl) hexamethylenediamine, N, N '
-Bis (5-methyl-1,3,2-dioxathiane-2)
-Oxido-5-ylmethoxycarbonyl) p-xylylenediamine, N, N'-bis (1,3,2-dioxothiolane-2-oxide-4-ylmethoxycarbonyl) p-xylylenediamine, bis (terephthalate) 5-
Methyl-1,3,2-dioxathiane-2,2-dioxide-5-yl) methyl, bis (1,3, terephthalate)
2-dioxothiolane-2,2-dioxide-4-yl) methyl, bis (5-ethyl-1,3, terephthalate)
2-Dioxathian-2-oxide-5-yl) methyl, bis (5-ethyl-1,3,2-dioxothiolane-2,2-dioxide-4-yl) methyl terephthalate, bis (5-ethyl-isophthalate) 1,3,2-dioxathiane-2,2-dioxide-5-yl) methyl,
Bis (5-ethyl-1,3,2-dioxathian-2,2-dioxide-5-yl) methyl phthalate, (5-methyl-1,3,2-dioxathian-2,2-phthalate)
Dioxido-5-ylmethyl), phthalic acid (1,3,2
-Dioxothiolane-2,2-dioxide-4-ylmethyl) and the like.

The method for producing the cyclosulfite derivative of the present invention is not particularly limited. For example, in equation (2), c and d
In the case of a cyclosulfite derivative in which is 0 and e and f are 1, the acid halide represented by the formula (3) and the cyclosulfites represented by the formulas (4) and (5) are used as a base. It can be obtained by reacting in the presence of.

[0008]

[Chemical 3] (In the formula, R ³ is the same as described above. X is a halogen atom.)

[0009]

[Chemical 4] (In the formula, R ¹ and a are the same as described above.)

[0010]

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

Examples of X include halogen atoms such as chlorine atom, bromine atom, fluorine atom and iodine atom. Bases are tertiary aliphatic amines such as trimethylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, diisopropylamine; 2,6-lutidine, N,
N-dimethylaniline, N, N-diethylaniline, 4
A third such as dimethylaminopyridine, pyridine, etc.
Examples include primary aromatic amines.

The amount of the acid halide represented by the formula (3) is usually 0.5 to 2 mol, preferably 1 to 1 mol of the cyclosulfites represented by the formula (4) and the formula (5). 0.7 to 1.5 mol is used. The amount of the base used is the cyclosulfites 1 represented by the formulas (4) and (5).
It is usually 1.0 to 5 moles, preferably 1.5 to 5 moles.
3.5 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 amount of the diluent used is appropriately selected within a range such that the total amount of the acid halide and the cyclosulfite compound is 5 to 50% by weight.

The reaction temperature is -50 to + 100 ° C, preferably -10 to + 90 ° C, and the reaction time is 1 to 10 hours, preferably 2 to 4 hours.

Further, in the case of the cyclosulfite derivative in which c and d are 1 and e and f are 1 in the formula (2), the isocyanate represented by the formula (6), the formula (4) and the formula ( It can be obtained by reacting with cyclosulfites represented by 5) in the presence of a base.

[0016]

[Chemical 6] (In the formula, R ³ has the same meaning as described above.)

Examples of the base used include the same ones as described above. The amount of the isocyanate represented by the formula (6) is usually 0.5 to 2 mol, preferably 0.7, relative to 1 mol of the cyclosulfites represented by the formula (4) and the formula (5). ~ 1.5 moles are used. The amount of the base used is the cyclosulfites 1 represented by the formulas (4) and (5).
It is usually 0.01 to 5 mol, preferably 0.0, relative to mol.
5-2 mol is used. In the reaction, the same diluent as described above may be used, and the amount thereof used is appropriately selected within a range such that the total amount of the isocyanate and the cyclosulfites is 5 to 50% by weight. Reaction temperature is -50 to +
The reaction time is 100 ° C, preferably -10 to + 90 ° C, and the reaction time is 1 to 20 hours, preferably 2 to 18 hours.

Further, in the case of a cyclosulfite derivative in which e and f are 2 in the formula (2), it was obtained by the above method.
It can be obtained by reacting a cyclosulfite derivative of the formula (7) in which e and f are 1 with an oxidizing agent.

[0019]

[Chemical 7] (In the formula, R ¹ , R ² , R ³ , a, b, c and d are the same as described above.)

Examples of the oxidizing agent include potassium permanganate, sodium permanganate, ruthenium tetroxide,
Examples thereof include ruthenium dioxide-sodium periodate and ruthenium trichloride-sodium periodate. The amount of the oxidizing agent used is usually 1 to 5 mol, preferably 1 to 1 mol, relative to 1 mol of the cyclosulfite derivative represented by the formula (7).
4 moles are used. A diluent may be used in the reaction, for example, the same diluent and water as described above are used.
The reaction temperature is -50 to + 30 ° C, preferably -20 to +1.
At 0 ° C., the reaction time is 1 to 10 hours, preferably 2 to 4 hours.

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

The cyclosulfite derivative thus obtained can easily crosslink the polymer even at a temperature of 100 ° C. or lower, preferably 20 to 100 ° C. As the polymer, a polymer having an active hydrogen-containing functional group is used. The active hydrogen means a highly reactive hydrogen atom bonded to an oxygen atom, a nitrogen atom or a sulfur atom. The active hydrogen-containing functional group, for example, amino group, imino group, carboxyl group,
Examples thereof include a phenolic hydroxyl group, a sulfo group and a thiol group. Further, an anhydride group such as an acid anhydride group is also included in the active hydrogen-containing functional group. Among these, an amino group and an imino group are preferable. The content of the active hydrogen-containing functional group in the polymer is usually 0.01 meq or more per gram of the polymer.

The polymer having an active hydrogen-containing functional group is obtained by polymerizing a monomer having an active hydrogen-containing functional group, or a copolymer of the above monomer and another monomer copolymerizable with the monomer. It is a thing. Examples of the monomer having an active hydrogen-containing functional group include amides such as (meth) acrylamide; amines such as vinylethylamine and vinylbutylamine; (meth) acrylic acid, maleic acid, itaconic acid, fumaric acid and the like. Carboxylic acids; sulfonic acids such as styrene sulfonic acid. Other copolymerizable monomers include styrenes such as styrene and methylstyrene; carboxylic acid esters such as methyl (meth) acrylate and diethyl maleate; nitriles such as (meth) acrylonitrile; 1,3 -Conjugated dienes such as butadiene and isoprene.

The cyclosulfite derivative is usually used in the range of 0.01 to 20 mol of the cyclosulfite group with respect to 1 mol of the active hydrogen-containing functional group in the polymer. The cross-linking reaction is usually 100 ° C or lower, preferably 20 ° C.
It is carried out at a temperature of -100 ° C. Although the crosslinking proceeds even at a temperature of more than 100 ° C., the above range is preferable in terms of operability and economy. The reaction time cannot be unconditionally limited depending on the temperature, but is usually about 5 minutes to 50 hours.

[0025]

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 5-Hydroxymethyl-5-methyl-in a dry reactor
1,3,2-Dioxathiane-2-oxide 0.84 mmol, 1,2-dichloroethane 2 ml, 4-
Dimethylaminopyridine (0.04 mmol) and pyridine (0.98 mmol) were added, and the mixture was cooled to 0 ° C. Then, 1 ml of 1,2-dichloroethane containing 0.48 mmol of adipoyl chloride was added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 2 hours. After completion of the reaction, 12% hydrochloric acid was added to the reaction solution and the mixture was extracted with ethyl acetate. The organic layer was washed successively with water, saturated aqueous sodium hydrogen carbonate and saturated brine, and concentrated under reduced pressure to give bis (5) -adipate.
0.37 mmol (yield 88%) of -methyl-1,3,2-dioxathiane-2-oxide-5-yl) methyl (referred to as compound 1) was obtained. Table 1 shows the structural formula of Compound 1.
Table 2 shows the spectrum data.

Example 2 Except that 4-hydroxymethyl-1,3,2-dioxothiolane-2-oxide is used instead of 5-hydroxymethyl-5-methyl-1,3,2-dioxathian-2-oxide. The same reaction as in Example 1 was carried out to give bis (1,3,2-dioxothiolane-2-oxide-4-yl) methyl adipate (referred to as compound 2) in a yield of 71.
Earned in%. The structural formula of Compound 2 is shown in Table 1, and the spectral data thereof is shown in Table 2.

Example 3 The same reaction as in Example 1 was conducted except that terephthalic acid dichloride was used instead of adipoyl chloride, and bis (5-methyl-1,3,2-dioxathiane-2-oxide-5-terephthalate) was used. -Yl) methyl (referred to as compound 3) was obtained in a yield of 62%. The structural formula of Compound 3 is shown in Table 1.
Table 2 shows the spectrum data.

Example 4 The same reaction as in Example 2 was conducted except that terephthalic acid dichloride was used instead of adipoyl chloride, and bis (1,3,2-dioxothiolane-2-oxide-4-yl) terephthalate ( Compound 4) was obtained with a yield of 83%. The structural formula of compound 4 is shown in Table 1, and the spectral data thereof is shown in Table 3.

Example 5 The same reaction as in Example 1 was carried out except that malonic acid dichloride was used instead of adipoyl chloride, and bis (5-methyl-1,3,2-dioxathiane-2-oxide-5 malonate was used. -Yl) methyl (referred to as compound 5) was obtained in a yield of 62%. The structural formula of Compound 5 is shown in Table 1, and the spectral data thereof is shown in Table 3.

Example 6 A dry reactor was charged with 5-hydroxymethyl-5-methyl-
1,3,2-Dioxathian-2-oxide 2.14 mmol, benzene 2 ml, triethylamine 0.1 mmol and hexamethylene diisocyanate 1.14 mmol were added and the mixture was heated under reflux for 18 hours. After completion of the reaction, N, N'-bis (5-
0.46 mmol (yield 43%) of methyl-oxo-1,3,2-dioxathian-2-oxide-5-ylmethoxycarbonyl) hexamethylenedithymine (referred to as compound 6) was obtained. The structural formula of Compound 6 is shown in Table 2, and the spectral data thereof is shown in Table 3.

Example 7 5-hydroxymethyl-5-methyl-1,3,2-dioxathiane-2-oxide is replaced by 4-hydroxymethyl-1,3,2-dioxothiolane-2-oxide. The same reaction as in Example 6 was performed to obtain N,
N'-bis (1,3,2-dioxothiolane-2-oxide-4-ylmethoxycarbonyl) hexamethylenediamine (referred to as compound 7) was obtained in a yield of 79%. The structural formula of compound 7 is shown in Table 2, and the spectrum data is shown in Table 4.

Example 8 The same reaction as in Example 6 was conducted except that p-xylylene diisocyanate was used instead of hexamethylene diisocyanate, and N, N'-bis (5-methyl-1,
3,2-Dioxathian-2-oxide-5-ylmethoxycarbonyl) xylylenediamine (referred to as compound 8) was obtained with a yield of 92%. The structural formula of compound 8 is shown in Table 2.
Table 4 shows the spectrum data.

Example 9 N, N'-bis (1,3,2-dioxothiolane-2-oxide) was prepared by the same reaction as in Example 7 except that p-xylylene diisocyanate was used instead of hexamethylene diisocyanate. Yield of 4--4-ylmethoxycarbonyl) xylylenediamine (referred to as compound 9) was 9
Obtained at 2%. The structural formula of compound 9 is shown in Table 2, and the spectrum data is shown in Table 5.

Example 10 Bis (5-methyl-1, terephthalate,
0.16 mmol of 3,2-dioxathiane-2-oxide-5-yl) methyl, 2 ml of a mixed solvent of acetonitrile and carbon tetrachloride (1: 1) were added, and the mixture was cooled to 0 ° C. 1.5 ml of an aqueous solution containing 0.54 mmol of sodium periodate was added thereto, 0.005 mmol of ruthenium dioxide was further added, and the mixture was stirred for 20 minutes. After completion of the reaction, water was added to the reaction solution and extracted with ethyl acetate. The organic layer was washed successively with saturated brine and then concentrated under reduced pressure,
The resulting oily substance was purified by silica gel chromatography (developing solvent: a mixed solvent of n-hexane and ethyl acetate 1: 2), and bis (5-methyl-1,3,2,2-terephthalate).
-Dioxathian-2,2-dioxide-5-yl) methyl (referred to as compound 10) was obtained in a yield of 15%. The structural formula of Compound 10 is shown in Table 2, and the spectral data thereof is shown in Table 5.

Example 11 Bis (1,3,2-dioxothiolane-2 terephthalate was used instead of bis (5-methyl-1,3,2-dioxathian-2-dioxide-5-yl) methyl terephthalate.
A reaction similar to that in Example 10 was conducted except that -oxido-4-yl) methyl was used, and terephthalic acid (1,3,2) was used.
-Dioxothiolane-2,2-dioxide-4-yl)
Methyl (referred to as compound 11) was obtained with a yield of 53%. The structural formula of Compound 11 is shown in Table 2, and the spectrum data is shown in Table 5.

[0036]

[Table 1]

[0037]

[Table 2]

[0038]

[Table 3]

[0039]

[Table 4]

[0040]

[Table 5]

Reference Example 1 280 parts of isopropyl alcohol and 124.6 parts of n-butoxyethanol were charged into a reactor equipped with a thermometer, a stirrer, a reflux condenser, a supply pipe and a nitrogen introduction pipe, and then nitrogen was introduced. And heated to 80 ° C. Next, methacrylic acid 8
A mixture of 0.5 parts, 136.5 parts of methyl methacrylate, 70 parts of styrene and 9 parts of azobisisobutyronitrile was added to the reactor over 2 hours. After the addition was completed, the mixture was further reacted at 80 ° C for 6 hours and cooled to 20 ° C. Next, after adding 33 parts of triethylamine and stirring for 30 minutes and mixing uniformly, ethyleneimine 37% aqueous solution 61.6
Parts were added, heated to 80 ° C. and reacted for 4 hours. Then, 8.4 parts of triethylamine and deionized or 75 parts were added and cooled to 20 ° C. to obtain a polymer solution having a nonvolatile content of 40%.

Compound 46 was added to 46 parts of the above-mentioned polymer solution.
5 parts were added and mixed with stirring to obtain a polymer composition. The polymer composition was cast on a glass plate with a frame and left standing at 20 ° C. for 48 hours to obtain a film (referred to as film 1). No generation of formalin was observed when obtaining the film. The film 1 was placed in a 100-mesh wire net and immersed in tetrahydrofuran at 20 ° C. for 24 hours, then the constant amount of the solid content remaining in the wire net was determined, and the weight percentage relative to the constant weight of the film initially placed in the wire net was determined. %Met.
A film 1 having a thickness of 0.4 mm was punched with a standard No. 2 dumbbell punching blade to obtain a test piece, and a chuck-to-chuck distance of 5 cm was obtained using a constant-speed tension type tensile tester for this test piece.
When measured under the conditions of a tensile speed of 300 mm / min, the tensile strength at break was 45 (Kgf / cm ² ) and the elongation at break was 270%.

Claims (1)

[Claims] 1. A cyclosulfite derivative represented by the formula (1). [Chemical 1] (In the formula, R ¹ and R ² represent a hydrogen atom or a lower alkyl group. R ³ represents an alkylene group, a phenylene group or a xylylene group. A, b, c and d represent 0 or 1, and e and f represent 1
Or 2 is shown. R ¹ and R ² , a, b, c and d, e and f may be the same or different. )