JPH01207287A - Production of chlorothidphene dioxamine and production of polymer using said compound - Google Patents

Abstract

PURPOSE:To industrially and advantageously obtain the title compound having controlling action on microorganisms and aquatic organisms, by reacting 3,3,4,4- tetrachlorotetrahydrothiophene-1,1-dioxide with a secondary or tertiary amine. CONSTITUTION:3,3,4,4,-Tetrachlorotetrahydrothiophene-1-1-dioxide expressed by the formula is reacted with a secondary or tertiary amine (example; diethylamiune) to afford the aimed compound. By using the secondary or tertiary amine having C-C double bond (example; N,N-dimethyl-aminoethylelmethecrylate) as the secondary or tertiary amine, there is obtained an unsaturated chlorothiophenedioxiamine, which can be polymerized to afford a polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing chlorothiophene dioxyamine, and more specifically, 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide. and a saturated or unsaturated secondary amine or tertiary amine. The present invention relates to a method for producing a polymer by polymerization.

3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide, which is represented by the following formula, is disclosed in U.S. Patent No. 2.
It is a known compound as described in US Pat. No. 957,887. This compound has, for example, biological activity as described below, but on the other hand, it is extremely unstable to alkali and easily decomposes, so it is not easy to handle.

As a result of intensive research aimed at stabilizing 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide, the present inventors found that: This compound easily reacts with secondary or tertiary amines to give stable lorothiophene dioxyamines, and also reacts with secondary or tertiary amines having a carbon-carbon double bond in the molecule. It was discovered that chlorothiophenedioxyamine having a polymerizable double bond in the molecule could be obtained by the reaction, and further, in this way, 3,3,4,4-tetrachlorotetrahydrothiophene-1 , discovered that a polymer obtained by reacting 1-dioxide with a secondary or tertiary amine having a carbon-carbon double bond in the molecule has film-forming properties, and also discovered that these chlorothiophene dioxyamines and their The polymer has a highly bioactive effect, and is effective against microorganisms such as bacteria, molds, and yeasts, as well as aquatic organisms such as freshwater and seawater algae, Fujitbo, sea squirts, Serpura, mussels, Japanese snails, and snails. The present invention was made based on the discovery that this method has an effect.

A method for producing chlorothiophene dioxyamine according to the present invention includes adding a secondary amine or a tertiary amine to 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide. It is characterized by reacting with an amine.

Examples of the saturated secondary amine or tertiary amine that can be used in the production of the chlorothiophene dioxyamine according to the present invention include diethylamine, diisopropylamine, di-N-butylamine, triethylamine, jetanolamine, triethanolamine, Examples include morpholine and the like.

According to the present invention, by using an unsaturated amine having a carbon-carbon double bond in the molecule as a secondary amine or a tertiary amine, an unsaturated chlorothiophene dioxyamine having a carbon-carbon double bond in the molecule can be obtained.

Such secondary amines or tertiary amines having a carbon-carbon double bond in the molecule include, for example, N-methylallylamine, N,N-dimethylallylamine, N-t-butylaminoethyl acrylate, N-t-butyl Aminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, N,N-dimethylamine ethyl methacrylate, N,N-dimethylaminoethyl acrylamide, N,
N-dimethylaminopropylacrylamide, N,N-
Dimethylaminopropylmethacrylamide, 2-(1
-aziridinyl)ethyl methacrylate, 2-(1-aziridinyl)ethyl acrylate, poly(N, N-
dimethylaminoethyl methacrylate), poly(N-
t-butylaminoethyl acrylate), poly(N,
N-dimethylaminoethyl acrylamide), vinylpyridine, and the like.

According to the method of the invention, -m formula % formula %) (wherein A represents a saturated or unsaturated amine residue, R1
represents a hydrocarbon group or a cyclic hydrocarbon group formed together with A. ) When using a secondary amine represented by A mixture of can be obtained. That is, the obtained reaction products are trichlorotetrahydrothiophenedioxyamine (IIla), dichlorotrihydrothiophenedioxyamine (■b) and monochlorodihydrothiophenedioxyamine (II[c), as shown in the following formula. A mixture of chlorothiophene dioxyamines represented by:

0□ (IIIa) I 0□ (I[[b) (II[c) (wherein, A represents an amine residue, R2 each independently represents a hydrocarbon group, or two R2s form together When using a tertiary amine represented by (representing a cyclic hydrocarbon group), a mixture of quaternized amines can be obtained by the same dehydrochlorination as described above. That is, the obtained reaction products are quaternized trichlorotetrahydrothiophenedioxyammonium (IVa), dichlorotrihydrothiophenedioxyammonium (TVb), and monochlorodihydrothiophenedioxyammonium (
IVc).

(IVb) (IVc) In the method of the present invention, the reaction of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and the above-mentioned secondary amine or tertiary amine is performed to The reaction may be carried out in molar amounts, or one of them may be used in excess. However, since the reaction is exothermic, it is usually carried out in an organic solvent to facilitate cooling of the reaction mixture.

In particular, in order to suppress undesirable side reactions, lower aliphatic alcohols such as methanol and ethanol, nitriles such as acetonitrile, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic alcohols such as acetone and methyl ethyl ketone, etc. Ketones, lower aliphatic carboxylic acid alkyl esters such as methyl acetate and ethyl acetate, acid amides such as dimethylformamide and dimethylacetamide, cyclic ethers such as dioxane and tetrahydrofuran, ethylene glycol motsubutyl ether, diethylene glycol dimethyl ether, etc. Mono- or diethers of poly)alkylene glycol are preferably used. The reaction is usually carried out at a temperature ranging from room temperature to the reflux temperature of the solvent used.

When using an unsaturated amine as the secondary amine or tertiary amine, 3, 3, 4, 4. In order to prevent these amines from polymerizing in the reaction with -tetrachlorotetrahydrothiophene-1,1-dioxide, it is preferable to carry out the reaction in the presence of an appropriate amount of a polymerization inhibitor. Examples of the polymerization inhibitor used include hydroquinone monomethyl ether, hydroquinone, catechol,
Examples include t-butylcatechol. These polymerization inhibitors are usually 10 to 1
Used in the range of 0000 ppn+.

According to the present invention, by the reaction of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide with an unsaturated secondary or tertiary amine having a carbon-carbon double bond in the molecule. The obtained chlorothiophene dioxyamine having a carbon-carbon double bond in its molecule has radical, anionic or cationic polymerizability due to the carbon-carbon double bond, and can be polymerized by its own homopolymerization or by other appropriate polymerization. A (co)polymer is obtained by copolymerization with a polymerizable monomer.

Further, as the polymerization method, block polymerization, solution polymerization, emulsion polymerization in water, suspension polymerization, etc. are appropriately employed.

However, in view of ease and economy of polymerization, solution or emulsion radical polymerization is preferably employed in many cases.

In radical polymerization, common radical polymerization initiators such as azo compounds, peroxides, persulfates, etc. are used. Specifically, for example, azobisisobutyronitrile, benzoyl peroxide, potassium persulfate, etc. are generally used.

When employing solution radical polymerization, the solvent usually includes, for example, lower aliphatic alcohols such as methanol, ethanol, and isopropanol, lower aliphatic carboxylic acid esters such as ethyl acetate, ethylene glycol monobutyl ether, and diethylene glycol. Mono- or diethers of (poly)alkylene glycol such as dimethyl ether, cyclic ethers such as dioxane and tetrahydrofuran, lower aliphatic carboxylic acid amides such as dimethylformamide and dimethylacetamide, aromatic hydrocarbons such as benzene, toluene and xylene. is used. especially,
Methanol, ethanol, dimethylformamide, and ethylene glycol monobutyl ether are preferably used.

In radical polymerization, the reaction temperature is preferably higher than the decomposition temperature of the polymerization initiator used, and is usually in the range from room temperature to about 150°C, although it depends on the polymerization initiator used. In order to lower the decomposition temperature of the polymerization initiator, a reducing agent may be used together with the polymerization initiator, such as sodium metahydrosulfide, sodium formaldehyde hydrosulfite, ascorbic acid, diethylaniline, etc. is used.

Next, emulsion (co)polymerization of the chlorothiophene dioxyamine mixture having a double bond in the molecule is usually carried out in water using an emulsifier.

As the emulsifier, any of anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants can be used.

Various monomers can be used as the monomer copolymerizable with the unsaturated chlorothiophene dioxyamine according to the present invention. Examples of such monomers include α-olefins such as ethylene and propylene, conjugated dienes such as butadiene and isoprene, and α-olefins such as acrylic acid and methacrylic acid.
, β-unsaturated carboxylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate,
α of butyl methacrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminopropyl acrylate, N-t-butylaminoethyl methacrylate, glycidylethyl methacrylate, etc.
, β-unsaturated carboxylic acid ester, acrylonitrile,
Unsaturated nitriles such as methacrylonitrile, aromatic vinyl compounds such as styrene, vinyl esters such as vinyl acetate and vinyl chloroacetate, halogenated vinyl compounds such as vinyl chloride, vinyl ethers such as ethyl vinyl ether and 2-chloroethyl vinyl ether, etc. N-vinylpyrrolidone, itaconic acid, maleic acid, crotonic acid, acrylamide, methacrylamide, orylamine and the like can be mentioned.

As described above, by copolymerizing the chlorothiophene dioxyamine obtained by the present invention with other polymerizable monomers, it can be imparted with water resistance and a crosslinked structure, or made water-soluble, compared to a single polymer. Also, flexible or hard coatings can be formed.

3) 3.3.4.4-Tetrachlorotetrahydrothiophene-1,1-dioxide is, as mentioned above,
It is known that it is extremely unstable to alkali and easily decomposed, but according to the method of the present invention, as explained above, it can be reacted with a secondary or tertiary amine. By this, a stable rolothiophene dioxyamine can be obtained.

In particular, according to the method of the present invention, 3,3.4.4-tetrachlorotetrahydrothiophene-1,1-dioxide is treated with an unsaturated secondary or tertiary amine having a carbon-carbon double bond in the molecule. By reacting, a polymerizable chlorothiophene dioxyamine having a polymerizable double bond in the molecule can be obtained.

This polymerizable amine is formed into a homopolymer or a copolymer by radical polymerization or ionic polymerization, and the copolymer has film-forming properties by selecting the copolymerization monomer component.

Furthermore, the chlorothiophene dioxyamine or its (co)polymer obtained by the method of the present invention has a high biological activity, and is effective against microorganisms such as bacteria, molds, and yeasts, freshwater and seawater algae, and Fujibo. It has a controlling effect on aquatic organisms such as sea squirts, sea squirts, mussels, Japanese mussels, and snails. Therefore, the chlorothiophene dioxyamine mixture or its polymer obtained by the method of the present invention can be used as these pesticidal compositions.

The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples in any way.

Example 1 80 g of acetonitrile was charged into a 500 ml reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, and 3.
3.4.4-Tetrachlorotetrahydrothiophene-1
, 1 to 51.6 g (0.2 mol) of dioxide was dissolved and the temperature was adjusted to 20°C.

N,N-dimethylaminoethyl methacrylate 3)゜4
A solution prepared by dissolving 10 g (0.2 mol) of acetonitrile in 10 g of acetonitrile was added dropwise to the above solution over a period of about 20 minutes. The reaction mixture was heated to approximately 50°C. Next, after heating to reflux temperature (approximately 81°C) on an oil bath,
It was held at this temperature for an hour.

After completion of the reaction, the solvent was removed from the reaction mixture under reduced pressure using a rotary evaporator at a temperature below 45°C to obtain 81 g of a pale yellow, slightly moist waxy substance (melting point 55-60
°C) was obtained as a crude product.

This product was dissolved in 30 g of methanol, and about 400 m
After washing with hexane (1), it was allowed to stand, and the lower layer was collected using a liquid separator. This hexane washing operation was repeated five more times to purify the reaction product. Thereafter, the solvent was further removed using a rotary evaporator at 35° C. under reduced pressure of 150 μg to obtain reaction product A.

The proton nuclear magnetic resonance spectrum of this reaction product A is shown in FIG. This spectrum contains 4.23 ppm and 4
．． A signal is observed at 37 ppm. These represent hydrogen in the tetrahydrothiophene skeleton, and N shown in the following formula,
N'-dimethyl-N-methacrylooxyethyl-N-
Indicates the presence of trichlorotetrahydroxythiophenedioxime ammonium chloride (Va).

Furthermore, a signal is observed between 6.67 and 7.33 ppm. These are assigned to the hydrogens of the trihydrothiophene and dihydrothiophene skeletons, and include N,N'-dimethyl-N-methacrylooxyethyl-N-dichlorotrihydroxythiophenedioxime ammonium chloride (Vb) and N,N''-dimethyl -N-Methacryloxyethyl-N-chlorothiophenedioxime indicates the presence of ammonium chloride (Vc).On the other hand, 5.50~
A signal assigned to hydrogen on vinyl carbon (=Cl) is observed at 6.30 ppm.

(Va) (vb) (Vc) Example 2 193 g of isopropanol was placed in the same reaction vessel as in Example 1.
, 20 g of the reaction product A obtained in Example 1 and 180 g of butyl methacrylate were charged, and 0.7 g of azobisisobutyronitrile was added thereto, heated to about 65°C on an oil bath, and at this temperature. The reaction was allowed to proceed for 6 hours. Next, 0.7 g of azobisisobutyronitrile was added, and the mixture was reacted at a temperature of 60 to 70°C for 6 hours. After that, 0.7 g of azobisisobutyronitrile was further added and the operation of reacting for 6 hours was repeated twice.

As a result, a pale yellow and transparent copolymer solution was obtained.

This solution had a non-volatile content (measured after removing the solvent at 105°C for 3 hours. The measurement method is the same below): 49.8%,
Viscosity (B-type rotational viscosity needle, 25°C, same hereinafter) 720
The residual monomer butyl methacrylate (as determined by gas chromatography) was 720 ppm. Moreover, the weight average molecular weight of the polymer was 18,300.

The above copolymer solution was applied to a glass plate and dried to a film thickness of about 100A! A transparent coating film of m was obtained. This coating showed anti-blocking properties at room temperature and did not dissolve in water even after being immersed in water for 24 hours.

Example 3 200 g of ethanol and 300 g of the compound A obtained in Example 1 were charged into a reaction vessel similar to that in Example 1, and abbisisobutyronitrile 1). While adding 7g over 9 times,
Polymerization was carried out at a temperature of about 70° C. for 62 hours to obtain a dark brown transparent polymer solution. This solution had a nonvolatile content of 60.3% and a viscosity of 1000 centivoise.

An increase in the viscosity of the solution was observed during the reaction, indicating that a homopolymer of the reaction product A could be obtained.

As is clear from the comparison with the spectrum shown in Figure 1,
Signals were observed at 4.27 ppm and 4.40 ppm, indicating hydrogen in the tetrahydroxythiophene skeleton, and at 6.87 ppm and 7°30 ppm.
The signal indicates trihydroxythiophene and hydrogen in the thiophene skeleton. On the other hand, unsaturated carbon (=C1(2)
The signal at 5.50 to 6.30 ppm assigned to hydrogen above has disappeared, indicating the formation of a polymer by copolymerization of monomers.

Example 4 In a reaction vessel similar to Example 1, methanol 275
In g, 100 g of the reaction product A obtained in Example 1, 62.5 g of n-butyl acrylate, and 62 g of methyl methacrylate.
．． 5 g of azobisisobutyronitrile (10.5 g (1
, 5g added 7 times every 10 hours) at reflux temperature (
Polymerization was carried out at a temperature of about 63° C. for 70 hours. The resulting reaction solution was pale yellow and transparent, and the nonvolatile content was 44.3%.

After applying this solution to a glass plate, the solvent was removed by heating, and the resulting coating film was subjected to measurement of proton nuclear magnetic resonance spectra. The spectrum is shown in FIG.

As is clear from the comparison with the spectrum shown in Figure 1,
Signals were observed at 4.27 ppm and 4.40 ppm, indicating hydrogen in the tetrahydroxythiophene skeleton, and at 6.87 ppm and 7°30 ppm.
The m signal indicates trihydroxythiophene and hydrogen in the thiophene skeleton. On the other hand, unsaturated carbon (= CH2
), the signal at 5,50-6°30 ppm assigned to hydrogen has disappeared, indicating the formation of a polymer by copolymerization of monomers.

Example 5 In a 1 volume reaction vessel equipped with a thermometer, stirrer and reflux condenser, 557 g of deionized water, surfactant "Triton
105J (manufactured by Rohm & Haas, nonionic surfactant consisting of octylphenol-ethylene oxide adduct) 16 g, compound A70 obtained in Example 1
g, 140 g of ethyl acrylate, and [perbutyl H-
70J (t-butyl hydroperoxide, active content 7
0%, manufactured by Nihon Yushi@) was charged, and the temperature was raised to 50°C. After this, while maintaining the temperature at 50-60℃,
5.6 g of Superlite CJ (sodium formaldehyde hydrosulfite, manufactured by Mitsubishi Chemical Industries) was added in four portions every 1.5 hours, and emulsion-polymerization was performed to obtain a milky white polymer emulsion. This emulsion has a nonvolatile content of 25.3%, a viscosity of 7.5 centipoise, a pH of 1.0, and a residual monomer of ethyl acrylate of 500%.
It was ppm.

Example 6 80 g of acetonitrile was charged into a 500 ml reaction vessel equipped with a thermometer, a stirrer and a reflux condenser, and 3.
3,4.4-Tetrachlorotetrahydrothiophene-1
, 51.6 g (0.2 mol) of 1-dioxide? The container was placed and the temperature was adjusted to 20°C.

N-t-butylaminoethyl methacrylate 37g (0
, 2 moles) to 10 g of acetonitrile? The solution in the container was added dropwise to the above solution over a period of about 20 minutes. The reaction mixture was heated to approximately 50°C. Next, the mixture was heated to reflux temperature (approximately 81°C) on an oil bath, and then maintained at this temperature for an additional 2 hours.

After the reaction was completed, the solvent was removed from the reaction mixture using a rotary evaporator at a temperature of 45° C. or lower to obtain 89 g of a pale yellow, transparent, and viscous liquid as a crude reaction product at room temperature.

This product was dissolved in 30 g of methanol, purified by washing with hexane in the same manner as in Example 1, and the solvent was removed using a rotary evaporator at 35°C under reduced pressure of 15 mmHg to obtain reaction product B. Ta.

The proton nuclear magnetic resonance spectrum of this reaction product B is shown in FIG. This spectrum contains 4.20 ppI1)
and a signal is observed at 4.33 ppm.

These signals are attributed to hydrogen in the tetrahydrothiophene skeleton and indicate the presence of N-t-butyl-N-methacrylooxyethyl-N-trichlorotetrahydrothiophene dioxyamine (Vla).

Furthermore, a signal is observed between 6.67 and 7.33 ppm. These are assigned to hydrogen of trihydrothiophene and dihydrothiophene skeleton, and Nt-butyl-N
-Methacryloxyethyl-N-dichlorodihydroxythiophenedioxyamine (■b) and N-t-butyl-N-methacrylooxyethyl-N-chlorodihydrothiophenedioxyamine (■C) are shown. On the other hand,
A signal attributed to hydrogen on vinyl carbon (=Cth) is observed at 5.3 to 6.3 ppm.

(Vla) z (Vlc) Example 7 67 g of methanol and 8100 g of the reaction product obtained in Example 5 were placed in the same reaction vessel as in Example 1, and 1.6 g of azobisisobutyronitrile was added four times. ,
Polymerization was carried out at a temperature of about 70° C. for 24 hours to obtain a dark yellow transparent polymer solution. This solution had a nonvolatile content of 60.1% and a viscosity of 4700 centiboise.

Example 8 In a reaction vessel similar to Example 1, 250 g of methanol, 8125 g of the reaction product obtained in Example 6, 62.5 g of n-butyl acrylate, and 62.5 g of methyl methacrylate were charged, and azobisisobutyro Nitrile 7.5g (1.5g
was added 5 times every 8 hours), and the reaction was carried out in the same manner as in Example 4 for 40 hours. The reaction solution thus obtained was pale yellow and transparent, and had a nonvolatile content of 49.6%.

The proton nuclear magnetic resonance spectrum of this copolymer is shown in FIG. As is clear from the comparison with the spectrum shown in Figure 3, signals were observed at 4.28 ppm and 4.40 ppI, and these signals indicate hydrogen in the tetrahydrothiophene skeleton at 6.88 ppm and 7.28 ppm.
The digal in pm indicates trihydroxythiophene and the hydrogen of the thiophene skeleton, while the unsaturated carbon (-CH2
), the signal at 5.30 to 6.3 ppm attributed to hydrogen had disappeared, and an increase in the viscosity of the solution was observed during the above reaction, so It is shown that the union was successfully obtained.

Example 9 In a reaction vessel similar to Example 1, 158 g of ethanol, 870 g of the compound obtained in Example 5, and 72 g of butyl methacrylate were added.
3.2 g of azobisisobutyronitrile was added four times at a temperature of 60 to 70° C., and the mixture was reacted for 24 hours to obtain a yellow transparent copolymer solution. This solution had a nonvolatile content of 47.5% and a viscosity of 1200 centivoise.

Example 10 80 g of acetonitrile was charged into a 500 ml reaction vessel equipped with a thermometer, a stirrer and a reflux condenser, and 3.
3,4.4-Tetrachlorotetrahydrothiophene-1
, 1-dioxide (51.6 g (0.2 mol)) was dissolved, and the temperature was adjusted to 20°C.

N,N-dimethylaminopropylacrylamide 30.
A solution of 5 g (0.2 mol) dissolved in 10 g of acetonitrile was added dropwise to the above solution over a period of about 20 minutes. The reaction mixture was heated to approximately 50°C. Then,
After heating to reflux temperature (approximately 81°C) on an oil bath, further
It was held at this temperature for 2 hours.

After the reaction was completed, the solvent was removed from the reaction mixture using a rotary evaporator at a temperature of 45° C. or lower to obtain 78 g of a dark yellow, transparent, and viscous liquid as reaction product C.

From the measurement of its proton nuclear magnetic resonance spectrum, this reaction product was found to be N,N-dimethyl-N-acrylamidopropyl-N-trichlorotetrahydrothiophenedioxyammonium chloride, NlN-dimethyl-N-acrylamidopropyl-N-dichlorotrichloride, It was confirmed that it was a mixture of hydrothiophenedioxyammonium chloride and N,N-dimethyl-N-acrylamidopropyl-N-monochlorodihydrothiophenedioxyammonium chloride.

Example 1) In a reaction vessel similar to Example 1, 25 g of methanol, 27 g of isopropanol, and the reaction product CI 4 obtained in Example 8 were added.
．． 5 g of azobisisobutyronitrile and 33.5 g of butyl methacrylate were added at a temperature of 60 to 70°C.
．． Add 0g over 4 times, react for 24 hours,
A pale yellow and transparent copolymer solution was obtained. This solution had a nonvolatile content of 47.5% and a viscosity of 500 centivoise.

Example 12 80 g of acetonitrile was charged into a 500 ml reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, and 3.
3,4.4-Tetrachlorotetrahydrothiophene-1
, 1-dioxide (51.6 g (0.2 mol)) was dissolved, and the temperature was adjusted to 20°C.

N,N-dimethylaminoethyl acrylate 28.6g
(0.2 mol) dissolved in 10 g of acetonitrile was added dropwise to the above solution over a period of about 20 minutes. The reaction mixture was heated to approximately 50°C. Next, the mixture was heated to reflux temperature (approximately 81°C) on an oil bath, and then maintained at this temperature for an additional 2 hours.

After the reaction was completed, the solvent was removed from the reaction mixture using a rotary evaporator at a temperature of 45° C. or lower to obtain 78 g of a deep yellow viscous liquid as a reaction product.

From the measurement of its proton nuclear magnetic resonance spectrum, this reaction product was found to be N,N-dimethyl-N-acrylooxyethyl-N-trichlorotetrahydrothiophenedioxyammonium chloride, N,N-dimethyl-N-acrylooxy It was confirmed that it was a mixture of ethyl-N-dichlorotrihydrothiophene dioxyammonium chloride and N,N-dimethyl-N-acrylooxyethyl-N-monochlorodihydrothiophene ammonium chloride.

Example 13 50 g of methanol, 014 g of the reaction product obtained in Example 10, and 36 g of butyl methacrylate were placed in the same reaction vessel as in Example 1, and 1.2 g of azobisisobutyronitrile was added at a temperature of 60 to 70°C. The mixture was added four times and reacted for 24 hours to obtain a pale yellow and transparent copolymer solution. This solution had a nonvolatile content of 49.8% and a viscosity of 225 centipoise.

The above copolymer solution was applied onto a glass plate using a bar coater and dried to obtain a film having a thickness of about 100 μm. The specific resistance value of this film surface was measured at a humidity of 70% and a temperature of 25°C.
When measured, it was 3×10 6 Ω·(2).

On the other hand, the specific resistance value of the film surface of a homopolymer of butyl methacrylate prepared in the same manner is 7×10"Ω・salt, and the specific resistance value of the film surface of the polymer obtained in Example 7 is 3×1010Ω・■ Therefore, the polymer obtained by polymerizing the reaction product in this example showed about 1000 times more conductivity than the polymer obtained in Example 5, and the cationic polymer of quaternized amine It had the characteristics of

Example 14 500Ill equipped with thermometer, stirrer and reflux condenser
80 g of acetonitrile was charged into a capacity reaction vessel, and 51.6 g (0.2 mol) of 3.3,4.4-tetrachlorotetrahydrothiophene-1,1-dioxide was dissolved therein, and the temperature was adjusted to 20°C. .

N,N-diethylamine ethyl methacrylate 37゜1
(0.2 mol) dissolved in 10 g of acetonitrile was added dropwise to the above solution over a period of about 20 minutes. The reaction mixture was heated to approximately 50°C. Next, after heating to reflux temperature (approximately 81°C) on an oil bath,
It was held at this temperature for an hour.

After the reaction was completed, the solvent was removed from the reaction mixture using a rotary evaporator at a temperature of 45° C. or lower to obtain 82 g of a dark brown, transparent, and viscous liquid as reaction product E.

This reaction product was determined to be N,N-dimethyl-N-methacrylooxyethyl-N-trichlorotetrahydrothiophenedioxyammonium chloride, N, from the measurement of its proton nuclear magnetic resonance spectrum.

It may be a mixture of N-dimethyl-N-methacrylooxyethyl-N-dichlorotrihydrothiophenedioxyammonium chloride and N,N-dimethyl-N-methacrylooxyethyl-N-monochlorodihydrothiophenedioxyammonium chloride. confirmed.

Example 15 In a reaction vessel similar to Example 1, 100 g of methanol, 5 g of the reaction product El obtained in Example 12, 40 g of butyl acrylate, 40 g of methyl methacrylate, and 5 g of methacrylic acid were added.
1.6 g of azobisisobutyronitrile was added four times at a temperature of 60 to 70°C, and the mixture was reacted for 24 hours to obtain a pale yellow transparent copolymer solution. This solution had a nonvolatile content of 45.8% and a viscosity of 900 centivoise.

Example 16 150 g of methanol was charged into a 500 ml reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, and 3.3 g of methanol was added to it.
,4.4-tetrachlorotetrahydrothiophene-1,
51.6 g (0.2 mol) of 1-dioxide? The temperature was adjusted to 20°C.

17.4 g (0.2 mol) of morpholine in methanol Lo
About 10 g of the solution was added dropwise from the funnel to the above solution.
It took several minutes to drip. The reaction mixture was heated to approximately 36°C. Next, the mixture was heated to reflux temperature (approximately 64° C.) on an oil bath, and then kept at this temperature for an additional 2 hours.

After the reaction was completed, about 0.5 g of black floating matter was filtered off, and the solvent was removed in a rotary evaporator under reduced pressure at a temperature of 45° C. to obtain 67 g of a tan waxy solid as a crude product.

Dissolve 20 g of this product in 20 g of methanol, -1
After recrystallizing at 0° C., the reaction product F was obtained by washing with 10 g of hexane to remove unreacted morpholine.

From the measurement of its proton nuclear magnetic resonance spectrum, this reaction product was found to be 3-(N-morpholino)-3,4,4-)
Dichlorotetrahydrothiophene-1,1-dioxide chloride, 3-(N-morpholino)-3,4-dichlorotrihydrothiophene-1,1-dioxide chloride, and 3-(N-morpholino)-4-chloro It was confirmed that it was a mixture of dihydrothiophene-1,1-dioxide chloride.

Reference Example In Example 13, polymerization was carried out without using the reaction product and with the other conditions being the same, and as a result, a cloudy homopolymer of butyl methacrylate was obtained. This indicates that the butyl methacrylate homopolymer is methanol insoluble.

On the other hand, the polymers obtained in Examples 7.1) and 13 were both methanol soluble, indicating that the polymers obtained in these Examples were copolymers.

[Brief explanation of the drawing]

FIG. 1 shows the proton nuclear magnetic resonance spectrum of the reaction product A obtained in Example 1, FIG. 2 shows the proton nuclear magnetic resonance spectrum of the copolymer of this reaction product A, and FIG.
The figure shows the proton nuclear magnetic resonance spectrum of the reaction product B obtained in Example 6, and Figure 4 shows the reaction product B.
This shows the proton nuclear magnetic resonance spectrum of the copolymer. Patent applicant: Takeda Pharmaceutical Co., Ltd. Patent attorney: Itsube Makino

Claims (3)

[Claims] (1) A method for producing chlorothiophene dioxyamine, which comprises reacting 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide with a secondary amine or a tertiary amine. (2) Carbon-carbon double bond characterized by reacting 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide with a secondary amine or tertiary amine having a carbon-carbon double bond. A method for producing an unsaturated chlorothiophene dioxyamine having a heavy bond. (3) Carbon-carbon double bond obtained by reacting 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide with a secondary amine or tertiary amine having a carbon-carbon double bond 1. A method for producing a polymer, which comprises polymerizing an unsaturated chlorothiophene dioxyamine having the following.