JP2783266B2 - Novel azoamidine salt and its production method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel azoamidine salt useful as a polymerization initiator in the production of various polymer compounds, and a method for producing the same.

[0002]

2. Description of the Related Art Certain azoamidine compounds have excellent decomposition activity and polymerization activity in a solvent suitable for a polymerization system.
It is widely used as an excellent polymerization initiator in polymerization of acrylamide, allylamine, vinylpyrrolidone, etc., production of cationic polymers, production of fluororesins, various emulsion polymerizations, photopolymerization and the like. However, since these are usually used as mineral salts represented by hydrohalides, they may corrode the reaction equipment and the like in some cases. When used for cationic electrodeposition coating, there is a concern that the rust prevention effect is reduced.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polymerization initiator in the production of a polymer compound, which has excellent decomposition activity and polymerization activity, has a problem of corrosion of reaction equipment, and uses this as a polymerization initiator. It is an object of the present invention to provide a novel azoamidine salt and a method for producing the same, which do not cause a problem such as a decrease in rust prevention effect when the polymer produced by the above method is used for electrodeposition coating.

[0004]

The present invention provides a compound represented by the general formula [1]:

[0005]

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(Wherein, R ¹ represents a methyl group or an ethyl group, R ² represents a lower alkylene group which may have a substituent, and R represents a lower alkyl group, a lower alkenyl group, an aryl group or an aralkyl group. Azoamidine organic sulfonate represented by the formula:

Further, the present invention provides a compound represented by the general formula [2]:

[0008]

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(Wherein R ¹ represents a methyl group or an ethyl group, and R ′ represents a lower alkyl group having 1 to 4 carbon atoms), and a free form of an azoimino ether represented by the general formula [3]: —SO ₃ H.H ₂ N—Y [3] [wherein, R represents a lower alkyl group, a lower alkenyl group, an aryl group or an aralkyl group, and Y represents —R ² —NH ₂ (R ²
Represents a lower alkylene group which may have a substituent. ). Reacting with an organic sulfonic acid diamine salt represented by the formula in a water-soluble organic solvent,
General formula [1]

[0010]

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(Wherein R ¹ , R ² and R are the same as above)
And a method for producing an azoamidine organic sulfonate represented by the formula: Furthermore, the present invention provides a compound represented by the general formula [2]:

[0012]

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(Wherein R ¹ represents a methyl group or an ethyl group, R ′ represents a lower alkyl group having 1 to 4 carbon atoms), and a free form of an azoimino ether represented by the general formula [4] H ₂ NY [4] [wherein, Y represents -R ² -NH ₂ (R ² represents a lower alkylene group which may have a substituent). After reacting a diamine represented by the water-soluble organic solvent in], general formula _{[5] R-SO 3 H} [5] ( wherein, R is a lower alkyl group, lower alkenyl group, an aryl group or an aralkyl group Wherein the compound is reacted with an organic sulfonic acid represented by the general formula [1]:

[0014]

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(Wherein R ¹ , R ² and R are as defined above)
And a method for producing an azoamidine organic sulfonate represented by the formula:

In the general formula [1], the lower alkylene group of the lower alkylene group which may have a substituent represented by R ² may be linear or branched. Examples thereof include 2 to 5 alkylene groups, and examples of the substituent include a hydroxyl group. Specific examples include ethylene, propylene, 1-methylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, 1-ethyl-2-methylethylene, and 2-hydroxypropylene. Examples of R include lower alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and isobutyl group, and lower alkenyl groups such as vinyl group, 1-propenyl group, allyl group and 2-methylallyl group. Groups such as phenyl, tolyl, xylyl,
An aryl group such as a naphthyl group or an aralkyl group such as a benzyl group, a methylbenzyl group, a dimethylbenzyl group, a phenethyl group, a methylphenethyl group, a dimethylphenethyl group, and the like can be given.

The method for producing the compound of the present invention will be described. First, the corresponding azoimino ether mineral acid salt is prepared according to the method described in, for example, JP-A-56-61343.
For example, azoimino ether hydrochloride is neutralized with ammonia gas or amines in a non-polar solvent to obtain a free azoimino ether. Then, this is reacted with an organic sulfonic acid diamine salt in a water-soluble organic solvent, whereby the target compound of the present invention can be synthesized. In addition, this method is represented as follows.

[0018]

(Equation 1)

(Wherein, R ′ represents an alkyl group having 1 to 4 carbon atoms, Y represents —R ² —NH ₂ , and R, R ¹ and R ² are the same as described above.)

In addition to the above method, the compound of the present invention can be obtained by the following method. That is, after obtaining a free form of azoimino ether in the same manner as described above, this is first reacted with a diamine in a water-soluble organic solvent to obtain a free form of azoamidine, and then reacted with a corresponding organic sulfonate. Then, the desired compound of the present invention can be easily obtained. In addition, this method is represented as follows.

[0021]

(Equation 2)

(Wherein, R, R ¹ , R ² , R ′ and Y are the same as described above.) Examples of the water-soluble organic solvent used in the amidination reaction include:
For example, lower alcohols such as methanol, ethanol and propanol, acetone, ethyl methyl ketone, acetonitrile, dioxane, dimethyl sulfoxide, dimethylformamide and the like can be mentioned. Usually, the amount of the water-soluble organic solvent used in the amidination reaction is preferably 1 to 6 times (volume / weight) the theoretically obtained amount of the target azoguanyl compound. In the amidination reaction, the presence of the water-soluble organic solvent is indispensable, but other non-polar solvents may be mixed.

The reaction temperature of the amidination reaction slightly varies depending on other factors and is not particularly limited, but is usually 40 ° C. or lower, preferably about 25 to 35 ° C. The reaction time varies depending on the compound, the reaction temperature and other reaction conditions, but is usually several hours to several tens of hours. The reaction is completed in an appropriate time according to the progress of the reaction.

The azoimino ether hydrochloride can be prepared by a conventional method,
For example, Japanese Patent Publication No. 58-2230, U.S. Pat.
According to the method described in No. 9, etc., the corresponding azonitrile is easily subjected to an iminoetherification reaction with an alcohol and hydrogen chloride gas, or easily reacted by reacting a hydrazo form of azonitrile with chlorine gas in the presence of an alcohol. Can be synthesized. The method is represented, for example, as follows.

[0025]

(Equation 3)

Wherein R ¹ and R ′ are the same as above.

[0027]

(Equation 4)

(In the formula, R ¹ and R ′ are the same as described above.) The compound of the present invention is not a mineral salt of an azoamidine compound but an organic sulfonate, but its solubility in water is practically sufficient. Especially in the case of lower aliphatic sulfonates, such as methanesulfonate,
Mineral salts such as hydrochlorides tend to have higher solubility in water.

On the other hand, the solubility of the compound of the present invention in an organic solvent shows practically sufficient solubility except for a solvent such as n-hexane, toluene, which is generally considered to be extremely difficult to dissolve salts. In particular, the solubility in polar organic solvents such as dimethylformamide (DMF) tends to be significantly improved as compared with the case of mineral salts such as hydrochloride.

Therefore, the compound of the present invention is difficult to be applied to acrylonitrile, which is not only soluble in aqueous solution polymerization of acrylamide or vinylpyrrolidone or the like, or in methanol solution of vinyl acetate, but also in the case of azoamidine compound mineral acid salt because it is almost insoluble in DMF. Can be sufficiently applied to DMF solution polymerization.

The compound of the present invention shows high activity equivalent to the corresponding mineral acid salt in terms of decomposition activity and polymerization activity in aqueous solution and methanol. Since the compound of the present invention is not a mineral salt such as hydrochloride, there is no danger of corroding the reaction equipment and the like when used as a polymerization initiator. Even when used for applications such as color coating, there is no concern that the rust prevention effect will be reduced. Examples are shown below, but the present invention is not limited to these examples.

[0032]

【Example】

Example 1 To 27.7 g of 2,2'-azobisisobutyronitrile, 22.3 g of methanol and 186 g of toluene were added, and 25.5 g of hydrogen chloride was introduced with stirring under cooling, followed by stirring at room temperature for 5 hours. I let it. After standing overnight, 13.4 g of ammonia gas was introduced into the reaction solution while stirring under cooling. The precipitated ammonium chloride was removed by filtration to obtain a toluene solution of the corresponding free azoimino ether. Add methanol 1
After adding 2.4 g of ethylenediamine 2 with stirring.
9.5 g was gradually added dropwise over 1 hour, and the mixture was further stirred and reacted at 30 to 35 ° C. for 5 hours. After standing overnight, the mixture was cooled, and the precipitated crystals were collected by filtration and dried to obtain 51 g of 2,2′-azobis (N, N′-dimethyleneisobutylamidine). Add 50 methanol
g and 50 g of acetone, and then 38.4 g of methanesulfonic acid was gradually added while stirring at 10 to 15 ° C.
After stirring at 10 to 15 ° C. for another hour, the mixture is filtered and dried.
2,2'-azobis (N, N'-dimethyleneisobutylamidine)
-76 g of methanesulfonic acid was obtained. mp: 136-143 ° C (decomposition). UV: λ _max 363.5 nm.

Example 2 50 g of methanol and 50 g of acetone were added to 51 g of 2,2'-azobis (N, N'-dimethyleneisobutylamidine) obtained in the same manner as in Example 1, and p-toluenesulfone was added with stirring. A solution consisting of 76.1 g of acid and 118 g of acetone was slowly added at 10-15 ° C. 1 more at 10-15 ° C
After stirring for an hour, the precipitated crystals were collected by filtration and dried to obtain 99 g of 2,2′-azobis (N, N′-dimethyleneisobutylamidine) · p-toluenesulfonic acid salt. mp: 131-134 ° C (decomposition). UV: λ _max 361.8 nm.

Example 3 76.9 g of 2,2'-azobis (2-methylbutyronitrile)
Was added with 38.5 g of methanol and 320 g of toluene,
After introducing 58 g of hydrogen chloride with stirring under cooling, the mixture was reacted with stirring under ice cooling for 140 hours. After the reaction, 26 g of ammonia gas was introduced with stirring under cooling, and the precipitated ammonium chloride was removed by filtration to obtain a toluene solution of the corresponding azoimino ether derivative. To this solution, 17.6 g of methanol was added, and 40.9 g of ethylenediamine was gradually added, followed by a stirring reaction at 30 to 35 ° C. for 5 hours. After standing overnight, the reaction solution was concentrated under reduced pressure, and after cooling, the precipitated crystals were collected by filtration and dried to obtain 38.7 g of 2,2′-azobis (N, N′-dimethylene 2-methylbutylamidine). . 73.8 g of methanol and 54.5 g of acetone were added thereto, and 26.6 g of methanesulfonic acid was gradually added while stirring under cooling. After stirring for another 30 minutes, the precipitated crystals were collected by filtration, dried and 2,2'-
47.4 g of azobis (N, N'-dimethylene 2-methylbutylamidine) .methanesulfonate was obtained. mp: 149 ° C (decomposition). UV: λ _max 370.7 nm.

Example 4 To 38.7 g of 2,2'-azobis (N, N'-dimethylene 2-methylbutylamidine) obtained in the same manner as in Example 3, 73.8 g of methanol and 54.5 g of acetone were added. Then, while stirring under cooling, 52.8 g of p-toluenesulfonic acid was added.
And 94 g of acetone were slowly added. After stirring for an additional 30 minutes, the precipitated crystals were collected by filtration and dried to give 2,2′-azobis (N, N′-dimethylene 2-methylbutylamidine) · p
83.4 g of toluenesulfonate were obtained. mp: 126 ° C (decomposition). UV: λ _max 370.6 nm.

Example 5 38.5 g of methanol and 320 g of toluene were added to 82.1 g of 2,2'-azobisisobutyronitrile, and while cooling, 44 g of hydrogen chloride was introduced with stirring, followed by stirring at room temperature for 5 hours. Reacted. After standing overnight, 23 g of ammonia gas was introduced while stirring under cooling, and the precipitated ammonium chloride was filtered off to obtain a corresponding toluene solution of a free azoimino ether. After adding 24 g of methanol to this, 1,2
-Slowly add 63 g of diaminopropane, 30-35 ° C
For 5 hours. After standing overnight, the reaction solution was concentrated under reduced pressure, and after cooling, the precipitated crystals were collected by filtration, dried and 87 g of 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] 87 g. I got 34 g of methanol
And 200 g of acetone, 59 g of methanesulfonic acid was gradually added while stirring under cooling, and the reaction was further stirred for 1 hour under cooling. The precipitated crystals are collected by filtration, dried and
-Azobis [2- (5-methyl-2-imidazoline-2
-Yl) propane] .109 g of methanesulfonate was obtained. mp: 127-128.2C (decomposition). UV: λ _max 361.9 nm.

Example 6 2,2'-Azobis [2- (5-
Methyl-2-imidazolin-2-yl) propane] 87
After adding 38.5 g of methanol and 226 g of acetone to the resulting mixture, the mixture was stirred under cooling while stirring p-toluenesulfonic acid 1
A solution consisting of 20 g and 259 g of acetone was slowly added. After further stirring and reacting for 1 hour, the precipitated crystals were collected by filtration, dried and 140 g of 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] .p-toluenesulfonate. I got mp: 131-132 ° C (decomposition). UV: λ _max 362.4 nm.

Example 7 After adding 38.5 g of methanol and 320 g of toluene to 82.1 g of 2,2'-azobisisobutyronitrile, 44 g of hydrogen chloride was introduced with stirring under cooling, and the mixture was stirred at room temperature. The reaction was stirred for a period of time. After standing overnight, 23 g of ammonia gas was introduced with stirring under cooling, and the precipitated ammonium chloride was filtered off to obtain a corresponding toluene solution of a free azoimino ether. After 24 g of methanol was added thereto, 74.9 g of 2-methyl-1,2-diaminopropane was gradually added, and the mixture was stirred and reacted at 30 to 35 ° C. for 5 hours. After standing overnight, the reaction solution was concentrated under reduced pressure, cooled, and the precipitated crystals were collected by filtration, dried and dried to give 2,2′-azobis [2- (5,5-dimethyl-
2-imidazolin-2-yl) propane] was obtained. After adding 60 g of methanol and 380 g of acetone thereto, 75 g of methanesulfonic acid was stirred under cooling.
Was gradually added, and the mixture was stirred and reacted for 1 hour. The precipitated crystals were collected by filtration, dried, and 2,2′-azobis [2- (5,5-dimethyl-
2-imidazolin-2-yl) propane] • methanesulfonate (150 g) was obtained. mp: 142-150 ° C (decomposition). UV: λ _max 361.3 nm.

Example 8 2,2′-Azobis [2- (5,5-) obtained in the same manner as in Example 7.
Dimethyl-2-imidazolin-2-yl) propane] 1
After adding 60 g of methanol and 262 g of acetone to 21 g, p-toluenesulfonic acid 8 was added with stirring under cooling.
A solution consisting of 0 g and 170 g of acetone was slowly added.
After further reacting with stirring for 1 hour, the precipitated crystals were collected by filtration and dried.
186 g of 2,2'-azobis [2- (5,5-dimethyl-2-imidazolin-2-yl) propane] .p-toluenesulfonic acid salt was obtained. mp: 121-124 ° C (decomposition). UV: λ _max 361.8 nm.

[0040]

According to the present invention, there is provided a novel azoamidine organic sulfonate having excellent decomposition activity and polymerization activity as a polymerization initiator in the production of a polymer compound, and a method for producing the same. That is, when the azoamidine organic sulfonate of the present invention was used as a polymerization initiator, there was no problem of corrosion of the reaction equipment, and the azoamidine organic sulfonate of the present invention was produced using the polymerization initiator as a polymerization initiator. When the polymer is used for the purpose of cationic electrodeposition coating, the polymer has a remarkable effect in that the problem of the reduction of the rust prevention effect does not occur, and is a great invention that contributes to the industry.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C07D 233/64 106 C08F 2/50 C08F 4/04 CA (STN)

Claims (5)

(57) [Claims] 1. A compound of the general formula [1] (Wherein, R ¹ represents a methyl group or an ethyl group, R ² represents a lower alkylene group which may have a substituent, and R represents a lower alkyl group, a lower alkenyl group, an aryl group or an aralkyl group. Azoamidine organic sulfonate represented by the formula: 2. A compound of the general formula [2] (Wherein R ¹ represents a methyl group or an ethyl group, and R ′ represents a lower alkyl group having 1 to 4 carbon atoms), and a azoimino ether free product represented by the following general formula [3]: R—SO ₃ H · H ₂ N—Y [3] [wherein, R represents a lower alkyl group, a lower alkenyl group, an aryl group or an aralkyl group, and Y represents —R ² —NH ₂ (R ²
Represents a lower alkylene group which may have a substituent. ). Reacting with an organic sulfonic acid diamine salt represented by the formula in a water-soluble organic solvent,
General formula [1] (Wherein R ¹ , R ² and R are the same as described above). 3. A compound of the general formula [2] (Wherein R ¹ represents a methyl group or an ethyl group, R ′ represents a lower alkyl group having 1 to 4 carbon atoms), and an azoimino ether free product represented by the general formula [4] H ₂ N— Y [4] [wherein, Y represents —R ² —NH ₂ (R ² represents a lower alkylene group which may have a substituent). After reacting a diamine represented by the water-soluble organic solvent in], general formula _{[5] R-SO 3 H} [5] ( wherein, R is a lower alkyl group, lower alkenyl group, an aryl group or an aralkyl group Wherein the compound is reacted with an organic sulfonic acid represented by the general formula [1]: (Wherein R ¹ , R ² and R are the same as described above). 4. The process for producing an azoamidine organic sulfonate according to claim 2, wherein the water-soluble organic solvent is a lower alcohol, acetone, ethyl methyl ketone, acetonitrile, dioxane, dimethyl sulfoxide or dimethylformamide. 5. The method for producing an azoamidine organic sulfonate according to claim 4, wherein the lower alcohol is methanol, ethanol or propanol.