JPH1149788A - Phosphonium compound having (meth) acryloylurethane bond and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phosphonium compound having a (meth) acryloylurethane bond, which is a cationic polymer having an unsaturated bond, and a method for producing the same. SOLUTION: A hydroxyorganophosphonium salt is reacted with a (meth) acryloyl isocyanate compound to obtain a compound represented by the following general formula (1): To produce a phosphonium compound having a (meth) acryloylurethane bond.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The phosphonium compound having a (meth) acryloylurethane bond according to the present invention is a cationic polymer having a novel unsaturated bond. By homopolymerization or copolymerization, an antistatic agent and an antibacterial agent can be obtained. It is useful as a flame retardant, conductive agent, dye improver, polymer modifier, flocculant and the like.

[0002]

2. Description of the Related Art Conventionally, as a phosphonium compound having an unsaturated bond, a compound having an acrylate bond has been known. A method for producing such a compound is to convert an aliphatic carboxylic acid having an unsaturated carboxylic acid halide such as methacrylic acid chloride and a halogen such as 2-chloroethanol into an amine, as shown in the following reaction formula (A). A method is known in which the reaction is carried out in the presence, purified by distillation, and then reacted with triorganophosphine (JP-A-7-25714).

[0003]

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The problem with this production method is that the first stage reaction is carried out using a basic catalyst such as pyridine or triethyl-amine, so that the product must be purified and separated by distillation. The operation is also very complicated. In addition, the compounds that can be synthesized are limited because the boiling point of the product increases as the alkylene chain increases. Furthermore, in the second reaction, the reaction of reacting triorganophosphine with a halide having an unsaturated bond to form a quaternary phosphonium salt requires a high reaction temperature and a long reaction time.
Moreover, such a compound having a functional group which is easily polymerized,
Usually, even if a polymerization inhibitor is added, polymerization cannot be completely prevented by heating the reaction temperature to a high temperature for a long time.
For this reason, the yield is generally low, and a high-purity product cannot be obtained because a polymer or an unreacted product is mixed in the obtained target product.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies on a novel phosphonium compound monomer having an unsaturated bond, which has never existed before. As a result, they have found a novel phosphonium compound having a (meth) acryloylurethane bond. Then, as a result of diligent research on the production method, high purity and high yield by simple operation,
A method for producing a phosphonium compound having a (meth) acryloylurethane bond has been found, and the present invention has been completed.
That is, the present invention provides a phosphonium compound having a (meth) acryloylurethane bond in high yield and high purity by reacting a hydroxyorganophosphonium salt with a vinyl compound having an isocyanate group, and a method for producing the same. Aim.

[0006]

That is, the present invention provides the following general formula (1):

[0007]

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Wherein R ₁ is H or CH ₃ , x is 1 to
2, y is 0 or 1, A is a linear or branched alkylene, R ₂ , R ₃ and R ₄ are a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, The present invention provides a phosphonium compound having a (meth) acryloylurethane bond represented by either a reel group or an aralkyl group, each of which may be the same group or a different group. Also,
The production method is represented by the following general formula (2):

[0009]

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Wherein A is a linear or branched alkylene, X is Cl, Br or I, R ₂ , R ₃ and R ₄ are a linear or branched alkyl group having 1 to 18 carbon atoms; An alkyl group, an aryl group, an alkaryl group or an aralkyl group, each of which may be the same or different) and a hydroxyorganophosphonium salt represented by the following general formula (3):

[0011]

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(Wherein R ₁ is H or CH ₃ , x is 1 to
2. A method for producing a phosphonium compound having a (meth) acryloylurethane bond of the general formula (1), characterized by reacting a (meth) acryloyl isocyanate compound represented by the formula (2), wherein 0 or 1) is provided. Is what you do.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. (Starting substance) (Hydroxyorganophosphonium salt) In the hydroxyorganophosphonium salt represented by the general formula (2),
A in the formula is, for example, a linear or branched alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and an ethyl-ethylene group. It is a chain alkylene group. R ₁ , R ₂ and R ₃ may be the same group or different groups, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, heptyl group, octyl Group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, 1-methylpentyl group, 2-methylpentyl group, 5-methylhexyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group , An isopentyl group, a neopentyl group, a tert-pentyl group, an isohexyl group, and the like. X is Cl, Br and I halogen.
Particularly preferred is Cl or Br. The reaction raw material of the general formula (2) is not particularly limited as long as it is industrially available, but the following two known methods for producing the same are typically exemplified. deep. (I) When A is a methylene group, the following general formula (4):

[0014]

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(Wherein R ₁ , R ₂ and R ₃ have the same meanings as described above), the reaction is carried out by reacting triorganophosphine with paraformaldehyde in the presence of hydrogen halide. By B), a hydroxymethylphosphonium compound which is a compound of the general formula (2) can be obtained. [Hellmann, H., J. Bader, H. Birkner, and O. Schuma
cher, Ann., 659, 49 (1962)]

[0016]

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(II) A is an ethylene group or a triethylene group,
In the case of a tetramethylene group or the like, the triorganophosphine represented by the general formula (4) and the following general formula (5):

[0018]

HO-AX (5)

(Wherein, A and X have the same meanings as described above)
The hydroxyorganophosphonium compound of the starting compound (2) can be obtained by the following reaction formula (C). [Petrov, K., A. Gavriliva, V. Nam, and V. Chuchkan
ova, Zh. Obsheh. Khim., 32, 3711 (1962)]

[0020]

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(Acyl Isocyanate Compound) The compound of the general formula (3) which is a raw material of the present invention is (meth) acryloyl isocyanate, (meth) acryloyloxyethyl isocyanate or the like. (Reaction conditions) The reaction formula of the present invention is the following reaction formula (D):

[0022]

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The reaction temperature is generally 0-100 ° C, preferably 0-50 ° C, and the reaction time is generally 0.5-24 hours, preferably 1-3 hours. Further, an aging reaction may be performed if necessary. The molar ratio in the reaction between the hydroxyorganophosphonium salt of the general formula (2) and the (meth) acryloyl isocyanate compound of the general formula (3) is 1: 1.
A molar ratio of １ ： 1: 2, preferably 1: 1 to 1: 1.2 is suitable. At this time, the reaction is carried out by adding a polymerization inhibitor and a reaction solvent as needed. The type of polymerization inhibitor is
For example, hydroquinone, hydroquinone monomethyl ether, phenothiazine, 2,6-ditert-butylparacresol, thiourea, urea, N-phenyl-N'-
Examples thereof include isopropyl paraphenylenediamine, but are not particularly limited thereto.

The polymerization inhibitor is added in an amount of 100 to 10,000 ppm, preferably 500 to 5,000 ppm, based on the obtained target substance, and the amount of the solvent is usually 2 to 10 parts by weight based on the phosphonium compound. Times, preferably 2
These are about 5 times, but they are not particularly limited. The solvent is acetonitrile, propionitrile, nitrile compounds such as butyronitrile, benzene, toluene, aromatic hydrocarbons such as xylene, hexane, heptane, aliphatic hydrocarbons such as cyclohexane, acetone,
Ketones such as methyl ethyl-ketone and MIBK, DMS
O, sulfolane and the like can be mentioned, but it is not particularly limited. It is desirable to perform azeotropic dehydration in order to remove a trace amount of water in the solvent and the raw material. The water content in the reaction system after the azeotropic dehydration is 10 to 1,000 ppm, preferably 10 to 100 ppm.

(Product: phosphonium compound having a (meth) acryloylurethane bond) The phosphonium compound having a (meth) acryloylurethane bond represented by the general formula (1) obtained by the above-mentioned production method is, for example,
Triethyl- (N-methacryloylcarbamoyloxymethyl) phosphonium chloride, tri-n-butyl-
(N-methacryloylcarbamoyloxymethyl) phosphonium chloride, tri-n-octyl (N-methacryloylcarbamoyloxymethyl) phosphonium
Chloride, tri-n-butyl- (N-methacryloylcarbamoyloxymethyl) phosphonium bromide, tri-n-butyl- (N-methacryloylcarbamoyloxyethyl) phosphonium iodide, tri-
n-butyl- (N-methacryloylcarbamoyloxyethyl) phosphonium chloride, tri-n-butyl- (N-methacryloylcarbamoyloxypropyl)
Phosphonium chloride, tri-n-butyl- (N-
Methacryloylcarbamoyloxybutyl) phosphonium chloride; tri-n-butyl- (N-methacryloyloxyethylcarbamoyloxyethyl) phosphonium chloride; The compounds of the present invention
By homopolymerization or copolymerization, various industrial fields, for example, slime prevention or control agent in papermaking, water, oil and fat, emulsion, paper, wood, rubber, plastic, fiber, film, antiseptic, antibacterial, paint, etc. Antistatic properties, flame retardancy and antifouling properties can be imparted.

[0026]

The present invention is a novel compound represented by the general formula (1). Further, the production method can be easily achieved by reacting the starting compounds represented by the general formulas (2) and (3). In the present invention, as shown in the following reaction formula (E), a phosphonium compound having a vinyl group can be obtained in a very high purity and a high yield by a simple operation by reacting an acyl isocyanate compound with a hydroxyorganophosphonium salt. Can be. Since the isocyanate group has a very high reactivity with a compound having active hydrogen such as an alcohol or an amine, almost 100% of the reaction is usually completed only by mixing and stirring at room temperature. In addition, since a by-product such as hydrogen halide is not generated in the reaction, the target product can be obtained with high purity. Further, in recent years, acyl isocyanate compounds have also become commercially available at relatively low cost, and thus it has become possible to implement them industrially.

[0027]

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[0028]

The present invention will be described in more detail with reference to the following examples, but it should not be construed that the invention is limited thereto. Example 1 Production of tri-n-butyl- (N-methacryloylcarbamoyloxyethyl) phosphonium chloride 5 equipped with a stirrer, thermometer, dropping funnel, and condenser
A 00 ml four-necked flask was sufficiently purged with nitrogen, and 150 g (0.741 mol) of tri-n-butylphosphine was added.
Was charged. 62.7 2-chloroethanol at 80 ° C
g (0.779 mol) was added dropwise over 30 minutes. It became cloudy with dropping. Further, it was aged at 120 ° C. for 2 hours. The reaction solution was a very viscous colorless transparent liquid. Unreacted trialkylphosphine was checked with carbon disulfide, but was not detected. Concentration with an evaporator and drying with a vacuum pump gave 206.4 g of a colorless transparent viscous liquid. The titration purity is 100.
At 0%, the yield was 98.5%. According to the analysis results,
The product is tri-n-butyl- (2-hydroxyethyl)
It was phosphonium chloride.

FAB-MS (Pos.); 247 FAB-MS (Neg.); 35, 37 ¹ H-NMR (TMS, δ): 0.97 (t, J = 6.9)
Hz, 9H), 1.49 to 1.70 (m, 12H), 2.
31 to 2.50 (m, 6H), 2.50 to 2.70 (m,
2H), 4.04 (d, t, J = 20.9 Hz, J = 9.0.
FT-IR (liquid film, cm ^-1 ): 3200, 2975, 2
950, 2790, 1468, 1418, 1385, 1
320, 1238, 1160, 1070, 1002, 9
20, 810, 720

In a 300 ml four-necked flask equipped with a stirrer, a thermometer and a distillation line, the obtained tri-n-
14.1 g (0.05 mol) of butyl- (2-hydroxyethyl) phosphonium chloride was added to 200 ml of acetone.
Dissolved and charged. Heat while stirring at normal pressure,
About 100 ml of acetone was distilled off. After cooling, a condenser equipped with a calcium chloride tube was attached, 0.05 g of hydroquinone monomethyl ether was added as a polymerization inhibitor, and methacryloyl isocyanate was added with a dropping funnel.
2 g (0.05 mol, purity 90%) was added dropwise at room temperature over 1 hour, and the mixture was further stirred at 40 ° C. for 3 hours. After aging, the reaction solution was concentrated at a temperature of 40 ° C. or lower and dried with a vacuum pump to obtain 20.4 g of a slightly yellow viscous liquid. The non-aqueous titration with perchloric acid was 95.1%, and the yield was 98.3%. According to the analysis result, the product was tri-n-butyl- (N-methacryloylcarbamoyloxyethyl) phosphonium chloride.

FAB-MS (Pos.); 358 FAB-MS (Neg.); 35, 37 ¹ H-NMR (TMS, δ): 0.96 (t, J = 7.1)
Hz, 9H), 1.48 to 1.81 (m, 12H), 1.
95 (s, 3H), 2.22 to 2.50 (m, 6H),
2.89 to 3.18 (m, 2H), 4.60 (d, t, J
= 15.0 Hz, J = 9.0 Hz, 2H), 5.90
(S, 1H), 6.33 (s, 1H), 10.82 (s,
1H) FT-IR (liquid film, cm ^-1 ): 3200, 2940, ¹
773, 1680, 1636, 1510, 1460, 1
212, 1050, 918, 745

Example 2 Preparation of tri-n-butyl- (N-methacryloylcarbamoyloxyethyl) phosphonium bromide 5 equipped with a stirrer, thermometer, dropping funnel and condenser
A 00 ml four-necked flask was sufficiently purged with nitrogen, and 150 g (0.741 mol) of tri-n-butylphosphine was added.
Was charged. 97.3 2-bromoethanol at 50 ° C
g (0.779 mol) was added dropwise over 30 minutes. Further, it was aged at 120 ° C. for 2 hours. The reaction solution was confirmed to contain trialkylphosphine using carbon disulfide.
Not detected. By concentrating with an evaporator and further drying with a vacuum pump, a colorless transparent viscous liquid 23 is obtained.
7.4 g were obtained. The titration purity is 99.4% and the yield is 9
It was 7.3%. According to the analysis result, the product was tri-n
-Butyl- (2-hydroxyethyl) phosphonium bromide.

(. Pos); (. Neg ) [0033] FAB-MS 247 FAB-MS; 79,81 1 H-NMR (TMS, δ): 0.96 (t, J = 6.8
Hz, 9H), 1.48 to 1.70 (m, 12H), 2.
33 to 2.50 (m, 6H), 2.50 to 2.71 (m,
2H), 4.06 (d, t, J = 20.9 Hz, J = 9.
2Hz, 2H), 5.91 (s, 1H) FT-IR (liquid film, cm ^-1 ): 3285, 2950, 2
890, 1622, 1462, 1381, 1306, 1
230, 1055, 955, 904, 804, 730

In a 300 ml four-necked flask equipped with a stirrer, a thermometer and a distillation line, the obtained tri-n-
16.5 g (0.05 mol) of butyl- (2-hydroxyethyl) phosphonium bromide was added to 200 ml of acetone.
Dissolved and charged. Heat while stirring at normal pressure,
About 100 ml of acetone was distilled off. After cooling, a condenser equipped with a calcium chloride tube was attached, 0.05 g of hydroquinone monomethyl ether was added as a polymerization inhibitor, and methacryloyl isocyanate was added with a dropping funnel.
2 g (0.05 mol, purity 90%) was added dropwise at room temperature over 1 hour, and the mixture was further stirred at 40 ° C. for 3 hours. After aging, the reaction solution was concentrated at a temperature of 40 ° C. or lower and dried with a vacuum pump to obtain 21.8 g of a slightly yellow viscous liquid. The non-aqueous titration with perchloric acid was 99.5%, and the yield was 99.0%. According to the analysis result, the product was tri-n-butyl- (N-methacryloylcarbamoyloxyethyl) phosphonium bromide.

FAB-MS (Pos.); 358 FAB-MS (Neg.); 79, 81 ¹ H-NMR (TMS, δ): 0.98 (t, J = 7.0)
Hz, 9H), 1.45 to 1.81 (m, 12H), 1.
96 (s, 3H), 2.22 to 2.51 (m, 6H),
2.87-3.19 (m, 2H), 4.60 (d, t, J
= 15.0 Hz, J = 8.9 Hz, 2H), 5.92
(S, 1H), 6.32 (s, 1H), 10.81 (s,
1H) FT-IR (liquid film, cm ^-1 ): 3220, 2940, ¹
771, 1679, 1638, 1508, 1461, 1
211, 1048, 917, 745

Example 3 Production of tri-n-butyl- (N-methacryloylcarbamoyloxyethyl) phosphonium iodide 5 equipped with a stirrer, thermometer, dropping funnel and condenser
A 00 ml four-necked flask was sufficiently purged with nitrogen, and 150 g (0.741 mol) of tri-n-butylphosphine was added.
Was charged. 127.4 g of 2-iodoethanol (0.7
41 mol) was added dropwise over about 1 hour while maintaining the temperature at 50 to 55 ° C. Further, it was aged at 80 ° C. for 2 hours. In the reaction solution, residual trialkylphosphine was confirmed using carbon disulfide, but was not detected. Concentration with an evaporator and drying with a vacuum pump gave a melting point of 4.
273.5 g of a waxy white solid at 3.6-45.2 ° C. were obtained. There was almost no deliquescence. The titration purity is 100.
At 0%, the yield was 98.6%. According to the analysis results,
The product is tri-n-butyl- (2-hydroxyethyl)
It was a phosphonium iodide.

FAB-MS (Pos.); 247 FAB-MS (Neg.); 127 ¹ H-NMR (TMS, δ): 0.99 (t, J = 6.6)
Hz, 9H), 1.43-1.70 (m, 12H), 2.
31 to 2.50 (m, 6H), 2.62 to 2.79 (m,
2H), 4.07 (d, t, J = 20.8 Hz, J = 9.
1Hz, 2H), 5.91 (s, 1H) FT-IR (KBr, cm ^-1 ): 3295, 2870,
1440, 1380, 1300, 1215, 1050,
1000, 900, 788

In a 300 ml four-necked flask equipped with a stirrer, thermometer and distillation line, the obtained tri-n-
18.7 g (0.05 mol) of butyl- (2-hydroxyethyl) phosphonium bromide was added to 200 ml of acetone.
Dissolved and charged. Heat while stirring at normal pressure,
About 100 ml of acetone was distilled off. After cooling, a condenser equipped with a calcium chloride tube was attached, 0.05 g of hydroquinone monomethyl ether was added as a polymerization inhibitor, and methacryloyl isocyanate was added with a dropping funnel.
2 g (0.05 mol, purity 90%) was added dropwise at room temperature over 1 hour, and the mixture was further stirred at 40 ° C. for 3 hours. After aging, the reaction solution was concentrated at a temperature of 40 ° C. or lower and dried with a vacuum pump to obtain 22.9 g of a slightly yellow viscous liquid. The non-aqueous titration with perchloric acid was 93.9%, and the yield was 97.1%. According to the analysis result, the product was tri-n-butyl- (N-methacryloylcarbamoyloxyethyl) phosphonium iodide.

FAB-MS (Pos.); 358 FAB-MS (Neg.); 127 ¹ H-NMR (TMS, δ): 0.98 (t, J = 7.0)
Hz, 9H), 1.48 to 1.70 (m, 12H), 1.
97 (s, 3H), 2.48 to 2.53 (m, 6H),
2.90-3.19 (m, 2H), 4.61 (d, t, J
= 15.0 Hz, J = 8.9 Hz, 2H), 5.77
(S, 1H), 6.17 (s, 1H), 10.82 (s,
1H) FT-IR (liquid film, cm ^-1 ): 3330, 2975, 2
945, 2890, 1773, 1710, 1635, 1
502, 1460, 1380, 1216, 1153, 1
115, 1050, 1000, 920, 800

Example 4 Production of tri-n-butyl- (N-methacryloylcarbamoyloxymethyl) phosphonium chloride 1 equipped with a stirrer, thermometer, dropping funnel and condenser
L. The four-necked flask was sufficiently purged with nitrogen, and tri-n
Butylphosphine 150 g (0.741 mol), paraformaldehyde 23.4 g (0.779 mol), pure water 2
00 ml was added. At room temperature, (1 + 1) hydrochloric acid aqueous solution 1
When 62 g (0.779 mol) was gradually added dropwise over 30 minutes, the internal temperature rose to 38 ° C. Further, at 60 ° C
For 2 hours. In the reaction solution, residual trialkylphosphine was confirmed using carbon disulfide, but was not detected. By concentrating with an evaporator and further drying with a vacuum pump, 201.8 g of a white solid was obtained. Melting points could not be measured due to strong deliquescence. The purity determined by nonaqueous titration with perchloric acid was 98.7%, and the yield was 100%. According to the analysis result, the product was tri-n
-Butyl- (hydroxymethyl) phosphonium chloride.

FAB-MS (Pos.); 233 FAB-MS (Neg.); 35, 37 ¹ H-NMR (TMS, δ): 0.98 (t, J = 6.7)
Hz, 9H), 1.43 to 1.71 (m, 12H), 2.
31 to 2.50 (m, 6H), 3.89 to 4.10 (m,
2H), 5.91 (s, 1H) FT-IR (liquid film, cm ^-1 ): 3296, 2871, ¹
440, 1381, 1300, 1214, 1050, 1
000, 809, 785

In a 300 ml four-necked flask equipped with a stirrer, thermometer and distillation line, the obtained tri-n-
13.4 g (0.05 mol) of butyl- (hydroxymethyl) phosphonium chloride was dissolved in 200 ml of acetone and charged. The mixture was heated with stirring at normal pressure to distill off about 100 ml of acetone. After cooling, a condenser equipped with a calcium chloride tube was attached, 0.05 g of hydroquinone monomethyl ether was added as a polymerization inhibitor, and 6.2 parts of methacryloyl isocyanate was added with a dropping funnel.
g (0.05 mol, purity 90%) was added dropwise at room temperature over 1 hour, and the mixture was further stirred at 40 ° C. for 3 hours. After aging,
The reaction solution was concentrated at a temperature of 40 ° C. or lower and dried with a vacuum pump to obtain 19.4 g of a slightly yellow viscous liquid. The non-aqueous titration with perchloric acid was 96.2%, and the yield was 98.2%. According to the analysis result, the product was tri-n-butyl- (N-methacryloylcarbamoyloxymethyl) phosphonium chloride.

FAB-MS (Pos.); 344 FAB-MS (Neg.); 35, 37 ¹ H-NMR (TMS, δ): 0.97 (t, J = 6.7)
Hz, 9H), 1.44-1.70 (m, 12H), 1.
98 (s, 3H), 2.46 to 2.53 (m, 6H),
4.49 to 4.70 (m, 2H), 5.77 (s, 1
H), 6.18 (s, 1H), 10.82 (s, 1H) FT-IR (liquid film, cm ^-1 ): 3327, 2776, 2
945, 2890, 1772, 1710, 1635, 1
501, 1460, 1380, 1215, 1152, 1
114, 1050, 1000, 918, 745

Example 5 Production of tri-n-butyl- (N-methacryloylcarbamoyloxybutyl) phosphonium chloride 5 equipped with a stirrer, thermometer, dropping funnel and condenser
A 00 ml four-necked flask was sufficiently purged with nitrogen, and 150 g (0.741 mol) of tri-n-butylphosphine was added.
Was charged. At 140 ° C., 62.7 g (0.779 mol) of 4-chloro-1-butanol was gradually added dropwise over 4 hours without reflux. Further, it was aged at the same temperature for 3 hours. After checking the reaction with carbon disulfide,
The unreacted trialkylphosphine was detected from red coloring. Therefore, it is dissolved in 500 ml of pure water, and extracted and washed with 300 ml of toluene.
n-Butylphosphine was removed. By concentrating the aqueous layer with an evaporator and drying with a vacuum pump,
209.9 g of a colorless transparent viscous liquid were obtained. Titration purity is 9
At 9.8%, the yield was 90.9%. According to the analysis result, the product was tri-n-butyl- (4-hydroxybutyl) phosphonium chloride.

FAB-MS (Pos.); 275 FAB-MS (Neg.); 35, 37 ¹ H-NMR (TMS, δ): 0.97 (t, J = 6.9)
Hz, 9H), 1.49 to 1.70 (m, 12H), 1.
76 to 2.03 (m, 4H), 2.31 to 2.50 (m,
6H), 2.50-2.70 (m, 2H), 4.04
(D, t, J = 20.5 Hz, J = 9.0 Hz, 2H),
5.91 (s, 1H) FT-IR (liquid film, cm ^-1 ): 3240, 2920, 2
860, 1458, 1402, 1378, 1308, 1
227, 1090, 995, 960, 908, 802,
718

In a 300 ml four-necked flask equipped with a stirrer, a thermometer and a distillation line, the obtained tri-n-
15.6 g (0.05 mol) of butyl- (4-hydroxybutyl) phosphonium chloride was added to 200 ml of acetone.
Dissolved and charged. Heat while stirring at normal pressure,
About 100 ml of acetone was distilled off. After cooling, a condenser equipped with a calcium chloride tube was attached, 0.05 g of hydroquinone monomethyl ether was added as a polymerization inhibitor, and methacryloyl isocyanate was added with a dropping funnel.
2 g (0.05 mol, purity 90%) was added dropwise at room temperature over 1 hour, and the mixture was further stirred at 40 ° C. for 3 hours. After aging, the reaction solution was concentrated at a temperature of 40 ° C. or lower and dried with a vacuum pump to obtain 22.2 g of a slightly yellow viscous liquid. The non-aqueous titration with perchloric acid was 94.2%, and the yield was 99.3%. According to the analysis result, the product was tri-n-butyl- (N-methacryloylcarbamoyloxyethyl) phosphonium chloride.

FAB-MS (Pos.); 386 FAB-MS (Neg.); 35, 37 ¹ H-NMR (TMS, δ): 0.98 (t, J = 6.9)
Hz, 9H), 1.32-1.69 (m, 12H), 1.
79 to 2.03 (m, 7H), 2.30 to 2.51 (m,
6H), 2.90-3.08 (m, 2H), 4.18-4.
31 (m, 2H), 5.72 (s, 1H), 6.27
(S, 1H), 10.42 (s, 1H) FT-IR (liquid film, cm ^-1 ): 3155, 2950, ¹
772, 1678, 1627, 1517, 1460, 1
220, 1162, 1099, 912, 805, 720

Example 6 Production of tri-n-butyl- (N-methacryloylcarbamoyloxybutyl) phosphonium chloride 5 equipped with a stirrer, thermometer, dropping funnel and condenser
A 00 ml four-necked flask was sufficiently purged with nitrogen, and 150 g (0.741 mol) of tri-n-butylphosphine was added.
Was charged. At 140 ° C., 62.7 g (0.779 mol) of 4-chloro-1-butanol was gradually added dropwise over 4 hours without reflux. Further, it was aged at the same temperature for 3 hours. After checking the reaction with carbon disulfide,
The unreacted trialkylphosphine was detected from red coloring. Therefore, it is dissolved in 500 ml of pure water, and extracted and washed with 300 ml of toluene.
n-Butylphosphine was removed. By concentrating the aqueous layer with an evaporator and drying with a vacuum pump,
209.9 g of a colorless transparent viscous liquid were obtained. Titration purity is 9
At 9.8%, the yield was 90.9%. According to the analysis result, the product was tri-n-butyl- (4-hydroxybutyl) phosphonium chloride.

FAB-MS (Pos.); 275 FAB-MS (Neg.); 35, 37 ¹ H-NMR (TMS, δ): 0.97 (t, J = 6.9)
Hz, 9H), 1.49 to 1.70 (m, 12H), 1.
76 to 2.03 (m, 4H), 2.31 to 2.50 (m,
6H), 2.50-2.70 (m, 2H), 4.04
(D, t, J = 20.5 Hz, J = 9.0 Hz, 2H),
5.91 (s, 1H) FT-IR (liquid film, cm ^-1 ): 3240, 2920, 2
860, 1458, 1402, 1378, 1308, 1
227, 1090, 995, 960, 908, 802,
718

In a 300 ml four-necked flask equipped with a stirrer, a thermometer and a distillation line, the obtained tri-n-
15.6 g (0.05 mol) of butyl- (4-hydroxybutyl) phosphonium chloride was added to 200 ml of acetone.
Dissolved and charged. Heat while stirring at normal pressure,
About 100 ml of acetone was distilled off. After cooling, a condenser equipped with a calcium chloride tube was attached, 0.05 g of hydroquinone monomethyl ether was added as a polymerization inhibitor, and methacryloyl isocyanate was added with a dropping funnel.
2 g (0.05 mol, purity 90%) was added dropwise at room temperature over 1 hour, and the mixture was further stirred at 40 ° C. for 3 hours. After aging, the reaction solution was concentrated at a temperature of 40 ° C. or lower and dried with a vacuum pump to obtain 22.2 g of a slightly yellow viscous liquid. The non-aqueous titration with perchloric acid was 94.2%, and the yield was 99.3%. According to the analysis result, the product was tri-n-butyl- (N-methacryloylcarbamoyloxyethyl) phosphonium chloride.

FAB-MS (Pos.); 386 FAB-MS (Neg.); 35, 37 ¹ H-NMR (TMS, δ): 0.98 (t, J = 6.9)
Hz, 9H), 1.32-1.69 (m, 12H), 1.
97 (s, 3H), 2.30-2.51 (m, 6H), 2.
90 to 3.08 (m, 2H), 4.18 to 4.31 (m,
2H), 5.72 (s, 1H), 6.27 (s, 1H),
10.42 (s, 1H) FT-IR (liquid film, cm ^-1 ): 3155, 2950, ¹
772, 1678, 1627, 1517, 1460, 1
220, 1162, 1099, 912, 805, 720

Example 7 Production of triethyl- (N-methacryloylcarbamoyloxyethyl) phosphonium chloride 1 equipped with a stirrer, thermometer, dropping funnel and condenser
The four-necked L flask was sufficiently purged with nitrogen, and 100 g (0.846 mol) of triethylphosphine and 4 ml of toluene
00 ml was charged. At 80 ° C., 74.9 g (0.930 mol) of 2-chloroethanol was added dropwise over 1 hour.
Further, it was aged at 100 ° C. for 3 hours. In the reaction solution, residual trialkylphosphine was confirmed using carbon disulfide, but was not detected. The mixture was concentrated by an evaporator and dried by a vacuum pump to obtain 165.0 g of a colorless transparent viscous liquid. The titration purity was 99.0% and the yield was 97.2%. The product was triethyl- (2-hydroxyethyl) phosphonium chloride.

FAB-MS (Pos.); 163 FAB-MS (Neg.); 35, 37 ¹ H-NMR (TMS, δ): 0.98 (t, J = 6.8)
Hz, 9H), 2.18 to 2.42 (m, 6H), 2.4
9 to 2.71 (m, 2H), 4.01 (d, t, J = 2
0.4 Hz, J = 9.0 Hz, 2H), 5.90 (s, 1
H) FT-IR (liquid film, cm ^-1 ): 3200, 2976, 2
949, 2788, 1465, 1415, 1382, 1
311, 1238, 1160, 1068, 1000, 9
11,808,712

In a 300 ml four-necked flask equipped with a stirrer, a thermometer and a distillation line, 10.0 g (0.05 mol) of the obtained triethyl- (2-hydroxyethyl) phosphonium chloride was dissolved in 200 ml of acetone. I did it. The mixture was heated with stirring at normal pressure to distill off about 100 ml of acetone. After cooling, attach a condenser equipped with a calcium chloride tube, add 0.05 g of hydroquinone monomethyl ether as a polymerization inhibitor,
6.2 g of methacryloyl isocyanate with dropping funnel
(0.05 mol, purity 90%) was added dropwise at room temperature over 1 hour, and the mixture was further stirred at 40 ° C. for 3 hours. After aging, 4
The reaction solution was concentrated at a temperature of 0 ° C. or lower and dried with a vacuum pump to obtain 15.4 g of a slightly yellow viscous liquid.
The non-aqueous titration with perchloric acid is 98.6% and the yield is 9
It was 7.9%. According to the analysis result, the product was triethyl- (N-methacryloylcarbamoyloxyethyl)
It was phosphonium chloride.

FAB-MS (Pos.); 274 FAB-MS (Neg.); 35, 37 ¹ H-NMR (TMS, δ): 0.97 (t, J = 6.8)
Hz, 9H), 2.18 to 2.42 (m, 6H), 1.9
8 (s, 3H), 2.70-3.19 (m, 2H), 4.
60 (d, t, J = 15.3 Hz, J = 9.2 Hz, 2
H), 5.91 (s, 1H), 6.36 (s, 1H), 1
0.69 (s, 1H) FT-IR (liquid film, cm ^-1 ): 3192, 2943, ¹
774, 1680, 1636, 1508, 1460, 1
213, 1050, 917, 743

Example 8 Production of tri-n-octyl- (N-methacryloylcarbamoyloxyethyl) phosphonium chloride 5 equipped with a stirrer, thermometer, dropping funnel and condenser
A 00 ml four-necked flask was sufficiently purged with nitrogen and charged with 150 g (0.405 mol) of tri-n-octylphosphine and 39.1 g (0.486 mol) of 2-chloroethanol. The mixture was separated into two layers without mixing, and no heat generation due to the reaction was observed. The temperature was gradually increased while stirring under a nitrogen stream, and finally the reaction was carried out at 150 ° C. for 8 hours. After cooling, residual trialkylphosphine was confirmed in the reaction solution using carbon disulfide, but was not detected. The reaction solution was concentrated by an evaporator and further dried by a vacuum pump to obtain 190.1 g of a waxy white solid.
The titration purity was 96.1% and the yield was 100.0%. The product was tri-n-octyl- (2-hydroxyethyl) phosphonium chloride.

FAB-MS (Pos.); 415 FAB-MS (Neg.); 35, 37 ¹ H-NMR (TMS, δ): 0.96 (t, J = 6.7)
Hz, 9H), 1.13 to 2.10 (m, 36H), 2.
31 to 2.50 (m, 6H), 2.50 to 2.70 (m,
2H), 4.02 (d, t, J = 20.6 Hz, J = 9.0.
0 Hz, 2H), 5.90 (s, 1H) FT-IR (liquid film, cm ^-1 ): 3200, 2974, 2
948, 2792, 1465, 1415, 1383, 1
320, 1235, 1160, 1068, 1001, 9
20, 810, 725

In a 300 ml four-necked flask equipped with a stirrer, a thermometer and a distillation line, the obtained tri-n-
Octyl (2-hydroxyethyl) phosphonium chloride (23.5 g, 0.05 mol) was added to 200 ml of acetone.
Dissolved and charged. Heat while stirring at normal pressure,
About 100 ml of acetone was distilled off. After cooling, a condenser equipped with a calcium chloride tube was attached, 0.05 g of hydroquinone monomethyl ether was added as a polymerization inhibitor, and methacryloyl isocyanate was added with a dropping funnel.
2 g (0.05 mol, purity 90%) was added dropwise at room temperature over 1 hour, and the mixture was further stirred at 40 ° C. for 3 hours. After aging, the reaction solution was concentrated at a temperature of 40 ° C. or lower and dried with a vacuum pump to obtain 27.9 g of a slightly yellow viscous liquid. The non-aqueous titration with perchloric acid was 98.5%, and the yield was 97.7%. According to the analysis result, the product was tri-n-octyl- (N-methacryloylcarbamoyloxyethyl) phosphonium chloride.

FAB-MS (Pos.); 526 FAB-MS (Neg.); 35, 37 ¹ H-NMR (TMS, δ): 0.96 (t, J = 7.0)
Hz, 9H), 1.09-2.10 (m, 39H), 2.
31 to 2.50 (m, 6H), 2.88 to 3.20 (m,
2H), 4.61 (d, t, J = 15.0 Hz, J = 9.
0 Hz, 2H), 5.89 (s, 1H), 6.32 (m,
1H), 10.71 (s, 1H) FT-IR (liquid film, cm ^-1 ): 3200, 2942, ¹
771, 1679, 1634, 1508, 1458, 1
213, 1048, 916, 745

Example 9 Production of tri-n-butyl- (N-methacryloyloxyethylcarbamoyloxyethyl) phosphonium chloride 100 ml equipped with a stirrer, a thermometer, and a nitrogen inlet tube.
, 14.1 g (0.05 mol) of tri-n-butyl- (2-hydroxyethyl) phosphonium chloride obtained in Example 1, 0.05 g of hydroquinone monomethyl ether as a polymerization inhibitor, methacryloyl 7.85 g of oxyethyl isocyanate (0.05 mol, manufactured by Showa Denko, purity 98.8%) was added dropwise at room temperature.
The reaction was performed at 80 ° C. for 4 hours. The reaction solution was dried with a vacuum pump to obtain 22.2 g of a slightly yellow viscous liquid. The non-aqueous titration with perchloric acid is 98.6% and the yield is 99.
9%. According to the analysis result, the product was tri-n-butyl- (N-methacryloyloxyethylcarbamoyloxyethyl) phosphonium chloride.

FAB-MS (Pos.); 402 FAB-MS (Neg.); 35, 37 ¹ H-NMR (TMS, δ): 0.97 (t, j = 6.6)
Hz, 9H), 1.43-1.69 (m, 12H), 1.
94 (s, 3H), 2.25 to 2.51 (m, 6H),
2.51-2.71 (m, 2H), 2.80-3.01
(M, 2H), 3.42 to 3.56 (m, 2H), 4.1
8-4.31 (m, 2H), 5.56 (s, 1H), 6.
17 (s, 1H), 9.33 (s, 1H), FT-IR (liquid film, cm ^-1 ): 2961, 2933, 2
875, 1718, 1671, 1638, 1562, 1
461, 1260, 1161, 1050, 817

[0062]

According to the present invention, since the present invention is constituted as described above, an antistatic agent, an antibacterial agent, a flame retardant, a conductive agent, a dye improving agent,
Disclosed is a phosphonium compound having a (meth) acryloylurethane bond, which is a cationic polymer having a novel unsaturated bond, which is useful as a polymer modifier, a flocculant, and the like. The present invention also provides a method for industrially easily producing the novel compound.

Claims (2)

[Claims] 1. The following general formula (1): (Wherein R ₁ is H or CH ₃ , x is 1-2, y is 0 or 1, A is a linear or branched alkylene, X is Cl, B
r or I, R ₂ , R ₃ and R _{4 each} have 1 to 1 carbon atoms
8 represents any of a straight-chain or branched alkyl group, cycloalkyl group, aryl group, alkaryl group and aralkyl group, each of which may be the same or different. A) a phosphonium compound having a (meth) acryloylurethane bond; 2. The following general formula (2): (Wherein A is a linear or branched alkylene, X is Cl,
Br or I, R ₂ , R ₃ and R _{4 each} represent a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an alkaryl group or an aralkyl group, A hydroxyorganophosphonium salt represented by the following general formula (3): (Wherein, R ₁ is H or CH ₃ , x is 1-2, y is 0 or 1), and reacted with a (meth) acryloyl isocyanate compound represented by the following general formula (1): (Wherein R ₁ is H or CH ₃ , x is 1-2, y is 0 or 1, A is a linear or branched alkylene, X is Cl, B
r or I, R ₂ , R ₃ and R _{4 each} represent a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an alkaryl group or an aralkyl group, The same group or different groups may be used. A method for producing a phosphonium compound having a (meth) acryloylurethane bond, characterized by producing a phosphonium compound having a (meth) acryloylurethane bond represented by the formula (1).