JPH0424364B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a novel method for producing a polymeric quaternary salt, and more particularly to a novel method for producing a novel polymeric quaternary salt having an imidazolium salt in its main chain. The novel quaternary polymer salt produced by the method of the present invention can be used as a modifier for synthetic resins, a textile post-treatment agent, a paper treatment agent, a flocculant, an antistatic agent, an auxiliary agent for detergents, cosmetics, shampoos, etc. It is expected to be used as a medicine, such as a preservative, an antibacterial agent, and a cholesterol-lowering agent. Prior Art and Problems to be Solved by the Invention Conventionally, polymers having ammonium salts, pyrinidium salts, etc. are known as polymer quaternary salts. However, this type of polymeric quaternary salt has poor thermal stability, so when used, especially when heated, it emits an extremely unpleasant amine odor, which worsens the working environment or creates materials that should be improved. It had drawbacks such as deterioration of quality. The present inventors completed the present invention through extensive research in order to overcome these drawbacks of conventional products. The present invention aims to make the polymer quaternary salt odorless and improve its heat resistance, and to produce a novel polymer quaternary salt that has no odor in the polymer and does not have an unpleasant odor even when used when heating is required. The present invention provides a method. Structure of the invention The present invention is based on the following formula () (In the formula, _R1 is a hydrogen atom, _{a C1-17 alkyl} group or _{a C6-8 aryl} group, _R2 and _R3 are the same or different substituents and are a hydrogen atom or _{a C1-3} alkyl group, R ₄ represents a hydrogen atom or a methyl group, X represents a halogen atom, and n represents an integer of 2 or more. R ₁ used in the above formula () of the polymer quaternary salt produced by the method of the present invention is a hydrogen atom, a C ₁ to ₁₇ alkyl group such as methyl, ethyl, propyl, hexyl, undecyl, heptadecyl group, or _C6-8 aryl group such _as phenyl, tolyl _{, xylyl group, R2 and R3 are the same or different substituents and hydrogen atom or C1-3 alkyl group such} as methyl, ethyl, propyl group, _R4 is A hydrogen atom or a methyl group, and X are selected from halogen atoms such as chlorine and bromine. Among these, specific examples of particularly preferred polymeric quaternary salts have the following structure.

【table】

[Table] The molecular weight of the polymeric quaternary salt specified by these substituents is not particularly limited as long as it is water-soluble, but it is preferably a polymeric quaternary salt in which n is 2 or more, preferably 2 to 5000. . The method for producing the polymer quaternary salt of the present invention is carried out by the following formula () (In the formula, R ₁ is a hydrogen atom, _a C _1-17 alkyl group or a C _6-8 aryl group, _and R ₂ and R ₃ are the same or different substituents and represent a hydrogen atom or _a C _1-3 alkyl group. The imidazoles represented by the following formula () (In the formula, R ₄ is a hydrogen atom or a methyl group,
represents a halogen atom). The imidazoles represented by the formula () used in the above production method include imidazole, 2
-ethylimidazole, 2-methylimidazole, 2-propylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-
Examples include heptadecylimidazole, 2-ethyl-4-methylimidazole, 2,4-dimethylimidazole, and 2-phenyl-4-methylimidazole. Examples of the halomethyloxirane compound represented by the formula () include epichlorohydrin, β-methylepichlorohydrin, and epibromohydrin. Water is used as the reaction solvent, and thereby a high molecular weight product can be obtained. The reaction molar ratio is preferably 0.5 to 2.0 mol, particularly preferably 0.9 to 1.1 mol, of the halomethyloxirane compound per 1 mol of the imidazole. The reaction temperature used is 30 to 150℃, but especially 50 to 150℃.
120°C is preferred. Below 30℃, the reaction rate is slow;
If the temperature exceeds 120°C, side reactions tend to occur, which is not preferable. A suitable reaction time is 2 to 30 hours. When using water as a solvent, the reaction method is preferably to drop the halomethyloxirane compound into an aqueous solution of imidazoles, but they can also be added at the same time. At the end of the reaction, the resulting viscous reaction solution is poured into a poor solvent for the polymer quaternary salt produced by the method of the present invention, such as ethanol or acetone, to obtain a white powdery polymer quaternary salt. be able to. Example (Production Example 1) 30 g (0.441 mol) of imidazole was dissolved in 60 ml of water and placed in a 300 ml four-necked flask. Next, 40.8 g (0.441 mol) of epichlorohydrin was added via a dropping funnel at 50°C over 2 hours, and then the temperature was raised to 100°C and the reaction was carried out at this temperature for 14 hours. The resulting viscous reaction solution was poured into 200 ml of ethanol to precipitate a polymer. After separation, the mixture was washed and dried under reduced pressure to obtain 68.6 g of a white powder resin (referred to as Resin A). The resulting resin was analyzed and the following results were obtained. (1) Infrared absorption spectrum characteristic absorption position (KBr
law, unit cm ^-1 ) 3400, 2040, 1620, 1560, 1440, 1340, 1160,
1100, 760, 630 (2) Proton nuclear magnetic resonance spectral characteristics Absorption position (solvent: D ₂ O, unit δ (ppm)) 3.9-4.4 (m,
5H,

【formula】) 7.37(s, 2H,

【formula】) 8.71(s, 1H,

[Formula]) (3) ¹³ C-nuclear magnetic resonance spectral characteristics Absorption position (solvent: D ₂ O, unit δ (ppm)) 51.97 (C-4,6)

【formula】 67.72 (C-5) 123.04 (C-2,3) 136.86 (C-1) (4) Elemental analysis

[Table] (5) Intrinsic viscosity [η] (solvent: water, 25℃) 0.72 From the above results, resin A is It can be seen that it has the following structure. (In the formula, the value of n calculated from nuclear magnetic resonance spectrum data is 31.) (Production Example 2) 41 g (0.5 mol) of 2-methylimidazole was added to 60 g of water.
ml and put it in a 300 ml four-necked flask. Next, 46.3 g (0.5 mol) of epichlorohydrin was added using a dropping funnel at 50°C over 2 hours, and then
The temperature was raised to 0.degree. C., and the reaction was carried out at this temperature for 14 hours. The same post-treatment as in Production Example 1 was performed to obtain 83.9 g of a white powdery resin (referred to as Resin B). The obtained resin was analyzed in the same manner as in Production Example 1, and the following results were obtained. (1) Infrared absorption spectrum characteristic absorption position (KBr
Act, unit cm ^-1 ) 3400, 2050, 1620, 1580,
1520, 1420, 1340, 1260, 1180, 1100, 1030,
870, 760, 660 (2) Proton nuclear magnetic resonance spectral characteristics Absorption position (solvent: D ₂ O, unit δ (ppm)) 2.52 (s, 3H,
_CH3 ) 4.0~4.4(m, 5H,

【formula】) 7.32(s, 2H,

[Formula]) (3) ¹³ C-nuclear magnetic resonance spectral characteristics Absorption position (solvent: D ₂ O, unit δ (ppm)) 9.53 (C-7) 50.45 (C-4, 6) 68.16 (C-5) 121.63 (C-2, 3) 145.81 (C-1)

【formula】 (4) Elemental analysis

[Table] (5) Intrinsic viscosity [η] (solvent: water, 25℃) Based on the results of 1.00 or more, the resin B obtained in this production example was It can be seen that it has the following structure. (In the formula, the value of n calculated from nuclear magnetic resonance spectrum data is 35.) (Production Example 3) 63.5 g (0.44 mol) of 2-phenylimidazole was partially dissolved and dispersed in 100 ml of water. Pour into a 300ml four-necked flask. Then epichlorohydrin
After adding 40.8g (0.44 mol) using a dropping funnel at 50℃ over 2 hours, the temperature was raised to 100℃ and at this temperature 16
A time reaction was performed. After the same post-treatment as in Production Example 1, 99.7g of white powdery resin (referred to as Resin C) was obtained.
I got it. This resin was analyzed in the same manner as in Production Example 1. (1) Infrared absorption spectrum characteristic absorption position (KBr
Act, unit: cm ^-1 ) 3400, 3200, 1620, 1600,
1580, 1500, 1470, 1430, 1260, 1170, 1100,
1030, 870, 770, 690 (2) Proton nuclear magnetic resonance spectral characteristics Absorption position (solvent: D ₂ O, unit: δ (ppm)) 3.6-3.9 (m, 5H,

【formula】) 7.10(d, 2H,

【formula】) 7.34(s, 2H,

【formula】) 7.40 (m, 2H,

【formula】) 7.56 (m, 1H,

[Formula]) (3) ¹³ C-nuclear magnetic resonance spectral characteristics Absorption position (solvent: D ₂ O, unit δ (ppm)) 50.53 (C-4, 6) 67.35 (C-5) 119.67 (C-7) 122.40 (C-2, 3) 129.63 (C-8, 12) 129.83 (C-9, 11) 132.77 (C-10) 145.35 (C-1)

【formula】 (4) Elemental analysis

[Table] (5) Intrinsic viscosity [η] (solvent: water, 25℃) 0.41 From the above results, resin C has It can be seen that it has the following structure. (In the formula, the value of n calculated by nuclear magnetic resonance spectrum is 23.) (Production Example 4) 2-Undecylimidazole 97.9 g (0.44 mol)
was partially dissolved and dispersed in 120 ml of water and placed in a 300 ml four-necked flask. Next, 40.8 g (0.44 mol) of epichlorohydrin was added at 50℃ using a dropping funnel.
After adding it for a while, raise the temperature to 100℃ and keep it at this temperature.
The reaction was carried out for 16 hours. The same post-treatment as in Production Example 1 was carried out to obtain 134.7 g of a white powdery resin (referred to as Resin D). This resin was analyzed in the same manner as in Production Example 1. (1) Infrared absorption spectrum characteristic absorption position (KBr
Law, unit: cm ^-1 ) 3400, 3200, 2900, 2850, 1620, 1580, 1520,
1460, 1440, 1370, 1260, 1180, 1100, 870,
760, 720 (2) Proton nuclear magnetic resonance spectral characteristics Absorption position (solvent: D ₂ O, unit δ (ppm)) 0.7 to 1.4 (m, 23H, C ₁₁ H ₂₃ ) 3.7 to 4.4 (m, 5H,

【formula】) 7.38(s, 2H,

[Formula]) (3) ¹³ C-nuclear magnetic resonance spectral characteristics Absorption position (solvent: D ₂ O, unit δ (ppm)) 13.56, 22.34 26.35, 28.71 29.25, 31.76 (C-C ₁₁ ) 50.79 (C-4 , 6) 68.24 (C-5) 121.89 (C-2, 3) 210.83 (C-1)

【formula】 (4) Elemental analysis

[Table] (5) Intrinsic viscosity [η] (solvent: water, 25℃) 0.27 From the above results, resin D is It can be seen that it has the following structure. (In the formula, the value of n calculated from nuclear magnetic resonance spectrum data is 12.) (Production Example 5) 48.6 g of 2-ethyl-4-methylimidazole
(0.44 mol) was dissolved in 60 ml of water and placed in a 300 ml four-necked flask. Next, 40.8g of epichlorohydrin
(0.44 mol) was added through a dropping funnel at 50°C over 2 hours, then the temperature was raised to 100°C and the reaction was carried out at this temperature for 14 hours. The same post-treatment as in Production Example 1 was carried out to obtain 89.3 g of a white powdery resin (referred to as Resin E). This resin was analyzed in the same manner as in Production Example 1. (1) Infrared absorption spectrum characteristic absorption position (KBr method,
Unit: cm ^-1 ) 3400, 3000, 2050, 1630, 1520, 1450, 1390,
1240, 1180, 1100, 1060, 880, 780 (2) Proton nuclear magnetic resonance spectral characteristics Absorption position (solvent: D ₂ O, unit δ (ppm)) 1.09 (s, 3H, -CH ₂ CH ₃ ) 2.14 (s , 3H, −CH ₃ ) 2.92 (brd, 2H, −CH ₂ CH ₃ ) 4.1 to 4.6 (m, 5H,

【formula】) 7.09(s, 1H,

[Formula]) (3) ¹³ C-nuclear magnetic resonance spectral characteristics Absorption position (solvent: D ₂ O, unit δ (ppm)) 8.67 (C-8), 10.65 (C-9), 16.82 (C-7) , 47.63 (C-4) 49.96 (C-6) 67.67 (C-5) 118.43 (C-3) 130.78 (C-2) 149.13 (C-1)

【formula】 (4) Elemental analysis

[Table] (5) Intrinsic viscosity [η] (solvent: water, 25℃) 0.20 From the above results, resin E is It can be seen that it has the following structure. (In the formula, the value of n calculated from nuclear magnetic resonance spectrum data is 15.) (Example of heat resistance test) In order to investigate the heat resistance of the polymer quaternary salt produced by the method of the resin of the present invention, Resins A and B obtained in Production Examples 1 and 2 and a commercially available polymer quaternary salt (polydiallyldimethylammonium chloride manufactured by Aldrich Co., Ltd.) were tested using a differential thermometer (manufactured by Rigaku Denki, constant temperature differential thermobalance model 8002H). The thermal loss was measured under the following conditions. Atmosphere: Air Temperature rising rate: 10°C/min The results are shown in Figure 1. As is clear from the figure, the polymer quaternary salt produced by the method of the present invention showed almost no weight loss up to 300°C. On the other hand, commercially available polymeric quaternary salts show a weight loss from around 100°C, and are found to have a heat loss of about 17% at 300°C.

[Brief explanation of drawings]

FIG. 1 is a thermobalance chart showing the heat resistance of the polymer quaternary salt produced by the method of the present invention and a conventional product.

Claims (1)

[Claims] 1. The following formula () (In the formula, R ₁ is a hydrogen atom, _a C _1-17 alkyl group or a C _6-8 aryl group, _and R ₂ and R ₃ are the same or different substituents and represent a hydrogen atom or _a C _1-3 alkyl group. , R ₄ is a hydrogen atom or a methyl group,
represents a halogen atom, and n represents an integer from 2 to 5000, respectively). (In the formula, R ₁ is a hydrogen atom, _a C _1-17 alkyl group or a C _6-8 aryl group, _and R ₂ and R ₃ are the same or different substituents and represent a hydrogen atom or _a C _1-3 alkyl group. The imidazoles represented by the following formula () (In the formula, R ₄ is a hydrogen atom or a methyl group,
A method for producing a novel quaternary polymer salt represented by the above formula (), which comprises reacting the compound with a halomethyloxirane compound represented by the following formula (2 and 3 each representing a halogen atom) in an aqueous solvent.