JPH0412294B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a novel quaternary polymer salt, and more particularly to a novel quaternary polymer salt having an imidazolium salt in its main chain. The novel quaternary polymer salt of the present invention is a modifier for synthetic resins, a post-treatment agent for textiles, a paper treatment agent, a flocculant, an antistatic agent, an auxiliary agent for detergents, cosmetics, shampoos, etc., a preservative, and an antibacterial agent.・It is expected to be applied as a medicine such as a cholesterol-lowering agent. Improvements of the invention in relation to the prior art Polymers having ammonium salts, pyridinium 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 a polymeric quaternary salt odorless and improve its heat resistance, and provides a novel polymeric quaternary salt that has no odor in the polymer and does not have an unpleasant odor even when used when heating is required. It is something to do. Structure of the invention The present invention is based on the general formula [] (In the formula, R ₁ is a hydrogen atom, a C _2-17 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 12 to 31, respectively. _R1 used in the general formula [] of the polymer quaternary salt of the present invention is a hydrogen atom, _{a C2-17} alkyl group such as ethyl, propyl, hexyl, undecyl, heptadecyl group, or phenyl, tolyl, xylyl group, etc. _{R2 and R3} are the same or different substituents and are a hydrogen atom or _{a C1-3} alkyl group such as _methyl , ethyl, propyl group, _R4 is a hydrogen atom or a methyl group, is selected from halogen atoms such as chlorine and bromine. Among these, specific examples of particularly preferred polymeric quaternary salts have the following structure.

[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. . Method for producing a polymer quaternary salt of the present invention As a method for producing a polymer quaternary salt of the present invention, for example, the general formula [] (In the formula, R ₁ is a hydrogen atom, a C _2-17 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. respectively) and the general formula [], (In the formula, R ₄ is a hydrogen atom or a methyl group,
(indicates a halogen atom, respectively). The imidazoles represented by the general formula [] used in the above production method include imidazole, 2
-ethylimidazole, 2-propylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole,
2-ethyl-4-methylimidazole, 2,4-
Examples include dimethylimidazole and 2-phenyl-4-methylimidazole. Examples of the halomethyloxirane compound represented by the general 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. In the reaction method, when water is used as a solvent, it is preferable to drop the halomethyloxirane compound into an aqueous solution of imidazoles, but they can also be added at the same time. After the reaction is completed, the resulting viscous reaction solution is poured into a poor solvent for the polymer quaternary salt of the present invention, such as ethanol or acetone, to obtain a white powdery polymer quaternary salt. 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 by nuclear magnetic resonance spectrum is 31.) (Production Example 2) 63.5 g (0.44 mol) of 2-phenylimidazole
was partially dissolved and dispersed in 100 ml of water and placed in a 300 ml four-necked flask. Next, 40.8 g (0.44 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 16 hours. The same post-treatment as in Production Example 1 was carried out to obtain 99.7 g of a white powdery resin (referred to as Resin C). 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, 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 Spectrum Characteristic Absorption Position (Solvent: D ₂ O, Unit: δ (ppm)) 50.53 (C-4, 6)

【formula】 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) (4) Elemental analysis

[Table] (5) Intrinsic viscosity [η] (solvent: water, 25℃) 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 spectroscopy is 23.) (Production Example 3) 97.9 g (0.44 mol) of 2-undecylimidazole was partially dissolved and dispersed in 120 ml of water.
ml in a four-necked flask. Next, 40.8 (0.44 mol) of epichlorohydrin was added using a dropping funnel at 50°C.
After adding the mixture over a period of 2 hours, the temperature was raised to 100°C and the reaction was carried out at this temperature for 16 hours. After the same post-treatment as in Production Example 1, 134.7g of white powdered resin (Resin D
) was obtained. 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, 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)) 0.7-1.4 (m, 23H, C ₁₁ H ₂₃ ) 3.7-4.4 (m, 5H

【formula】) 7.38(s, 2H,

[Formula]) (3) ¹³ C-Nuclear Magnetic Resonance Spectrum Characteristic Absorption Position (Solvent: D ₂ O, Unit: δ (ppm)) 13.56, 22.34 26.35, 28.71 29.25, 31.76 (C-C ₁₁ )

【formula】 50.79 (C-4, 6) 68.24 (C-5) 121.89 (C-2, 3) 210.83 (C-1) (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 by nuclear magnetic resonance spectrum is 12.) (Production Example 4) 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 C H ₃ ) 2.14 (s, 3H, -CH ₃ ) 2.92 (brd, 2H, -CH ₂ CH ₃ ) 4.1-4.6 (m.5H,

【formula】) 7.09(s, 1H,

[Formula]) (3) ¹³ C-nuclear magnetic resonance spectral characteristic absorption position (solvent: D ₂ O, unit: δ (ppm)) 8.67 (C-8),

【formula】 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) (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. Note that in the formula, the value of n calculated from nuclear magnetic resonance spectrum data is 15. ) (Heat resistance test example) In order to examine the heat resistance of the novel polymer quaternary salt of the present invention, resin A obtained in Production Example 1 and a commercially available polymer quaternary salt (polydiallyldimethylammonium chloride manufactured by Aldrich Co., Ltd.) were used. The thermal loss was measured using a differential thermal balance device (manufactured by Rigaku Denki, constant temperature differential thermal balance model 8002H) 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 resin of the present invention is heated at 300°C.
Until then, almost no weight loss was observed. On the other hand, commercially available polymeric quaternary salts showed a weight loss from around 100°C, and were 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 of the present invention and a conventional product.

Claims (1)

[Claims] 1. General formula [] (In the formula, R ₁ is a hydrogen atom, a C _2-17 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 12 to 31.) A novel quaternary polymer salt represented by: