JPS62167771A - Imidazolium salt type polycationic compound and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [R1 is H, 1-17C alkyl or 6-8C aryl; R2 and R3 are H or 1-3C alkyl; X(-) is halide ion, hydroxide ion or 1/2(sulfate) ion; n is a number of 1-10,000; T1 and T2 are halogen or formula II]. EXAMPLE:A compound expressed by formula III. USE:A flocculant, paper strengthening agent, textile dyeability improver, softening finish for hair, antistaic agent, electrically conductive agent, raw material for electrically conductive high polymer compositions (radical complex salts of polycations), and raw material for medicines, e.g. antimicrobial agent, antifungal agent, cholesterol-lowering agent, etc., and ion exchange resins. PREPARATION:A compound expressed by formula IV is reacted with p-xylylene dichloride in a solvent capable of dissolving both while heating to afford the aimed compound expressed by formula I. The above-mentioned compound expressed by formula I has good thermal stability and is capable of exhibiting good electric conductivity when applied to a radical anionic complex salt type electrically conductive high polymer composition of polycations without any skin irritancy.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel polycationic compound having an imidazolium salt in its chain.

The novel polycation of the present invention is a flocculant, a paper strength enhancer,
Fiber dyeing improver, hair softening agent.

Antistatic agent, conductive agent, conductive polymer composition! It is useful as a raw material for polycation radical anion complex salts, pharmaceuticals such as antibacterial agents, fungicides, and cholesterol-lowering agents, and raw materials for ion exchange resins.

[Problems with conventional technology]

Conventionally, aliphatic amine polycations are known as polycation compounds and are used as antistatic agents and flocculants.

However, since aliphatic amine-based polycations have poor thermal stability, they decompose by °C during use under heating, emitting unpleasant amine odor and causing N color. In addition, many aliphatic amine-based polycations are highly irritating to the skin and ocular mucous membranes, and their use is regulated particularly in rinses and fabric softeners that come in direct contact with the skin and eyes. Furthermore, when a polycation radical anion complex type conductive polymer composition is synthesized using a conventional polycation,
There are also problems such as not being able to obtain good conductivity.

[Problem that the invention seeks to solve]

The present invention provides a polycation compound that has no thermal stability or skin irritation and exhibits good electrical conductivity when applied to a polycation radical anion complex type conductive polymer composition.

That is, the first aspect of the present invention provides an imidazolium salt type polycation compound represented by the following general formula (I).

[In the formula, R1 represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or an alkyl group having 6 to 8 carbon atoms; R2 and R3
may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; Xe represents a halogen ion, a hydroxide ion, or 1/2 (sulfate ion); n represents 1 to Represents the number 10,000: T1 and T2 may be the same or different, and each represents a halogen atom or the following formula (■): (In the formula, R1,
R2 and R3 have the same meanings as above. ) indicates a residue. ] The second aspect of the present invention is to combine a compound represented by the following general formula (I): Ih R1 (wherein rtl, R2 and R3 are the same as above) and p-xylylene dichloride into a compound/ The present invention provides a method for producing an imidazolium salt type polycation represented by the above formula (0) by carrying out a heating reaction in a solvent in which I) and p-xylylene dichloride are dissolved.

The third aspect of the present invention is a compound represented by the following general formula (+v): t1 (wherein R1, R2 and RJ have the same meanings as above) and p-xylylene dichloride in a solvent in which both are dissolved. After that, an inorganic base is added to the reaction solution, the precipitated inorganic salt is separated, and the solution is heated to produce an imidazolium salt type polycation compound represented by the general formula (I). This is what we provide.

(Polycation) As a specific example of the imidazolium salt type polycation represented by the general formula (I) of the present invention, in the general formula (I),
R1 is a hydrogen atom, a C1-17 alkyl group such as methyl, ethyl, propyl, hexyl, undecyl, heptadecyl group, or C6-B such as phenyl, tolyl, xylyl group
Ryl group; R2 and R3 are the same or different substituents, hydrogen atom or C such as methyl, ethyl, propyl group
1 to 3 alkyl groups: X is a halogen anion such as chlorine or bromine, a hydroxide ion, or 1/2 (sulfate ion).

Examples of specific compound structures include the following.

This polycation itself can act as a flocculant, antibacterial agent,
It is used as a fungicide, and when dissolved in a solvent, as an antistatic agent and a hair softening agent.

(Production Example of Polycation) The polycation of the present invention is an α, α′-p-xylene compound represented by the general formula (I1)% (wherein R,, R2 and R3 have the same meanings as above). It is obtained by reacting lyrubisimidazoles and p-xylylene dichloride in a solvent.

α, α′-p-xy, lilyrubisimidazoles represented by the above general formula (I) include α, α-bis-(imidazolyl(I))-p-xylene, α, α′-·bis- (2-methylimidazolyl(I))-p-xylene,
α,α′-Bis(2-methylimidazolyl(I))-
p-xylene, α,α′-bis-(2-propylimidazolyl(I))-p-xylene, α,α′-bis(2
-phenylimidazolyl(I)-p-xylene, α,
α′-bis(2-undecylimidazolyl(I))
-p-xylene, α,α'-bis(2-ethyl-4
-methylimidazolyl(I)-p-xylene, α, α
'-Bis(2,4-dimethylimidazolyl(I))-
p-xylene, α, α'-bis-(2-phenyl-4-
Examples include methylimidazolyl(I)-p-xylene.

As the solvent, a solvent is used that is inert to the reaction components and the polycation of the reaction product and in which the reaction components are dissolved. For example, methanol.

Examples include ethanol, dimethylformamide, dimethyl sulfoxide, hexamethylphosphortriamide, etc.
These may be used alone or in combination of two or more. Furthermore, water may be added to these solvents.

The reaction molar ratio is 1 mole of bisimidazoles:
p-xylylene dichloride is used in a proportion of 0.5 to 2.0 mol, and in order to make the molecule tya' large, especially 0.
．． 9 to 1.1 mol is preferred.

The reaction temperature is 30-150°C, preferably 50-100°C.
It is ℃. The reaction rate is slow below 30°C.

If the temperature exceeds 150°C, side reactions tend to occur, which is not preferable.

The reaction time is preferably 2 to 200 hours, and in particular K is preferably 20 hours or more in order to increase the molecule 't. 1. As a reaction procedure, bisimidazoles and p-xylylene dichloride are dissolved in a solvent. You can also use the method of adding them simultaneously into a solution of bisimidazoles.

A method of dropping p-xylylene dichloride solution may also be used. After the reaction is completed, a white powdery polycation can be obtained by pouring the reaction solution into a poor solvent for polycations such as a7tone or ether.

As another manufacturing method, general formula (Iv) (wherein R1,
It2 and R3 have the same meanings as above. ) and p-xylylene dichloride are heated in a solvent in which both are dissolved.

Thereafter, an inorganic base is added to the reaction solution, the precipitated inorganic salt is separated, and the solution is heated to obtain a polycation.

The imidazoles represented by the above general formula (Iv) include imidazole and 2-methylimidazole.

2-ethylimidazole, 2-propylimidazole,
2-phenylimidazole. 2-wandecylimidazole, 2-heptadecyl imidazole.

Examples include 2-ethyl-4-methylimidazole, 2,4-dimethylimidazole, and 2-phenyl-4-methylimidazole.

The reaction solvent used is one that is inert to imidazoles and xylylene dichloride and that dissolves the reaction components. An example is methanol.

Examples include ethanol, dimethylformamide, dimethyl sulfoxide, hexamethylphosphortriamide, etc.
These may be used alone or in combination of two or more. Preferably, the reaction is carried out in equimolar ratios. The reaction temperature is 30
-100°C, preferably 40-80°C, reaction time preferably 1-20 hours, tP! f preferably 2
~10 hours should be used. After the reaction is completed, an equimolar amount of an inorganic base is dissolved in an alcohol such as methanol or ethanol, and the solution is added to the reaction solution, followed by stirring for 1 to 10 hours while cooling to about 0 to 4°C. Thereafter, after separating the precipitated inorganic salt, the solution is heated to 30 to 150°C, preferably 50 to 100°C for 2 to 200°C.
Heat for an hour. In order to increase the molecular weight of the polycation obtained, heating for 20 hours or more is preferable. After the reaction is completed, the reaction solution is poured into a poor solvent for polycations such as setone or ether to obtain a white powdery polycation.

In the following examples, parts and parts are by weight. These examples are not intended to limit the scope of the invention.

(Example 1) 30.9 mol (0.13 mol) of α,α'-bis(imidazolyl(I))-p-xylene and 23.0 mol (0.13 mol) of p-xylylene dichloride were mixed in 100 sd. Dissolved in dimethylformamide and tooy water, 80
'CK and heated for about 60 hours.

Thereafter, the reaction solution was poured into about 1000 m of acetone to precipitate a polymer. After P separation, wash (・Dry under reduced pressure to remove white powder polycation (PC) 50
I got 5E.

The obtained polycation was analyzed and the following results were obtained.

O infrared absorption spectrum characteristics absorption position (KBr method.

Unit m) 3400.1630% 1560,1440°1360
．． 1150, 1020, 770.730°0 Proton nuclear magnetic resonance spectral characteristics Absorption position (solvent dimethyl sulfoxide-d6, unit δ (ppm)) 65.5-5.6 (H-3, 4, 9, 10: m , 4H)
67.3~7.5 (H-5,6,7,8:m, 4H
)o 7.7~7.9 (H-1,2: m, 2
H) O elemental analysis/Intrinsic viscosity 1 degree [η] (solvent, methanol, 30°C) 0
．． 18 From the above results, the PC-A obtained in this example is as follows.

general formula %formula%) It can be seen that it has the following structure.

(Example 2) 2-methylimidazole 16.49 (0.2 mol), p-xylylene dichloride 35 f (0.2 mol), Y200d dimethyl sulfoxide and 100d methanol were dissolved to give 5o6cK of about 8 Heating was performed for a period of time.

Thereafter, one reaction solution was ice-cooled in a water bath, and caustic soda 81 (
The mixture was added to a methanol-soluble reaction solution containing 0.2 mol of chloride, and after separating the precipitated IJ chloride, the reaction solution was heated at 70° C. for about 30 hours.

Then, pour the reaction solution Y into 1000 d of acetone to form a polymer! It was precipitated. After separation, the polycation is washed and dried under reduced pressure to form a white powder polycation (referred to as PC-B) 37
．． I got 59.

The obtained PC-Bv was analyzed and the following results were obtained.

] O infrared absorption is determined by Kutle characteristic absorption position fil (KBr method,
Unit cII & -1) 3400.1630.1530.1430°1360.
1260.11?0.750, O proton nuclear magnetic resonance spectrometer has a characteristic absorption position (solvent, dimethyl sulfoxide).
d6, unit δ (pI) m)) o 2.5 to 2.7 (I4-3.4,5: m
, 3H)65.3~5.4 (H-6,7,12
,13;m, 4H)07.3~7.6 (H-8,9
, 10, 11; m, 4H) 07.7-7.9 (H
-1,2:m, 2H) 0 Elemental analysis O Intrinsic viscosity (solvent, methanol, 306C) 0.08
From the above results, PC-B obtained in this example is (n
is approximately 10. ) It can be seen that it has the structure of

(Example 3) α,α′-bis(2-ethyl-4-methylimidanlyl(I))-1)-xylene 12.39 (0,0
38 mol) and p-xylylene dichloride 6.7y (
0,038 mol) and 7200 d of dimethylformamide and 100 mol of methanol at 64°C.
Heating was performed for 0 hours.

Thereafter, the reaction solution was poured into about ioog of acetone to precipitate a polymer. After separation, white powder polycation (referred to as PC-C) 11”a was washed and dried under reduced pressure.
'Obtained.

The obtained polycation was analyzed and the following results were obtained.

0 Infrared absorption spectrum characteristic absorption position # (KBr method.

Unit ct&) 3400% 1630, 1520, 1440° 1360
+ 1170, 1110.7600 proton nuclear magnetic resonance spectrum characteristic absorption position (solvent dimethyl sulfoxy t
'd6: unit δ(+)I)m)) o O,8~1.2 (ll-7,8,9:rn,
3H) o2,1~2.3(H-1,2,3:m,3l
-1) 02.9~3.0 (I-1-5,6; m, 2
H) 05.3 to 5.5 (H-10, 11, 16, 17
;m, 4H) o7.1~7.5 (H-12,13
, 14, 15:m, 4H) 07.5-7.8 (I-
i-4: m, IH) O elemental analysis O intrinsic viscosity [η] (solvent methanol: 30°C) 0.0
6 From the above results, it can be seen that the PC-C obtained in this example has the structure of the general formula (%).

(Application example l) and 100 parts of polyvinyl chloride with an average degree of polymerization of SOO.

1 g of octyltin mercaptan as a stabilizer and 2 parts of PC-A obtained in Example 1 as an antistatic agent were mixed, kneaded at 170°C, and then pressed at 175°C to a thickness of 1. I got Qas+ seatra. The surface resistivity value of the obtained sheet was 5.5×10 7 Ω. In addition, PC-A￥
The surface resistivity value of a polyvinyl chloride sheet produced in the same manner without addition was 5XtOΩ.

Claims (1)

[Claims] 1) An imidazolium salt type polycation compound represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, R_1 represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or an aryl group having 6 to 8 carbon atoms; R_2 and R_3 are the same and may be different, and each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
■ represents a halogen ion, hydroxide ion, or 1/2 (sulfate ion); n represents a number from 1 to 10,000; T_1 and T_2 may be the same or different, and each represents a halogen atom Or the following formula (II): ▲ Numerical formula, chemical formula, table, etc. ▼ (II) (In the formula, R_1, R_2 and R_3 have the same meanings as above.) Represents a residue represented by the following formula (II): ] 2) General formula (III) below: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) The compound represented by (III) and p-xylylene dichloride are dissolved in the compound (III) and p-xylylene dichloride. A method for producing an imidazolium salt type polycation compound represented by the following general formula (I) by carrying out a heating reaction in a solvent. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, R_1 represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or an aryl group having 6 to 8 carbon atoms; R_2 and R_3 are the same and may be different, and each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
■ represents a halogen ion, hydroxide ion, or 1/2 (sulfate ion); n represents a number from 1 to 10,000; T_1 and T_2 may be the same or different, and each represents a halogen atom Or the following formula (II): ▲ Numerical formula, chemical formula, table, etc. ▼ (II) (In the formula, R_1, R_2 and R_3 have the same meanings as above.) Represents a residue represented by the following formula (II): ] 3) The following general formula (IV): ▲There are mathematical formulas, chemical formulas, tables, etc.▼The compound represented by (IV) and p-xylylene dichloride are heated in a solvent in which both are dissolved, and then added to the reaction solution. A method for producing an imidazolium salt type polycation compound represented by the following general formula (I) by adding an inorganic base to the solution, separating the precipitated inorganic salt, and then heating the solution to react. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or an aryl group having 6 to 8 carbon atoms; R_2 and R_3 may be the same or different. each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
■ represents a halogen ion, hydroxide ion, or 1/2 (sulfate ion); n represents an integer of 1 or more; T_1 and T_2 may be the same or different, and each represents a halogen atom or the following formula (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) Represents a residue represented by (In the formula, R_1, R_2, and R_3 have the same meanings as above.) ]