JP2006182716A - Pyridinium salt - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new pyridinium=bis(trifluoromethanesufonyl)imidate salt capable of imparting conductivity comparatively stabilized against the change of the environment, particularly against humidity to a resin. <P>SOLUTION: The pyridinium=bis(trifluoromethanesulfonyl)imidate salt is represented by formula (1) (wherein R is a 5-20C straight-chain or branched-chain alkyl group (other than an 8C alkyl group); and R<SP>1</SP>is a 1-4C straight-chain or branched-chain alkyl group). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel pyridinium salt that is effectively used as a conductivity imparting agent.

Conventionally, in order to impart conductivity to a resin or the like, a method of adding an ionic surfactant having a halogen ion, sulfate ion or nitrate ion as an anion to the resin is known (for example, , See Patent Document 1). However, since resins with ionic surfactants are highly environmentally dependent, especially on humidity, they are not satisfactory in terms of quality. There is a need for agents.
JP 2002-363246 A

It is an object of the present invention to provide a novel pyridinium salt that can impart to a resin a relatively stable conductivity against environmental changes.

  The present invention relates to a pyridinium salt represented by the formula (1) (hereinafter referred to as pyridinium salt (1)). Formula (1):

［式中、Ｒは炭素数５〜２０のアルキル基（但し、炭素数８のアルキル基は除く）を示し、Ｒ^１は炭素数１〜４のアルキル基を示す。］

[Wherein, R represents an alkyl group having 5 to 20 carbon atoms (excluding an alkyl group having 8 carbon atoms), and R ¹ represents an alkyl group having 1 to 4 carbon atoms. ]

By using the pyridinium salt (1) of the present invention as a conductivity-imparting agent in a resin, it is possible to produce a resin having less conductive environmental dependency as compared with conventional ionic surfactants.

The present invention will be specifically described below.
In the formula (1), R represents a linear or branched alkyl group having 5 to 20 carbon atoms (excluding an alkyl group having 8 carbon atoms), and is preferably a linear alkyl group. Specifically, pentyl, hexyl, heptyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, etc. Is mentioned.

In the formula (1), R ¹ represents a linear or branched alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, or a tert-butyl group. And preferably a methyl group and an ethyl group.

  Specific examples of the pyridinium salt (1) include 1-pentyl-2-methylpyridinium bis (trifluoromethanesulfonyl) imidate, 1-hexyl-2-methylpyridinium bis (trifluoromethanesulfonyl) imidate, 1-heptyl-2 -Methylpyridinium bis (trifluoromethanesulfonyl) imidate, 1-nonyl-2-methylpyridinium bis (trifluoromethanesulfonyl) imidate, 1-decyl-2-methylpyridinium bis (trifluoromethanesulfonyl) imidate, 1-undecyl- 2-methylpyridinium bis (trifluoromethanesulfonyl) imidate, 1-dodecyl-2-methylpyridinium bis (trifluoromethanesulfonyl) imidate, 1-tridecyl-2-methylpi Dinium = bis (trifluoromethanesulfonyl) imidate, 1-tetradecyl-2-methylpyridinium = bis (trifluoromethanesulfonyl) imidate, 1-pentadecyl-2-methylpyridinium = bis (trifluoromethanesulfonyl) imidate, 1-hexadecyl-2- Methylpyridinium bis (trifluoromethanesulfonyl) imidate, 1-heptadecyl-2-methylpyridinium bis (trifluoromethanesulfonyl) imidate, 1-octadecyl-2-methylpyridinium bis (trifluoromethanesulfonyl) imidate,

1-pentyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imidate, 1-hexyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imidate, 1-heptyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imidate 1-nonyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imidate, 1-decyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imidate, 1-undecyl-3-methylpyridinium bis (trifluoromethanesulfonyl) Imidate, 1-dodecyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imidate, 1-tridecyl-3-methylpyridinium bis (trifluoromethanes) Phonyl) imidate, 1-tetradecyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imidate, 1-pentadecyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imidate, 1-hexadecyl-3-methylpyridinium bis (trifluoro) Romethanesulfonyl) imidate, 1-heptadecyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imidate, 1-octadecyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imidate,

  1-pentyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imidate, 1-hexyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imidate, 1-heptyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imidate 1-nonyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imidate, 1-decyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imidate, 1-undecyl-4-methylpyridinium bis (trifluoromethanesulfonyl) Imidate, 1-dodecyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imidate, 1-tridecyl-4-methylpyridinium bis (trifluoromethanes) Phonyl) imidate, 1-tetradecyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imidate, 1-pentadecyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imidate, 1-hexadecyl-4-methylpyridinium bis (trifluoro) Romethanesulfonyl) imidate, 1-heptadecyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imidate, 1-octadecyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imidate and the like.

The pyridinium salt (1) of the present invention is represented by, for example, the formula (2):

（式中、Ｒ^１は前記に同じ。）で表されるピリジン類（以下、ピリジン類（２）という）と式（３）：

(Wherein R ¹ is the same as above) and pyridines (hereinafter referred to as pyridines (2)) and formula (3):

RX (3)
(Wherein, R is the same as above, and X represents a halogen atom) is reacted with an alkyl halide represented by the following formula (4):

（式中、Ｒ、Ｒ^１及びＸは前記に同じ。）で表されるピリジニウム＝ハライド（以下、ピリジニウム＝ハライド（４）という）を製造し、次いで得られたピリジニウム＝ハライド塩（４）をビス（トリフルオロメタンスルホニル）イミド酸又はそのアルカリ金属塩［以下、ビス（トリフルオロメタンスルホニル）イミド酸類という］を用いてイオン交換反応をすることで製造できる。

(Wherein R, R ¹ and X are the same as described above), and the resulting pyridinium halide salt (4) is produced. It can be produced by performing an ion exchange reaction using bis (trifluoromethanesulfonyl) imide acid or an alkali metal salt thereof [hereinafter referred to as bis (trifluoromethanesulfonyl) imide acid].

Examples of pyridines (2) include 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, and preferably 2- Methylpyridine, 3-methylpyridine and 4-methylpyridine.

  Examples of the alkyl halides (3) include pentyl chloride, hexyl chloride, heptyl chloride, nonyl chloride, decyl chloride, undecyl chloride, dodecyl chloride, tridecyl chloride, tetradecyl chloride, pentadecyl chloride, hexadecyl chloride, Heptadecyl chloride, octadecyl chloride, nonadecyl chloride, icosyl chloride, pentyl bromide, hexyl bromide, heptyl bromide, nonyl bromide, decyl bromide, undecyl bromide, dodecyl bromide, tridecyl bromide, tetradecyl bromide, pentadecyl bromide, hexadecyl Bromide, heptadecyl bromide, octadecyl bromide, nonadecyl bromide, icosyl bromide, pentyl iodide, hexyl iodide, Ptyl iodide, nonyl iodide, decyl iodide, undecyl iodide, dodecyl iodide, tridecyl iodide, tetradecyl iodide, pentadecyl iodide, hexadecyl iodide, heptadecyl iodide, octadecyl iodide, nonadecyl iodide, icosyl iodide Etc. The amount of the alkyl halides (3) used may be 0.5 mol to 3.0 mol, preferably 0.6 to 2.0 mol, more preferably 1 mol with respect to 1 mol of the pyridines (2). Is 0.8 to 1.5 mol.

  The reaction of the pyridines (2) and the alkyl halides (3) may or may not use a solvent. Examples of the solvent used include alcohols such as methanol, ethanol and isopropanol, acetonitrile and ethyl acetate. , Tetrahydrofuran, dimethylformamide and the like. Although there is no restriction | limiting in particular in the usage-amount of a solvent, It is 10.0 weight part or less normally with respect to 1 weight part of pyridines (2), Preferably it is 1.0-5.0 weight part.

  In order to carry out the reaction between the pyridines (2) and the alkyl halides (3), for example, a mixture of the pyridines (2), the alkyl halides (3) and the solvent can be used for the kind of solvent used in the reaction. However, it is usually only necessary to stir at 20 ° C or higher, preferably 60 ° C to 120 ° C.

  After obtaining a reaction mixture containing pyridinium = halide (4) as described above, the obtained reaction mixture is concentrated to dryness to obtain a residue containing pyridinium = halide (4) as a main component. This residue may be used as it is in the reaction for producing the pyridinium salt (1) of the present invention. If necessary, the residue is mixed with an organic solvent (for example, ethyl ether, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, etc.), and unreacted raw materials contained in the residue are dissolved in the organic solvent, followed by filtration. The resulting purified pyridinium halide (4) can also be used.

  Next, the manufacturing method of pyridinium salt (1) by the ion exchange reaction of pyridinium halide (4) and bis (trifluoromethanesulfonyl) imidic acid will be described.

Examples of the raw material bis (trifluoromethanesulfonyl) imidic acid include bis (trifluoromethanesulfonyl) imidic acid, sodium bis (trifluoromethanesulfonyl) imidic acid, lithium bis (trifluoromethanesulfonyl) imidic acid, and bis (trifluoromethanesulfonyl). Examples thereof include potassium imidoate, and lithium bis (trifluoromethanesulfonyl) imidate is preferable. The amount of bis (trifluoromethanesulfonyl) imidic acid used is usually 0.8 mol or more, preferably 0.9 mol to 1.5 mol, per 1 mol of pyridinium halide (4).

  The ion exchange reaction is usually performed in an aqueous solvent. The amount of water used is not particularly limited, but is usually 20.0 parts by weight or less, preferably 0.5-10.0 parts by weight, particularly preferably 1 with respect to 1 part by weight of pyridinium halide (4). 0.0 parts by weight to 5.0 parts by weight.

  The mixing order of pyridinium halide (4), bis (trifluoromethanesulfonyl) imidic acid and water is not particularly limited, and after adding pyridinium halide (4) and water, bis (trifluoromethanesulfonyl) imidic acid is added. Alternatively, pyridinium halide (4) may be added after mixing bis (trifluoromethanesulfonyl) imidic acid with water. In addition, when coloring becomes a problem, after the pyridinium halide (4) is mixed with water, it is treated with a decoloring agent such as activated carbon, and the filtrate obtained by filtration is used for the ion exchange reaction. it can.

The ion exchange reaction is usually 10 ° C to 80 ° C, preferably 15 ° C to 60 ° C, particularly preferably 20 ° C to 40 ° C, usually 15 minutes or longer, preferably 30 minutes to 2 hours, particularly preferably 45 minutes to 1 hour. Stir to complete.

  The reaction solution after completion of the reaction is separated into an aqueous layer and an organic layer because the water solubility of the pyridinium salt (1) is low. In order to separate the pyridinium salt (1) from the reaction solution, the pyridinium salt (1) is obtained by washing with water if desired and then drying the organic layer. If necessary, a water-insoluble organic solvent (for example, ethyl acetate, methylene chloride, etc.) may be added during or after the reaction to extract the pyridinium salt (1) into a water-insoluble organic solvent. The obtained organic layer is washed with water if desired, and then the organic solvent is distilled off to obtain a pyridinium salt (1) as a residue.

Next, the present invention will be specifically described based on examples, but it goes without saying that the present invention is not limited to these examples.

Example 1
9.3 g (0.10 mol) of 4-methylpyridine, 16.5 g (0.10 mol) of hexyl bromide, and 10.0 g of acetonitrile were mixed and reacted at 80 ° C. for 24 hours. After completion of the reaction, the obtained reaction mixture was concentrated, and the residue was dried under reduced pressure to obtain 14.8 g of 1-hexyl-4-methylpyridinium bromide (yield: 96%).

The 1-hexyl-4-methylpyridinium bromide 24.8 g (0.096 mol) obtained above, 49.6 g of water and 0.74 g of activated carbon were mixed, stirred for 1 hour at room temperature, and filtered. To the obtained filtrate, 28.1 g (0.096 mol) of lithium bis (trifluoromethanesulfonyl) imidoate and 28.1 g of methylene chloride were added, and the mixture was stirred at 25 ° C. for 1 hour. After completion of the reaction, the obtained organic layer was separated by a liquid separation operation and washed twice with 49.6 g of water. The organic layer was concentrated to remove methylene chloride, and then the residue was dried under reduced pressure to obtain 41.2 g of liquid 1-hexyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imidate (yield 89.9). %). The NMR data of 1-hexyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imidate are shown below.

¹ H-NMR (CDCl ₃ ) δ: 0.87 (t, 3H), 1.28-1.33 (m, 6H), 1.96 (m, 2H), 2.67 (s, 3H), 4.50 (t, 2H), 7.81 (d, 2H), 8.62 (d, 2H)

Example 2
7.8 g (0.084 mol) of 4-methylpyridine, 25.0 g (0.084 mol) of dodecyl iodide and 10.0 g of acetonitrile were mixed and reacted at 80 ° C. for 24 hours. After completion of the reaction, the resulting reaction mixture was concentrated, and the residue was dried under reduced pressure to obtain 31.2 g of 1-dodecyl-4-methylpyridinium iodide (yield: 95%).

31.2 g (0.095 mol) of 1-dodecyl-4-methylpyridinium iodide obtained above and 62.4 g of water were mixed, and 27.8 g of lithium bis (trifluoromethanesulfonyl) imidoate was added to the obtained aqueous solution. (0.095 mol) and 27.8 g of methylene chloride were added and stirred at 25 ° C. for 1 hour. After completion of the reaction, the obtained organic layer was separated by a liquid separation operation and washed twice with 62.4 g of water. The organic layer was concentrated to remove methylene chloride, and then the residue was dried under reduced pressure to obtain 69.8 g of liquid 1-dodecyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imidate (yield 86.3). %). The NMR data of 1-hexyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imidate are shown below.

¹ H-NMR (CDCl ₃ ) δ: 0.87 (t, 3H), 1.24-1.32 (m, 18H), 1.96 (m, 2H), 2.67 (s, 3H), 4.48 (t, 2H), 7.82 (d, 2H), 8.62 (d, 2H)

Examples 3-5
The corresponding pyridinium salt (1) was prepared in the same manner as in Example 2 except that 4-methylpyridine and dodecyl iodide of Example 2 were replaced with pyridines (2) and alkyl halides (3) shown in Table 1. Got. The NMR data of the corresponding pyridinium salt (1) is shown below.

1-dodecyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imidate
¹ H-NMR (CDCl ₃ ) δ: 0.87 (t, 3H), 1.24 to 1.33 (m, 18H), 1.95 (m, 2H), 2.60 (s, 3H), 4.56 (t, 2H), 7.91 (t, 1H), 8.22 (d, 1H), 8.65 (m, 2H)

1-Hexadecyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imidate
¹ H-NMR (CDCl ₃ ) δ: 0.88 (t, 3H), 1.24-1.32 (m, 26H), 1.96 (m, 2H), 2.67 (s, 3H), 4.50 (t, 2H), 7.81 (d, 2H), 8.61 (d, 2H)

1-octadecyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imidate
¹ H-NMR (CDCl ₃ ) δ: 0.86 (t, 3H), 1.24-1.32 (m, 30H), 1.96 (m, 2H), 2.67 (s, 3H), 4.50 (t, 2H), 7.81 (d, 2H), 8.61 (d, 2H)

Example 6
Epicoat 828 (registered trademark: manufactured by Japan Epoxy Resin Co., Ltd.) 100 parts by weight as an epoxy resin, 14.1 parts by weight of iminobispropylamine as a curing agent, and 1-hexyl-4-methylpyridinium obtained in Example 1 = 10.0 parts by weight of bis (trifluoromethanesulfonyl) imidate was mixed to obtain an epoxy resin composition. Such an epoxy resin composition is poured into a 50 mm × 50 mm × 5 mm deep mold, held at 50 ° C. for 1 hour, and further at 100 ° C. for 6 hours, thermally cured to prepare a sample for evaluation, and the surface resistance value is measured. did. The results are shown in Table 2. In Table 2, the surface resistance value was measured at an applied voltage of 500 V using Megaresta H0709 manufactured by Sicid Electric Industry Co., Ltd.

Examples 7-10
An evaluation sample was prepared in the same manner as in Example 6 except that the pyridinium salt (1) shown in Table 2 was used instead of 1-hexyl-4-methylpyridinium = bis (trifluoromethanesulfonyl) imidate in Example 6. The surface resistance value was measured. The results are shown in Table 2.

Comparative Example 1
A sample for evaluation was prepared in the same manner as in Example 6 except that 1-hexyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imidate of Example 6 was not used, and the surface resistance value was measured. The results are shown in Table 2.

From the results of Table 2, the epoxy resin composition to which the pyridinium salt (1) of the present invention is added as a conductivity-imparting agent is 10 ⁹ to 10 ⁹ Ω compared to the insulating state of the 10 ¹⁶ Ω level when the conductivity-imparting substance is not added. It was found that an extremely low surface resistance value on the order of 10 ¹¹ Ω can be obtained.

Example 11
100 parts by weight of a two-component cross-linking acrylic pressure-sensitive adhesive (SK Dyne 909A manufactured by Soken Chemical Co., Ltd.), 1 part by weight of 1-hexyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imidate obtained in Example 1, A pressure-sensitive adhesive coating solution was prepared by adding 0.2 parts by weight of a curing agent for acrylic resin (L-45, manufactured by Soken Chemical Co., Ltd.) and 150 parts by weight of ethyl acetate / methyl ethyl ketone (50/50) as a diluent solvent. The coating solution was coated on a polyester film with a bar coder at a dry thickness of about 10 μm, and then heat cured at 80 ° C. for 2 minutes to prepare a sample for evaluating an adhesive, and the surface resistance value was measured. As a result, 1 × 10 ¹¹ Ω was shown. In addition, the surface resistance value when 1-hexyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imidate was not added was 5 × 10 ¹⁶ Ω.

Claims (1)

A pyridinium salt represented by the formula (1). Formula (1):

[Wherein, R represents an alkyl group having 5 to 20 carbon atoms (excluding an alkyl group having 8 carbon atoms), and R ¹ represents an alkyl group having 1 to 4 carbon atoms. ]