JPWO2011052601A1 - Ionic organic compound and process for producing the same, and carbon nanotube dispersant comprising the ionic organic compound - Google Patents

Abstract

The present invention provides a novel ionic organic compound represented by the following general formula (I) useful as a carbon nanotube dispersant and a production method thereof by a simple process. Wherein R1, R2 and R3 are hydrogen or an alkyl group, A is a linking site having one or more aromatic rings, or a linking site consisting of a cyclohexane ring, X is an anion, n is nX is − The above compound is obtained from (A) a quaternization reaction between an aromatic diamide compound having a (chloromethyl) benzamide group at both ends or a cyclohexanediamide compound and (B) amines. can get. The obtained ionic organic compound can singly disperse multi-walled and single-walled carbon nanotubes in water as a CNT dispersant.

Description

  The present invention relates to an ionic organic compound useful as a carbon nanotube dispersant and a production method thereof, and also relates to a carbon nanotube dispersion using the compound as a dispersant.

Carbon nanotubes (CNT) have recently attracted attention as a new nanotechnology material (Non-patent Document 1). In particular, single-walled carbon nanotubes (SWCNTs) are expected to be applied to various fields due to their simple structure and unique physicochemical properties represented by metallic and semiconductor properties.
However, due to the association (bundling) of CNT itself due to the high van der Waals interaction, it is extremely difficult to solubilize and disperse CNT in a solvent, which greatly hinders material development and application.

So far, various investigations have been made chemically and physically on the method of dispersing CNTs in a solvent. For example, a method of generating a functional group that promotes solubility in a solvent at the CNT surface or terminal by sonicating CNT in an acidic solution (Non-patent Document 2), or a solvent by mixing a dispersant. There is a method to promote dispersion. As such a dispersant, an ionic amphiphilic compound, a compound having an aromatic functional group, a naturally-derived polymer, a synthetic polymer, and the like have been reported (Patent Document 1, Non-Patent Document 3).
However, chemical functional group generation still requires changes in the physical properties of CNTs, and even when dispersants are used, high-power ultrasonic irradiation using special equipment is often necessary. Many challenges remain.

Japanese Unexamined Patent Publication No. 2004-2850 (Publication Date: January 8, 2004)

S.Iijima, Nature, 354,56 (1991), S.Iijima, T.Ichihashi, Nature, 363,603 (1993) J. Chen, et al., Science, 282, 95 (1998). M.J.O'Connell, et al., Science, 297,593 (2002).

As described above, although various studies have been conducted on the method for producing a CNT dispersion, it has been sufficiently developed a dispersant that can easily and effectively disperse CNT without changing the properties of CNT. I can't say that.
The present invention has been made in view of the above problems, and it is an object of the present invention to provide a method for easily and rapidly producing a solution in which CNTs are stably dispersed in a solvent.

  As a result of intensive studies in view of the above problems, the present inventors have found that CNTs can be easily and effectively added to an aqueous solution by using an ionic organic compound having an ammonium-type cation moiety at both ends of the molecule as a solubilizer. The inventors have found that they can be dispersed, and have completed the present invention.

That is, according to this application, the following invention is provided.
(1) An ionic organic compound represented by the following general formula (I).
(Wherein R ¹ , R ² and R ³ are hydrogen or an alkyl group, A is a linking site having one or more aromatic rings, or a linking site consisting of a cyclohexane ring, X is an anion, n is nX is −2 It is a number that becomes a valence.)
(2) In the general formula (I), X is a halogen atom (F, Cl, Br, I), tetrafluoroboric acid group (BF ₄ ), hexafluorophosphoric acid (PF ₆ ), bis (trifluoromethanesulfonyl) Amide (TFSA), thioisocyanate (SCN), nitrate group (NO ₃ ), sulfate group (SO ₄ ), thiosulfate group (S ₂ O ₃ ), carbonate group (CO ₃ ), bicarbonate group (HCO ₃ ), Phosphoric acid group, phosphorous acid group, hypophosphorous acid group, each halogen acid compound acid group (AO ₄ , AO ₃ , AO ₂ , AO: A = Cl, Br, I), tris (trifluoromethylsulfonyl) carbon Acid group, trifluoromethylsulfonic acid group, dicyanamide group, acetic acid group (CH ₃ COO), halogenated acetic acid group ((CA _n H _3-n ) COO, A = F, Cl, Br, I; n = 1, 2, 3), Te Rafeniruhou acid (BPh ₄₎ and its derivative _{(B (Aryl) 4: Aryl} = substituted phenyl group), characterized in that at least one member selected from ionic organic compound according to (1).
(3) (A) Quaternizing a compound represented by the following general formula (II) having (chloromethyl) benzamide groups at both ends and (B) an amine represented by the following general formula (III) The method for producing an ionic organic compound according to (1), wherein the reaction is performed.
(In the formula, A represents a linking site having one or more aromatic rings or a linking site consisting of a cyclohexane ring.)
(In the formula, R ¹ , R ² and R ³ represent hydrogen or an alkyl group.)
(4) The method for producing an ionic compound according to (3), wherein the quaternization reaction is performed in dimethylformamide or acetonitrile at 50 to 80 ° C.
(5) The method for producing an ionic compound according to (3) or (4), further comprising substituting the anion of the obtained ionic compound with another anion by an anion exchange reaction.
(6) A CNT dispersant comprising the ionic organic compound described in (1).
(7) A CNT dispersion containing the CNT dispersant described in (6).

  By using the dispersant of the present invention, an aqueous dispersion in which CNTs are easily and efficiently dispersed can be easily provided. Furthermore, the dispersion is useful for the development of new composite materials (CNT-containing films, CNT-containing paints, etc.) using CNT as an elemental raw material.

FIG. 1 shows the multilayer CNT dispersion liquid of Example 23 (using the compound of formula (12) as a dispersant). FIG. 2 shows the SWCNT dispersion of Example 24 (using the compound of formula (12) as a dispersant). FIG. 3 is a diagram showing a UV-Vis-NIR spectrum of the SWCNT dispersion of Example 24 (using the compound of formula (12) as a dispersant in heavy water). FIG. 4 is a diagram showing a UV-Vis-NIR spectrum of the SWCNT dispersion of Example 25 (using the compound of formula (12) as a dispersant).

  Next, the best mode for carrying out the present invention will be described by way of examples, but the present invention is not limited to these examples. All modifications and other embodiments or examples within the scope of the technical idea of the present invention are included in the present invention.

As a preferable ionic organic compound represented by the above general formula (I), a compound represented by the following general formula (A1) is exemplified.
(In the formula, the amine moiety represented by R ¹ R ² R ³ N is ethyldimethylamine, n-propyldimethylamine, n-butyldimethylamine, n-hexyldimethylamine, n-octyldimethylamine, n-decyldimethyl. A functional group derived from amine, n-dodecyldimethylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, and X is a halogen ion (F, Cl, Br, I), bis (trifluoromethanesulfonyl) amide group (TFSA) , Tetrafluoroborate group (BF ₄ ), hexafluorophosphate group (PF ₆ ), thiocyanate (SCN), nitrate group (NO ₃ ), sulfate group (SO ₄ ), thiosulfate group (S ₂ O ₃ ), carbonate group _(CO 3), bicarbonate radical _(HCO 3), phosphoric acid group, phosphorous acid group, hypophosphorous acid group, each halogen Oxide groups _{(XO 4, XO 3, XO} 2, XO: X = Cl, Br, I), tris (trifluoromethylsulfonyl) carbon group, trifluoromethyl sulfonic acid, dicyanamide group, acetate group (CH ₃ COO), haloacetic acid group _{((CX n H 3-n} ) COO, X = F, Cl, Br, I; n = 1,2,3), tetraphenylborate group (BPh ₄₎ and its derivatives (At least one selected from B (Aryl) ₄ : Aryl = substituted phenyl group) is shown.)

Other representative compound examples (A2-A8) are also shown below.

  The ionic organic compound of the present invention represented by the above general formula (I) is a substituted (A) compound represented by the above general formula (II) having 4- (chloromethyl) benzamide groups at both ends. Obtained by a quaternization reaction of an aromatic diamide compound or a cyclohexanediamide compound which may have a group with an amine represented by the above general formula (III), followed by an anion exchange reaction. It is done. As the amines, those selected from amines having 1 to 12 carbon atoms in the substituent on the nitrogen atom are preferable. The condensation reaction solvent is preferably a polar organic solvent such as dimethylformamide or acetonitrile, but is not limited thereto. The reaction time is preferably 12 to 48 hours. The reaction temperature is preferably about 50 to 80 ° C, particularly about 80 ° C. Although it is desirable to use water as the solvent for the anion exchange reaction, the present invention is not limited to this. The reaction time is preferably about 5 minutes to 1 hour. The reaction temperature is preferably about 80-100 ° C.

  (A) Specific examples of the aromatic diamide compound having a 4- (chloromethyl) benzamide group at both ends include, for example, 4,4′-bis [(4-chloromethyl) benzamide] benzanilide, and 1,3- Bis {(4-chloromethyl) benzamido} benzene. Specific examples of the aromatic diamide compound having a 4- (chloromethyl) benzamide group at both ends and having a substituent include 4,4′-bis [(4-chloromethyl) benzamide] -3, 3 ′. -Dimethoxybiphenyl, 2,7-bis [(4-chloromethyl) benzamido] fluorene, 4,4'-bis [(4-chloromethyl) benzamido] -3,3'-dimethylbiphenyl, 4,4'-bis [(4-Chloromethyl) benzamide] -3,3 ′, 5,5′-tetramethylbiphenyl, 4,4′-bis [{(4-chloromethyl) benzamido} phenyl] methane. Specific examples of the cyclohexane diamide compound include trans-1,4-bis [(4-chloromethyl) benzamide] cyclohexane.

  Examples of the substituent on the nitrogen atom of (B) amines include alkyl groups having about 1 to 12 carbon atoms such as methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, and dodecyl groups, and phenethyl groups. It is done. Specific examples of such amine compounds include, for example, ethyldimethylamine, n-propyldimethylamine, n-butyldimethylamine, n-hexyldimethylamine, n-octyldimethylamine, n-decyldimethylamine, n-dodecyldimethyl. Amine, trimethylamine, triethylamine, tripropylamine, tributylamine, (R)-(+)-N, N-dimethyl-1-phenylethylamine, (S)-(−)-N, N-dimethyl-1-phenylethylamine Is mentioned.

  The ionic organic compound represented by the general formula (I) obtained by the above method has excellent properties as a CNT dispersing agent, and after the compound is heated and dissolved in neutral water, it is mixed with CNT. A CNT dispersion can be obtained by ultrasonic irradiation. In these compounds, ionic quaternized nitrogen atoms are responsible for water solubility, aromatic rings, hydrocarbon sites (hydrophobic interactions), and cation / anion charge (electrostatic interaction). Etc. are considered to be responsible for intermolecular interactions with CNTs and to break up the aggregation of CNTs to obtain a dispersion.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, the following specific examples do not limit this invention.
In the following examples, 4- (chloromethyl) benzoyl chloride, 4,4′-diamino-3,3′-dimethoxybiphenyl (o-dianisidine), 4,4′-, which is a raw material for producing an organic ionic compound Diaminobenzanilide, bis (4-aminophenyl) methane, 2,7-diaminofluorene, o-toluidine, 3,3 ′, 5,5′-tetramethylbenzidine, m-phenylenediamine, trans-1,4-diamino Cyclohexane, ethyldimethylamine, n-propyldimethylamine, n-butyldimethylamine, n-hexyldimethylamine, n-octyldimethylamine, n-decyldimethylamine, n-dodecyldimethylamine and acetonitrile were purchased from Tokyo Chemical Industry. Things were used. Dehydrated methylene chloride and N, N-dimethylformamide were purchased from Kanto Chemical. Triethylamine was purchased from Wako Pure Chemical Industries. The lithium bis (trifluoromethanesulfonyl) imide used was purchased from Kishida Chemical.

Example 1 Synthesis of 4,4′-bis [(4-chloromethyl) benzamide] -3,3′-dimethoxybiphenyl and Synthesis of Compound (A1) by Quaternary Amination
4,4′-Diamino-3,3′-dimethoxybiphenyl (o-dianisidine) (2.44 g, 10.0 mmol) and triethylamine (2.23 g, 22.0 mmol) were dehydrated methylene chloride (90 mL). Dissolved in. A solution of 4-chloromethylbenzoyl chloride (3.78 g, 20.0 mmol) in dehydrated methylene chloride (60 mL) was added thereto over 1 hour with stirring. Thereafter, the mixture was heated to reflux for 4 hours and then stirred at room temperature for 13 hours. The precipitate was filtered off to obtain the title compound represented by the following formula (2) as a yellow powder. Yield 4.69 g, 85% yield. The structure was confirmed from the proton NMR spectrum of the obtained compound. ¹ H-NMR (300 MHz, DMSO-d ₆ ) δ 3.97 (s, 6H), 4.86 (s, 4H), 7.33 (dd, J = 2Hz, 8Hz, 2H), 7.39 (d, J = 2Hz, 2H ), 7.60 (d, J = 8Hz, 4H), 7.90 (d, J = 8Hz, 2H), 7.99 (d, J = 8Hz, 4H), 9.53 (s, 2H).
4,4′-bis [(4-chloromethyl) benzamide] -3,3′-dimethoxybiphenyl (0.55 g, 1.0 mmol) obtained by the above reaction and n-hexyldimethylamine (0.39 g, 3 0.0 mmol) was heated and stirred in dimethylformamide (40 mL) at 80 ° C. for 48 hours. After cooling to room temperature, the ionic organic compound represented by the following formula (3) was obtained in a yield of 92% by filtering the precipitate produced by adding the reaction solution to a large amount of acetone. The structure was confirmed from the proton NMR spectrum of the obtained compound. ¹ H-NMR (300 MHz, DMSO-d ₆ ) δ 0.90 (t, J = 6.7 Hz, 6H), 1.33 (br, 12H), 1.80 (br, 4H), 3.00 (s, 12H), 3.26-3.30 (m, 4H), 3.97 (s, 6H), 4.63 (s, 4H), 7.34-7.40 (m, 4H), 7.72 (d, J = 8.2Hz, 4H), 7.85 (d, J = 8.2Hz, 2H), 8.12 (d, J = 8.2Hz, 4H), 9.67 (s, 2H).

Example 2 Synthesis of 4,4′-bis [(4-chloromethyl) benzamido] benzanilide and Synthesis of Compound (A2) by Its Quaternary Amination
In the same manner as in Example 1 except that 4,4′-diaminobenzanilide was used instead of 4,4′-diamino-3,3′-dimethoxybiphenyl (o-dianisidine) in Example 1 above, The title compound represented by the formula (4) was obtained. Yield 96%. The product was a compound that was hardly soluble in the solvent.
In Example 1 above, 4,4′-bis [(4-chloromethyl) benzamide] benzanilide was used instead of 4,4′-bis [(4-chloromethyl) benzamide] -3,3′-dimethoxybiphenyl. An ionic organic compound represented by the following formula (5) was obtained in the same manner as in Example 1 except that it was used. Yield 59%. The structure was confirmed from the proton NMR spectrum of the obtained compound. ¹ H-NMR (300 MHz, DMSO-d ₆ ) δ 0.88-0.92 (m, 6H), 1.33 (s, 12H), 1.81 (br, 4H), 2.99 (s, 12H), 3.26 (s, 4H) , 4.86 (s, 4H), 7.70-7.76 (m, 4H), 7.78 (s, 4H), 8.00 (q, J = 9.0Hz, 4H), 8.13 (t, J = 8.5Hz, 4H), 10.23 ( s, 1H), 10.42 (s, 1H), 10.70 (s, 1H).

(Example 3)
In Example 2 above, an ionic organic compound represented by the following formula (6) was obtained in the same manner as in Example 2 except that n-octyldimethylamine was used instead of n-hexyldimethylamine. . Yield 73%. The structure was confirmed from the proton NMR spectrum of the obtained compound. ¹ H-NMR (300 MHz, DMSO-d ₆ ) δ 0.86-0.88 (m, 6H), 1.28-1.32 (m, 20H), 1.81 (br, 4H), 2.99 (s, 12H), 3.26 (br, 4H), 4.61-4.62 (m, 4H), 7.70-7.78 (m, 8H), 8.00 (q, J = 8.5Hz, 4H), 8.13 (t, J = 8.5Hz, 4H), 10.23 (s, 1H ), 10.41 (s, 1H), 10.70 (s, 1H).

Example 4
In Example 2, an ionic organic compound represented by the following formula (7) was obtained in the same manner as in Example 2 except that ethyldimethylamine was used instead of n-hexyldimethylamine. Yield 69%. The structure was confirmed from the proton NMR spectrum of the obtained compound. ¹ H-NMR (300 MHz, DMSO-d ₆ ) δ 1.36 (t, J = 7.2 Hz, 6 H), 2.97 (s, 12 H), 3.35 (t, J = 7.3 Hz, 4 H), 4.61 (s, 4 H ), 7.71-7.78 (m, 8H), 8.00 (q, J = 9.1Hz, 4H), 8.13 (t, J = 8.6Hz, 4H), 10.23 (s, 1H), 10.42 (s, 1H), 10.71 (s, 1H).

Example 5 (Synthesis of 2,7-bis [(4-chloromethyl) benzamido] fluorene and synthesis of compound (A3) by its quaternary amination)
The following formula was used in the same manner as in Example 1 except that 2,7-diaminofluorene was used instead of 4,4′-diamino-3,3′-dimethoxybiphenyl (o-dianisidine) in Example 1 above. The title compound represented by (8) was obtained. Yield 99%. The structure was confirmed from the proton NMR spectrum of the obtained compound. ¹ H-NMR (300 MHz, DMSO-d ₆ ) δ 3.96 (s, 2H), 4.86 (s, 4H), 7.61 (d, J = 8Hz, 4H), 7.73-7.82 (m, 4H), 7.97 ( d, J = 8Hz, 4H), 8.07 (s, 2H), 10.34 (s, 2H).
In Example 1, 2,7-bis [(4-chloromethyl) synthesized in the above reaction instead of 4,4′-bis [(4-chloromethyl) benzamide] -3,3′-dimethoxybiphenyl Benzamide] An ionic organic compound represented by the following (9) was obtained in the same manner as in Example 1 except that n-butyldimethylamine was used instead of fluorene and n-hexyldimethylamine, respectively. Yield 84%. The structure was confirmed from the proton NMR spectrum of the obtained compound. ¹ H-NMR (300 MHz, DMSO-d ₆ ) δ 1.34 (qt, J = 7.4 Hz, 4H), 1.81 (br, 4H), 3.01 (s, 12H), 3.28 (br, 4H), 3.97 (s , 2H), 4.64 (s, 4H), 7.72-7.77 (m, 4H), 7.80-7.85 (m, 4H), 8.14 (d, J = 8.3Hz, 6H), 10.53 (s, 2H).

(Example 6)
In the above Example 5, an ionic organic compound represented by the following (10) was obtained in the same manner as in Example 5 except that n-ethyldimethylamine was used instead of n-butyldimethylamine. Yield 92%. The structure was confirmed from the proton NMR spectrum of the obtained compound. ¹ H-NMR (300 MHz, DMSO-d ₆ ) δ 1.37 (t, J = 7.2 Hz, 6H), 2.98 (s, 12H), 3.38-3.42 (m, 4H), 3.97 (s, 2H), 4.62 (s, 4H), 7.72-7.85 (m, 8H), 8.14 (d, J = 8.5Hz, 6H), 10.52 (s, 2H).

Example 7 Synthesis of 4,4′-bis [(4-chloromethyl) benzamide] -3,3′-dimethylbiphenyl and Synthesis of Compound (A4) by Its Quaternary Amination
In the same manner as in Example 1 except that o-toluidine was used instead of 4,4′-diamino-3,3′-dimethoxybiphenyl (o-dianisidine) in Example 1, the following formula (11) The title compound represented by was obtained. Yield 98%. The structure was confirmed from the proton NMR spectrum of the obtained compound. ¹ H-NMR (300 MHz, DMSO-d ₆ ) δ 2.33 (s, 6H), 4.86 (s, 4H), 7.46 (d, J = 8.2Hz, 2H), 7.53-7.62 (m, 8H), 8.01 (d, J = 8.2Hz, 4H), 9.94 (s, 2H).
In Example 1, 4,4′-bis [(4-chloromethyl) benzamide] -3,3′-dimethoxybiphenyl was replaced with 4,4′-bis [(4-chloromethyl) synthesized by the above reaction. ) Benzamide] -3, 3′-dimethylbiphenyl, ion represented by the following (12) in the same manner as in Example 1 except that n-butyldimethylamine was used instead of n-hexyldimethylamine, respectively. An organic compound was obtained. Yield 57%. The structure was confirmed from the proton NMR spectrum of the obtained compound. ¹ H-NMR (300 MHz, DMSO-d ₆ ) δ 0.97 (t, J = 7.1 Hz, 6H), 1.34 (qt, J = 7.1 Hz, 4H), 1.80 (br, 4H), 2.33 (s, 6H ), 3.00 (s, 12H), 3.27 (br, 4H), 4.63 (s, 4H), 7.44 (d, J = 8.3Hz, 2H), 7.56 (d, J = 9.1Hz, 2H), 7.63 (s , 2H), 7.73 (d, J = 8.3Hz, 4H), 8.15 (d, J = 8.1Hz,
4H), 10.12 (s, H).

(Example 8)
In the above Example 7, an ionic organic compound represented by the following (13) was obtained in the same manner as in Example 7 except that n-ethyldimethylamine was used instead of n-butyldimethylamine. Yield 89%. The structure was confirmed from the proton NMR spectrum of the obtained compound. ¹ H-NMR (300 MHz, DMSO-d ₆ ) δ 1.37 (t, J = 7.1 Hz, 6H), 2.33 (s, 6H), 2.98 (s, 12), 3.38-3.43 (m, 4H), 4.63 (s, 4H), 7.44 (d, J = 8.3Hz, 2H), 7.56 (d, = 8.3Hz, 2H), 7.63 (s, 2H), 7.74 (d, J = 8.3Hz, 4H), 8.15 ( d, J = 8.2Hz, 4H), 10.14 (s, 2H).

Example 9 Synthesis of (4,4′-bis [(4-chloromethyl) benzamide] -3,3 ′, 5,5′-tetramethylbiphenyl and its quaternary amination to synthesize compound (A5) )
Example 1 except that 3,3 ′, 5,5′-tetramethylbenzidine was used in place of 4,4′-diamino-3,3′-dimethoxybiphenyl (o-dianisidine) in Example 1 above. In the same manner as described above, the title compound represented by the following formula (14) was obtained. Yield 97%. The structure was confirmed from the proton NMR spectrum of the obtained compound. ¹ H-NMR (300 MHz, DMSO-d ₆ ) δ 2.26 (s, 12H), 4.86 (s, 4H), 7.46 (s, 4H), 7.61 (d, J = 8Hz, 4H), 8.02 (d, J = 8Hz, 4H), 9.84 (s, 2H).
In Example 1, 4,4′-bis [(4-chloromethyl) benzamide] -3,3′-dimethoxybiphenyl was replaced with 4,4′-bis [(4-chloromethyl) synthesized by the above reaction. ) Benzamide] -3,3 ', 5,5'-tetramethylbiphenyl was used in the same manner as in Example 1 to obtain an ionic organic compound represented by the following (15). Yield 62%. The structure was confirmed from the proton NMR spectrum of the obtained compound. ¹ H-NMR (300 MHz, DMSO-d ₆ ) δ 0.90 (t, J = 6.9 Hz, 6H), 1.33 (br, 12H), 1.81 (br, 4H), 2.27 (s, 12H), 3.01 (s , 12H), 3.27 (br, 4H), 4.63 (s, 4H), 7.47 (s, 4H), 7.73 (d, J = 8.1Hz, 4H), 8.17 (d, J = 8.2Hz, 4H), 10.02 (s, 2H).

Example 10 Synthesis of 4,4′-bis [{(4-chloromethyl) benzamido} phenyl] methane and Synthesis of Compound (A6) by Its Quaternary Amination
In the same manner as in Example 1 except that bis (4-aminophenyl) methane was used instead of 4,4′-diamino-3,3′-dimethoxybiphenyl (o-dianisidine) in Example 1 above, The title compound represented by the formula (16) was obtained. Yield 98%. The structure was confirmed from the proton NMR spectrum of the obtained compound. ¹ H-NMR (300 MHz, DMSO-d ₆ ) δ 3.90 (s, 2H), 4.84 (s, 4H), 7.20 (d, J = 8Hz, 4H), 7.58 (d, J = 8Hz, 4H), 7.68 (d, J = 8Hz, 4H), 7.94 (d, J = 8Hz, 4H), 10.21 (s, 2H).
In Example 1, instead of 4,4′-bis [(4-chloromethyl) benzamide] -3,3′-dimethoxybiphenyl, 4,4′-bis [{(4 An ionic organic compound represented by the following (17) was obtained in the same manner as in Example 1 except that -chloromethyl) benzamido} phenyl] methane was used. Yield 80%. The structure was confirmed from the proton NMR spectrum of the obtained compound. ¹ H-NMR (300 MHz, DMSO-d ₆ ) δ 0.89 (t, J = 6.5 Hz, 6H), 1.31 (br, 12H), 1.80 (br, 4H), 2.98 (s, 12H), 3.25-3.30 (m, 4H), 3.90 (s, 2H), 4.61 (s, 4H), 7.22 (d, J = 8.5Hz, 4H), 7.69-7.73 (m, 8H), 8.09 (d, J = 8.1Hz, 4H), 10.39 (s, 2H).

Example 11 Synthesis of 1,3-bis {(4-chloromethyl) benzamide} benzene and Synthesis of Compound (A7) by Its Quaternary Amination
Example 1 was used except that 1,3-diaminobenzene (m-phenylenediamine) was used in place of 4,4′-diamino-3,3′-dimethoxybiphenyl (o-dianisidine) in Example 1 above. Similarly, the title compound represented by the following formula (18) was obtained. Yield 98%. The structure was confirmed from the proton NMR spectrum of the obtained compound. ¹ H-NMR (300 MHz, DMSO-d ₆ ) δ 4.85 (s, 4H), 7.29-7.35 (m, 1H), 7.48-7.52 (m, 2H), 7.59 (d, J = 8.3Hz, 4H) , 7.98 (d, J = 8.3Hz, 4H), 8.32 (s, 1H), 10.33 (s, 2H).
In Example 1, 1,3-bis {(4-chloromethyl) synthesized by the above reaction instead of 4,4′-bis [(4-chloromethyl) benzamide] -3,3′-dimethoxybiphenyl An ionic organic compound represented by the following (19) was obtained in the same manner as in Example 1 except that benzamide} benzene was used and acetonitrile was used as a reaction solvent. Yield 50%. The structure was confirmed from the proton NMR spectrum of the obtained compound. ¹ H-NMR (300 MHz, DMSO-d ₆ ) δ 0.87-0.92 (m, 6H), 1.32 (s, 12H), 1.80 (br, 4H), 3.00 (s, 12H), 3.27 (s, 4H) , 4.63 (s, 4H), 7.34 (t, J = 7.8Hz, 1H), 7.52-7.55 (m, 2H), 7.72 (d, J = 8.3Hz, 4H), 8.12 (d, J = 8.3Hz, 4H), 8.40 (s, 1H), 10.50 (s, 2H).

(Example 12)
In the above Example 11, an ionic organic compound represented by the following (20) was obtained in the same manner as in Example 11 except that n-butyldimethylamine was used instead of n-hexyldimethylamine. Yield 59%. The structure was confirmed from the proton NMR spectrum of the obtained compound. ¹ H-NMR (300 MHz, DMSO-d ₆ ) δ 0.97 (t, J = 7.2 Hz, 6H), 1.34 (qt, J = 7.4 Hz, 4H), 1.80 (br, 4H), 3.00 (s, 12H ), 3.27 (br, 4H), 4.63 (s, 4H), 7.31-7.37 (m, 1H), 7.51-7.54 (m, 2H), 7.72 (d, J = 8.3Hz, 4H), 8.12 (d, J = 8.3Hz, 4H), 8.41 (s, 1H), 10.49 (s, 2H).

(Example 13)
In the above Example 11, an ionic organic compound represented by the following (21) was obtained in the same manner as in Example 11 except that ethyldimethylamine was used instead of n-hexyldimethylamine. Yield 55%. The structure was confirmed from the proton NMR spectrum of the obtained compound. ¹ H-NMR (300 MHz, DMSO-d ₆ ) δ 1.36 (t, J = 7.1 Hz, 6H), 2.98 (s, 12H), 3.35-3.43 (m, 4H), 4.63 (s, 4H), 7.34 (t, J = 8.5Hz, 1H), 7.52-7.55 (m, 2H), 7.73 (d, J = 8.3Hz, 4H), 8.12 (d, J = 8.2Hz, 4H), 8.41 (s, 1H) , 10.51 (s, 2H).

Example 14 Synthesis of trans-1,4-bis [(4-chloromethyl) benzamide] cyclohexane and Synthesis of Compound (A8) by Its Quaternary Amination
In the same manner as in Example 1 except that trans-1,4-diaminocyclohexane was used in place of 4,4′-diamino-3,3′-dimethoxybiphenyl (o-dianisidine) in Example 1 above, The title compound represented by the formula (22) was obtained. Yield 90%. The structure was confirmed from the proton NMR spectrum of the obtained compound. ¹ H-NMR (300 MHz, DMSO-d ₆ ) δ 1.43-1.49 (m, 4H), 1.89-1.91 (m, 4H), 3.77 (br, 2H), 4.81 (s, 4H), 7.51 (d, J = 8.2Hz, 4H), 7.84 (d, J = 8.2Hz, 4H), 8.29 (d, J = 7.8Hz, 2H).
In Example 1, trans-1, 4-bis [(4-chloro) synthesized in the above reaction instead of 4,4′-bis [(4-chloromethyl) benzamide] -3,3′-dimethoxybiphenyl Methyl) benzamide] An ionic organic compound represented by the following (23) was obtained in the same manner as in Example 1 except that cyclohexane was used. Yield 61%. The structure was confirmed from the proton NMR spectrum of the obtained compound. ¹ H-NMR (300 MHz, DMSO-d ₆ ) δ 0.86-0.91 (m, 6H), 1.31 (br, 12H), 1.47-1.53 (m, 4H), 1.78 (br, 4H), 1.89-1.91 ( m, 4H), 2.96 (s, 12H), 3.23-3.28 (m, 4H), 3.81 (br, 2H), 4.58 (s, 4H), 7.63 (d, J = 8.2Hz, 4H), 7.99 (d , J = 8.2Hz, 4H), 8.48 (d, J = 7.9Hz, 2H).

(Example 15)
In Example 14, the ionic organic compound represented by the following (24) was obtained in the same manner as in Example 12 except that n-butyldimethylamine was used instead of n-hexyldimethylamine. Yield 80%. The structure was confirmed from the proton NMR spectrum of the obtained compound. ¹ H-NMR (300 MHz, DMSO-d ₆ ) δ 0.95 (t, J = 7.2 Hz, 6H), 1.31 (qt, J = 7.5 Hz, 4H), 1.47-1.53 (m, 4H), 1.75-1.80 (m, 4H), 1.89-1.91 (m, 4H), 2.97 (s, 12H), 3.23-3.39 (m, 4H), 3.80 (br, 2H), 4.59 (s, 4H), 7.64 (d, J = 8.3Hz, 4H), 7.99 (d, J = 8.3Hz, 4H), 8.49 (d, J = 7.9Hz, 2H).

(Example 16)
In Example 14, an ionic organic compound represented by the following (25) was obtained in the same manner as in Example 12 except that ethyldimethylamine was used instead of n-hexyldimethylamine. Yield 82%. The structure was confirmed from the proton NMR spectrum of the obtained compound. ¹ H-NMR (300 MHz, DMSO-d ₆ ) δ 1.34 (t, J = 7.1 Hz, 6H), 1.47-1.54 (m, 4H), 1.89-1.91 (m, 4H), 2.94 (s, 12H ), 3.37 (br, 4H), 3.80 (br, 2H), 4.58 (s, 4H), 7.64 (d, J = 8.2Hz, 4H), 7.99 (d, J = 8.3Hz, 4H), 8.49 (d , J = 7.9Hz, 2H).

(Example 17)
In Example 14, the ionic organic compound represented by the following (26) was obtained in the same manner as in Example 12 except that n-octyldimethylamine was used instead of n-hexyldimethylamine. Yield 81%. The structure was confirmed from the proton NMR spectrum of the obtained compound. ¹ H-NMR (300 MHz, DMSO-d ₆ ) δ 0.85-0.89 (m, 6H), 1.27-1.30 (m, 20H), 1.47-1.53 (m, 4H), 1.78 (br, 4H), 1.89- 1.91 (m, 4H), 2.96 (s, 12H), 3.22-3.28 (m, 4H), 3.81 (br, 2H), 4.58 (s, 4H), 7.63 (d, J = 8.2Hz, 4H), 7.99 (d, J = 8.2Hz, 4H), 8.48 (d, J = 7.9Hz, 2H).

(Example 18)
In Example 14, the ionic organic compound represented by the following (27) was obtained in the same manner as in Example 12 except that n-decyldimethylamine was used instead of n-hexyldimethylamine. Yield 65%. The structure was confirmed from the proton NMR spectrum of the obtained compound. ¹ H-NMR (300 MHz, DMSO-d ₆ ) δ 0.84-0.88 (m, 6H), 1.26 (br, 28H), 1.47-1.53 (m, 4H), 1.78 (br, 4H), 1.89-1.91 ( m, 4H), 2.96 (s, 12H), 3.22-3.28 (m, 4H), 3.81 (br, 2H), 4.58 (s, 4H), 7.63 (d, J = 8.3Hz, 4H), 7.99 (d , J = 8.2Hz, 4H), 8.48 (d, J = 8.0Hz, 2H).

(Example 19)
In Example 14, the ionic organic compound represented by the following (28) was obtained in the same manner as in Example 12 except that n-dodecyldimethylamine was used instead of n-hexyldimethylamine. Yield 63%. The structure was confirmed from the proton NMR spectrum of the obtained compound. ¹ H-NMR (300 MHz, DMSO-d ₆ ) δ 0.83-0.88 (m, 6H), 1.25 (br, 36H), 1.47-1.53 (m, 4H), 1.78 (br, 4H), 1.89-1.91 ( m, 4H), 2.96 (s, 12H), 3.22-3.27 (m, 4H), 3.81 (br, 2H), 4.58 (s, 4H), 7.63 (d, J = 8.3Hz, 4H), 7.99 (d , J = 8.3Hz, 4H), 8.48 (d, J = 7.9Hz, 2H).

Example 20 (Anion Exchange Reaction)
The ionic compound (150 mg) represented by the formula (3) obtained in Example 1 was dissolved in water (20 mL) at 100 ° C., and 0.4 M concentration of lithium bis (trifluoromethanesulfonyl) amide was added to the solution. When an aqueous solution (7.6 mL) of (Li-TFSA) was added, a precipitate of the compound represented by the following formula (29) was quantitatively generated. The structure was confirmed from the proton NMR spectrum of the obtained compound. The structure was confirmed from the proton NMR spectrum of the obtained compound. ¹ H-NMR (300 MHz, DMSO-d ₆ ) δ 0.86 (t, J = 6.7 Hz, 6H), 1.29 (br, 12H), 1.77 (br, 4H), 2.95 (s, 12H), 3.22-3.29 (m, 4H), 3.93 (s, 6H), 4.55 (s, 4H), 7.31-7.36 (m, 4H), 7.67 (d, J = 8.2Hz, 4H), 7.82 (d, J = 8.2Hz, 2H), 8.08 (d, J = 8.3Hz, 4H), 9.59 (s, 2H).

(Example 21)
In Example 20 above, the ionic compound represented by Formula (5) was used instead of Formula (3) in the same manner as Example 20 except that the compound represented by Formula (30) below was used. A precipitate formed quantitatively.

(Example 22)
In Example 20 above, the ionic compound represented by Formula (23) was used instead of Formula (3) in the same manner as Example 20 except that the compound represented by Formula (31) below was used. A precipitate formed quantitatively.

(Example 23) (Preparation of multi-walled carbon nanotube dispersion using ionic organic compound)
30 mg of the ionic organic compound (12) obtained in Example 7 above was mixed with 3 mL of deionized pure water in a sample tube and heated to obtain a uniform solution. This solution is mixed with 1 mg of multi-walled carbon nanotubes produced by the arc discharge method, and is irradiated with ultrasonic waves for 30 minutes using a cleaning ultrasonic irradiation device (130 W, 35 kHz), thereby obtaining a black carbon nanotube uniformly dispersed aqueous solution. No precipitation occurred. The result is shown in FIG. (A) is before ultrasonic irradiation, and (b) is after ultrasonic irradiation.
Similarly, the compounds (3), (5), (6), (7), (9), (10), (13), (15), (17), (19), (20), ( 21), (26)-(28) was used, and the multilayer carbon nanotube uniform dispersion aqueous solution was able to be prepared.
The concentration range of the ionic organic compound for preparing the CNT dispersion is about 1 to 20 g / L, and preferably about 5 to 10 g / L. The content of the multi-walled carbon nanotube that can be dispersed was 1 to 3 g / L.

(Example 24) (Preparation of a single-walled carbon nanotube (SWCNT) dispersion using an ionic organic compound)
30 mg of the ionic organic compound (12) obtained in Example 7 was mixed with 3 mL of deionized pure water in a sample tube and heated to obtain a uniform solution. This solution was mixed with 1 mg of single-walled carbon nanotubes produced by the High-pressure carbon monoxide (HiPco) method, and irradiated with ultrasonic waves for 30 minutes using a cleaning ultrasonic irradiation device (130 W, 35 kHz). A single-walled carbon nanotube uniformly dispersed aqueous solution was obtained, and no precipitation occurred. The result is shown in FIG. (A) is before ultrasonic irradiation, and (b) is after ultrasonic irradiation. Furthermore, by using heavy water as a solvent, a similar SWCNT solution was obtained, and after centrifuging the solution for a total of 2 hours (4000 rpm), an isolated dispersion state was confirmed from the UV-vis-NIR spectrum (FIG. 3). ).
Similarly, using the compounds (3), (5), (6), (7), (9), (15), and (17), a SWCNT homogeneously dispersed aqueous solution could be prepared.
The concentration range of the ionic organic compound for preparing the SWCNT dispersion is about 1 to 20 g / L, and preferably about 5 to 10 g / L. Moreover, the content of SWCNT that can be dispersed was 1 to 3 g / L.

(Example 25) (Preparation of a single-walled carbon nanotube (SWCNT) dispersion using an ionic organic compound)
10 mg of the ionic organic compound (12) obtained in Example 7 was mixed with 20 mL of deionized pure water in a sample tube, and sonicated (90 W, 42 kHz) using an ultrasonic cleaning device BRANSONIC 2. And a homogeneous solution was obtained. This solution is mixed with 7 mg of single-walled carbon nanotubes produced by the High-pressure carbon monoxide (HiPco) method, put into a 50 mL wide-mouth bottle, and using an ultrasonic homogenizer BRANSON Advanced Digital Sonifire 250D (20 W, 19.9 kHz). By irradiating with ultrasonic waves for 4 hours, a black single-walled carbon nanotube uniformly dispersed aqueous solution was obtained. The solution was centrifuged for 15 hours (16400 rpm, 28500 × g) using a refrigerated centrifuge eppendorf Cetrifuge 5417R (angle rotor: FA45-24-11), and then measured by UV-vis-NIR spectrum (SHIMADZU UV-3150). A good dispersion state was confirmed (FIG. 4).

Claims (7)

An ionic organic compound represented by the following general formula (I).
(Wherein R ¹ , R ² and R ³ are hydrogen or an alkyl group, A is a linking site having one or more aromatic rings, or a linking site consisting of a cyclohexane ring, X is an anion, n is nX is −2 It is a number that becomes a valence.) In the general formula (I), X represents a halogen atom (F, Cl, Br, I), a tetrafluoroboric acid group (BF ₄ ), hexafluorophosphoric acid (PF ₆ ), bis (trifluoromethanesulfonyl) amide (TFSA). ), Thioisocyanate (SCN), nitrate group (NO ₃ ), sulfate group (SO ₄ ), thiosulfate group (S ₂ O ₃ ), carbonate group (CO ₃ ), bicarbonate group (HCO ₃ ), phosphate group , Phosphorous acid group, hypophosphorous acid group, each halogen acid compound acid group (AO ₄ , AO ₃ , AO ₂ , AO: A = Cl, Br, I), tris (trifluoromethylsulfonyl) carbon acid group, Trifluoromethylsulfonic acid group, dicyanamide group, acetic acid group (CH ₃ COO), halogenated acetic acid group ((CA _n H _3-n ) COO, A = F, Cl, Br, I; n = 1, 2, 3 ), Tetraph Niruhou acid (BPh ₄₎ and its derivative _{(B (Aryl) 4: Aryl} = substituted phenyl group), characterized in that at least one member selected from ionic organic compound according to claim 1. (A) A quaternization reaction of a compound represented by the following general formula (II) having (chloromethyl) benzamide groups at both ends and (B) an amine represented by the following general formula (III) The method for producing an ionic organic compound according to claim 1, wherein:
(In the formula, A represents a linking site having one or more aromatic rings or a linking site consisting of a cyclohexane ring.)
(In the formula, R ¹ , R ² and R ³ represent hydrogen or an alkyl group.)   The method for producing an ionic organic compound according to claim 3, wherein the quaternization reaction is carried out in dimethylformamide or acetonitrile at 50 to 80 ° C.   Furthermore, the anion of the obtained ionic compound is substituted with another anion by anion exchange reaction, The manufacturing method of the ionic organic compound of Claim 3 or 4 characterized by the above-mentioned.   A CNT dispersant comprising the ionic organic compound according to claim 1.   A CNT dispersion containing the CNT dispersant according to claim 6.