WO2017187985A1

WO2017187985A1 - Ionic compound and photoresponsive nano carbon material dispersant

Info

Publication number: WO2017187985A1
Application number: PCT/JP2017/014972
Authority: WO
Inventors: 啓邦神徳; 松澤　洋子; 秀元木原; 吉田　勝
Original assignee: 国立研究開発法人産業技術総合研究所
Priority date: 2016-04-26
Filing date: 2017-04-12
Publication date: 2017-11-02
Also published as: JP6755015B2; JPWO2017187985A1

Abstract

Provided is a dispersant which makes it possible to achieve the repeated dispersion and coagulation of a dispersoid in a dispersion containing the dispersant upon the irradiation of the dispersion with light for a short time. The dispersant contains an ionic compound represented by general formula (I) as an active ingredient. (In the formula, X represents an amide bond or an ester bond; A represents a substituent having a cation moiety; B represents an anion; and m represents such a numerical value that mB can have a valency of -2.)

Description

Ionic compounds and photoresponsive nanocarbon material dispersants

The present invention relates to a dispersant for dispersing nanocarbon materials such as carbon nanotubes and aromatic compounds in water and polar solvents.

Since carbon nanotubes (hereinafter sometimes referred to as “CNT”) have excellent electrical and optical properties, research on CNTs has been actively promoted. Dispersion of CNTs in a liquid is very difficult due to the strong cohesive force based on the van der waals force of the CNTs themselves. Many CNT dispersants using surfactants, polymers, biomolecules, etc. have been reported to disperse CNTs in water or organic solvents.

The surfactant type dispersant described in Non-Patent Document 1 requires an amount 10 times or more that of CNT. The dispersant described in Patent Document 1 uses an enzymatic decomposition reaction for desorption from CNTs. However, since the detachment of the dispersant from the CNT depends on the activity of the enzyme, the use environment of the dispersant is limited. Moreover, since this decomposition reaction is irreversible, the dispersant cannot be reused. The photoresponsive stilbene type dispersant described in Patent Document 2 can be detached from CNTs by light irradiation. However, since the optical response is multistage, several hours of light irradiation is required to desorb the dispersant from the CNT.

Patent Document 2 also describes an azo-based dispersant. However, since the thermal stability of the cis form of this dispersant is low and it is easy to return to the trans form, the efficiency when desorbing the dispersant from the CNT by light irradiation is low. Other methods for desorbing the dispersant from CNT include desorption methods using redox of metal complexes (Non-Patent Document 2 and Non-Patent Document 3), desorption methods using changes in temperature and pH (Non-Patent Documents) 4), and a desorption method using a difference in solubility in a solvent (Non-Patent Document 5). However, there are problems that the synthesis of these dispersants is complicated, and that these desorption methods use organic solvents with high environmental impact such as chloroform and toluene.

JP 2007-153716 A International Publication No. 2011/052604

The present invention has been made in view of such circumstances, and provides a dispersant capable of repeating dispersion and aggregation in a dispersion medium by irradiating the dispersion liquid with light for a short time. With the goal.

The ionic compound of the present invention is represented by the following general formula (I).

(In the formula, X is a kind selected from amide bonds and ester bonds shown below.

A is a substituent having a cation moiety represented by the following.

However, n is a number from 1 to 10, R ₁ is hydrogen, an alkyl group, a phenyl group, a polyethylene glycol group, or an allyl group, and R ₂ and R ₃ are independently hydrogen or an alkyl group. B represents an anion, and m is a number such that mB becomes -2 valent. )

The dispersant of the present invention is a dispersant for dispersing a dispersoid in a dispersion medium containing at least one of water and a polar organic solvent, and the ionic compound of the present invention is an active ingredient. The dispersion of the present invention has a dispersoid, a dispersion medium containing at least one of water and a polar organic solvent, and the dispersant of the present invention.

The method for producing a dispersion of the present invention comprises a mixing step of mixing a dispersoid, a dispersion medium containing at least one of water and a polar organic solvent, and a dispersant of the present invention to obtain a mixed solution, A dispersion step of vibrating by sound waves to disperse the dispersoid in the dispersion medium. In the method for producing an aggregating liquid of the present invention, the dispersion liquid of the present invention is irradiated with light having a predetermined wavelength of 250 to 450 nm to desorb the dispersing agent from the dispersoid, and the dispersoid is aggregated in the dispersion medium. To obtain an agglomerated liquid.

Another method for producing the dispersion of the present invention is to irradiate the dispersion of the present invention with light having a predetermined wavelength of 250 to 450 nm to desorb the dispersant from the dispersoid, and to disperse the dispersoid in the dispersion medium. Aggregating step of aggregating to obtain an aggregating liquid, and irradiating the aggregating liquid with light having a predetermined wavelength of 380 to 500 nm different from the wavelength of light used when desorbing the dispersant from the dispersoid in the aggregating step A dispersion step of dispersing a dispersoid in a dispersion medium to obtain a dispersion.

Another method for producing the dispersion of the present invention is to irradiate the dispersion of the present invention with light having a predetermined wavelength of 250 to 450 nm to desorb the dispersant from the dispersoid, and to disperse the dispersoid in the dispersion medium. An aggregating step for aggregating to obtain an aggregated liquid, a recovery step for recovering a solution containing at least part of the dispersant and at least part of the dispersion medium from the aggregated liquid, and mixing this solution with another dispersoid And a dispersion step of oscillating the obtained mixed liquid with ultrasonic waves to disperse the dispersoid in the dispersion medium.

According to the present invention, dispersion and aggregation of the dispersoid can be repeated by irradiating the dispersion with light for a short time.

The visible-near infrared (Vis-NIR) absorption spectrum of the SWCNT dispersion of Example 19. The image of SWCNT dispersion liquid of Example 19. The Vis-NIR absorption spectrum of the SWCNT dispersion of Example 20 Vis-NIR absorption spectrum of the SWCNT dispersion of Example 21. Vis-NIR absorption spectrum of the SWCNT dispersion of Example 22. Vis-NIR absorption spectrum of the SWCNT dispersion of Example 23. The Vis-NIR absorption spectrum of the SWCNT dispersion of Example 24. Vis-NIR absorption spectrum of the SWCNT dispersion of Example 25. Vis-NIR absorption spectrum of the SWCNT dispersion of Example 26. Vis-NIR absorption spectrum of the SWCNT dispersion of Example 27. The Vis-NIR absorption spectrum of the SWCNT dispersion of Example 28. The Vis-NIR absorption spectrum of the SWCNT dispersion of Example 28. The absorbance plot in wavelength 1155nm when repeating SWCNT aggregation and re-dispersion of the SWCNT dispersion liquid of Example 28. Vis-NIR absorption spectrum of the SWCNT dispersion of Example 29. Vis-NIR absorption spectrum of the SWCNT dispersion of Example 29-2. Vis-NIR absorption spectrum of the SWCNT dispersion of Example 29-3. 4 is a UV-vis-NIR absorption spectrum of the SWCNT dispersion of Example 30. FIG. 4 is a UV-vis-NIR absorption spectrum of the SWCNT dispersion of Example 31. FIG. 6 shows a UV-vis-NIR absorption spectrum of the MWCNT dispersion of Example 32. FIG. The image of the carbon black dispersion liquid of Example 33. The UV-vis-NIR absorption spectrum of the carbon black dispersion of Example 33. The image of the carbon black dispersion liquid of Example 34. 4 is a UV-vis-NIR absorption spectrum of the carbon black dispersion of Example 34. FIG. The graphene nanoplatelet dispersion liquid of Example 35. The UV-vis-NIR absorption spectrum of the graphene nanoplatelet dispersion of Example 35. The image of the copper phthalocyanine dispersion of Example 36. The image when the copper phthalocyanine dispersion liquid of Example 36 is spread on a slide glass. The image of the iron (III) oxide dispersion of Example 37. The UV-vis-NIR absorption spectrum of the iron (III) oxide dispersion of Example 37. The image of the coronene dispersion liquid of Example 38. The UV-vis-NIR absorption spectrum of the coronene dispersion of Example 38.

Hereinafter, the ionic compound, the dispersant, the dispersion, the method for producing the dispersion, and the method for producing the aggregated liquid according to the present invention will be described based on embodiments and examples. A duplicate description will be omitted as appropriate. In the case where a numerical range is indicated by describing “˜” between two numerical values, the two numerical values are also included in the numerical range.

A is a substituent having a cation moiety represented by the following.

The number of carbon atoms of the alkyl group represented by R ₁ is preferably 1 or more and 10 or less. As anions B, halogen anions (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ ), tetrafluoroborate anions (BF ₄ ⁻ ), hexafluorophosphate anions (PF ₆ ⁻ ), bis (trifluoromethanesulfonyl) ) Amide anion (TFSA), thioisocyanate anion (SCN ⁻ ), nitrate anion (NO ₃ ⁻ ), sulfate anion (SO ₄ ²⁻ ), thiosulfate anion (S ₂ O ₃ ²⁻ ), carbonate anion (CO ₃ ^{2 -),} bicarbonate anion (HCO ₃ ^-), phosphate anion (PO ₄ ^3-), phosphorous acid anion (PO ₃ ^3-), hypophosphorous acid anion (PO ₂ ^3-), halogen anion (ClO ₄ ⁻ , BrO ₄ ⁻ , IO ₄ ⁻ , ClO ₃ ⁻ , BrO ₃ ⁻ , IO ₃ ⁻ , ClO ₂ ⁻ , BrO ₂ ⁻ , IO ₂ ⁻ , ClO ⁻ , BrO ⁻ , IO ⁻ ), Tris (trifluoromethyl) Sulfonyl) carbonic acid anion, trifluoromethyl Sulfonic acid anion, dicyanamide anion, acetic acid anion (CH ₃ COO ⁻ ), halogenated acetic acid anion ((CA _n H _3−n ) COO ⁻ (A═F, Cl, Br, I, n = 1, 2, 3)), tetraphenylborate anion (BPh ₄ ⁻ ), or a derivative of tetraphenylborate anion (B (Aryl) ₄ ⁻ (Aryl is a substituted phenyl group)).

The ionic compound of the present invention is preferably a kind selected from substances represented by the following chemical formulas.

The dispersant of the present invention is a dispersant for dispersing a dispersoid in a dispersion medium containing at least one of water and a polar organic solvent. And the dispersing agent of this invention uses the ionic compound of this invention as an active ingredient. The dispersion of the present invention contains a dispersoid, a dispersion medium containing at least one of water and a polar organic solvent, and the dispersant of the present invention. Examples of the dispersoid include nanocarbon materials, hydrophobic fine particles, and hydrophobic molecules. The dispersoid is preferably at least one selected from single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon black, graphene, phthalocyanine, metal phthalocyanine, coronene, and iron oxide fine particles. This is because it is uniformly dispersed in the dispersion medium.

The method for producing a dispersion according to an aspect of the present invention includes a mixing step and a dispersion step. In the mixing step, a dispersion is obtained by mixing the dispersoid, a dispersion medium containing at least one of water and a polar organic solvent, and the dispersant of the present invention. In the dispersion step, the mixture is vibrated by ultrasonic waves to disperse the dispersoid in the dispersion medium. In the method for producing an aggregating liquid of the present invention, the dispersion liquid of the present invention is irradiated with light having a predetermined wavelength of 250 to 450 nm to desorb the dispersing agent from the dispersoid, and the dispersoid is aggregated in the dispersion medium. To obtain an agglomerated liquid. Examples of light having a predetermined wavelength of 250 to 450 nm include ultraviolet light having a wavelength of 365 nm. The “predetermined wavelength of 250 to 450 nm” is determined according to the structure of the dispersant used.

In addition, the method for producing a dispersion according to another aspect of the present invention includes an aggregation step and a dispersion step. In the flocculation step, the dispersion liquid of the present invention is irradiated with light having a predetermined wavelength of 250 to 450 nm to desorb the dispersant from the dispersoid and aggregate the dispersoid in the dispersion medium to obtain an aggregate liquid. In the dispersion step, the aggregate liquid is irradiated with light having a predetermined wavelength of 380 to 500 nm, which is different from the wavelength of light used when the dispersant is removed from the dispersoid in the aggregation step, and the dispersoid is dispersed in the dispersion medium. Is dispersed to obtain a dispersion. Examples of light having a predetermined wavelength of 380 to 500 nm include visible light having a wavelength of 436 nm.

“The predetermined wavelength of 250 to 450 nm” and “the predetermined wavelength of 380 to 500 nm” are determined according to the structure of the dispersant used. Since these two types of “predetermined wavelengths” are different, the wavelength of light used in the aggregation process and the wavelength of light used in the dispersion process can be distinguished. That is, for example, in a dispersion containing a certain dispersant, the wavelength of ultraviolet light used in the aggregation step is between 340 and 380 nm, and the wavelength of visible light used in the dispersion step is between 400 and 450 nm. On the other hand, in a dispersion containing another dispersant, the wavelength of ultraviolet light used in the aggregation step is between 360 and 400 nm, and the wavelength of visible light used in the dispersion step is between 420 and 480 nm.

In addition, the method for producing a dispersion according to another aspect of the present invention includes an aggregation step, a recovery step, and a dispersion step. In the flocculation step, the dispersion liquid of the present invention is irradiated with light having a predetermined wavelength of 250 to 450 nm to desorb the dispersant from the dispersoid and aggregate the dispersoid in the dispersion medium to obtain an aggregate liquid. In the recovery step, a solution containing at least a part of the dispersant and at least a part of the dispersion medium is recovered from the aggregate liquid. In the dispersion step, another dispersoid and a solution are mixed, and then the obtained mixture is vibrated by ultrasonic waves to disperse the dispersoid in the dispersion medium.

Examples 1 to 6-2: Preparation of photoresponsive ionic compound raw material (Example 1: Preparation of photoresponsive ionic compound raw material 1)
4- (Piperidin-1-ylmethyl) aniline (0.62 g, 3.3 mmol) and triethylamine (0.9 g, 8.9 mmol) were dissolved in dehydrated methylene chloride (10 mL). A solution prepared by dissolving 0.5 g (1.6 mmol) of azobenzene-4,4′-dicarbonyl chloride in 20 mL of dehydrated methylene chloride was added over 1 hour while stirring, and the mixture was further stirred at room temperature for 12 hours. The resulting precipitate was filtered with suction, washed with methylene chloride and dried to give 0.75 g of orange powder (75% yield). ^{From the 1} H-NMR spectrum, it was confirmed that this powder was a compound represented by the following formula (1).
¹ H-NMR (400MHz, Pyridine-d ₅ , δ): 1.32 (m, 4H), 1.49 (m, 8H), 2.33 (br, 8H), 3.42 (s, 4H), 7.48 (m, 4H), 8.04-8.16 (m, 8H), 8.41 (m, 4H), 11.2 (s, 2H)

(Example 2: Preparation of raw material of photoresponsive ionic compound 2)
An orange powder was obtained in the same manner as in Example 1 except that 4- (1H-imidazol-1-yl) aniline having the same substance amount was used instead of 4- (piperidin-1-ylmethyl) aniline. (Rate 85%). ^{From 1} H-NMR spectrum, it was confirmed that this powder was a compound represented by the following formula (2).
¹ H-NMR (400MHz, Pyridine-d ₅ , δ): 8.11-8.15 (m, 8H), 8.21 (m, 4H), 8.32 (s, 2H), 8.45 (m, 4H), 8.56 (m, 4H ), 11.4 (s, 2H)

(Example 3: Production of photoresponsive ionic compound raw material 3)
An orange powder was obtained in the same manner as in Example 1 except that the same amount of 1- (3-aminopropyl) imidazole was used instead of 4- (piperidin-1-ylmethyl) aniline (yield 81% ). ^{From the 1} H-NMR spectrum, it was confirmed that this powder was a compound represented by the following formula (3).
¹ H-NMR (400MHz, DMSO-d ₆ , δ): 1.95 (m, 4H), 3.25 (m, 4H), 6.86 (d, 2H), 7.19 (d, 2H), 7.63 (s, 2H), 7.94-8.04 (m, 8H), 8.68 (m, 2H)

(Example 4: Production 4 of photoresponsive ionic compound raw material)
An orange powder was obtained in the same manner as in Example 1 except that the same amount of 1- (3-aminoethyl) pyridine was used instead of 4- (piperidin-1-ylmethyl) aniline (yield 84%). ). ^{From the 1} H-NMR spectrum, it was confirmed that this powder was a compound represented by the following formula (4).
¹ H-NMR (400MHz, DMSO-d ₆ , δ): 2.89 (t, 4H), 3.25 (t, 4H), 7.26 (m, 4H), 7.94-8.01 (m, 8H), 8.45 (m, 4H ), 8.76 (m, 2H)

(Example 5: Preparation 5 of raw material of photoresponsive ionic compound)
An orange powder was obtained in the same manner as in Example 1 except that 4-hydroxyphenethyl bromide having the same substance amount was used instead of 4- (piperidin-1-ylmethyl) aniline (yield 68%). ^{From the 1} H-NMR spectrum, it was confirmed that this powder was a compound represented by the following formula (5).
¹ H-NMR (400MHz, Pyridine-d ₅ , δ): 3.12 (t, 4H), 3.67 (t, 4H), 7.33 (d, 4H), 7.42 (d, 4H), 8.16 (d, 4H), 8.46 (d, 4H)

(Example 6: Preparation of raw material of photoresponsive ionic compound 6)
4- (Chloromethyl) benzyl chloride (1.5 g, 7.9 mmol) was dissolved in dehydrated methylene chloride (20 mL). A solution prepared by dissolving 0.5 g (2.3 mmol) of 4,4′-dihydroxyazobenzene and 2 g (19 mmol) of triethylamine in 30 mL of dehydrated methylene chloride was added over 1 hour with stirring. Then, it stirred at room temperature for 24 hours. The precipitate was filtered off with suction, washed with methylene chloride and dried to give 1.1 g of yellow powder (88% yield). ^{From the 1} H-NMR spectrum, it was confirmed that this powder was a compound represented by the following formula (6).
^{1 H-NMR (400MHz, Pyridine} -d 5, δ): 4.81 (s, 4H), 7.46-7.73 (m, 8H), 8.17 (m, 6H), 8.40 (m, 2H)

(Example 6-2: Production of raw material of photoresponsive ionic compound 7)
0.55 g (3.3 mmol) of hordenine and 1.0 g (9.3 mmol) of triethylamine were dissolved in 20 mL of dehydrated methylene chloride. A solution prepared by dissolving 0.5 g (1.6 mmol) of azobenzene-4,4′-dicarbonyl dichloride in 20 mL of dehydrated methylene chloride was added dropwise thereto with stirring. Then, it stirred at room temperature for about 12 hours. The obtained reaction solution was concentrated under reduced pressure, and ethanol was added to precipitate a precipitate. The precipitate was separated by filtration, washed with ethanol, and then vacuum dried to obtain 0.56 g of orange powder (yield 61%). ^{From 1} H-NMR spectrum, it was confirmed that this powder was a compound represented by the following formula (6-2).
¹ H-NMR (400MHz, Pyridine-d ₅ , δ): 2.21 (s, 12H), 2.24 (t, J = 8Hz, 4H), 2.80 (t, J = 8Hz, 4H), 7.36-7.44 (m, 8H), 8.19 (dd, 4H), 8.49 (dd, 4H)

Examples 7 to 18-2: Preparation of photoresponsive ionic compound (Example 7: Preparation of photoresponsive ionic compound 1)
In 50 mL of dimethylformamide, 0.6 g (1.16 mmol) of the compound represented by the formula (6) obtained in Example 6 and 1 g (9.9 mmol) of N-butyldimethylamine were stirred at 80 ° C. for 48 hours. did. The reaction mixture was concentrated under reduced pressure, and the resulting precipitate was filtered with suction to obtain 0.56 g of a yellow powder (yield 67%). ^{From 1} H-NMR and ¹³ C-NMR spectra, it was confirmed that this powder was an ionic compound represented by the following formula (7).
¹ H-NMR (400MHz, D ₂ O, δ): 0.73 (t, 6H), 1.14 (m, 4H), 1.63 (m, 4H), 2.73-2.95 (m, 16H), 4.29 (s, 4H) , 7.05 (d, 4H), 7.23-7.65 (m, 8H), 7.87 (m, 4H)
¹³ C-NMR (400 MHz, DMSO-d ₆ , δ): 13.55, 19.28, 23.82, 49.30, 63.62, 65.13, 123.04, 123.96, 130.11, 130.22, 133.64, 134.14, 149.71, 152.76, 163.88

(Example 8: Preparation of photoresponsive ionic compound 2)
An orange powder was prepared in the same manner as in Example 7 except that instead of the compound represented by Formula (6), the same amount of the compound represented by Formula (5) obtained in Example 5 was used. Obtained (yield 60%). ^{From 1} H-NMR and ¹³ C-NMR spectra, it was confirmed that this powder was a compound represented by the following formula (8).
¹ H-NMR (400MHz, DMSO-d ₆ , δ): 0.96 (t, 6H), 1.38 (m, 4H), 1.69 (m, 4H), 3.11 (m, 20H), 3.53 (m, 4H), 7.35 (d, 4H), 7.45 (d, 4H), 8.15 (d, 4H), 8.37 (d, 4H)
¹³ C-NMR (400 MHz, DMSO-d ₆ , δ): 13.54, 19.26, 23.79, 27.53, 50.05, 63.19, 63.52, 122.01, 123.19, 130.22, 131.29, 131.52, 134.30, 149.43, 154.64, 163.93

(Example 9: Preparation of photoresponsive ionic compound 3)
In 100 mL of dimethylformamide, 0.5 g (0.9 mmol) of the compound represented by the formula (2) obtained in Example 2 and 2 g (12 mmol) of methyl trifluoromethanesulfonate were stirred at room temperature for 48 hours. The reaction solution was concentrated under reduced pressure, and the precipitate obtained by dropwise addition to acetone was suction filtered to obtain 0.76 g of an orange powder (yield 83%). ^{From 1} H-NMR and ¹³ C-NMR spectra, it was confirmed that this powder was an ionic compound represented by the following formula (9).
¹ H-NMR (400MHz, DMSO-d ₆ , δ): 3.95 (s, 6H), 7.78 (m, 4H), 7.94 (m, 4H), 8.04-8.11 (m, 8H), 8.22-8.27 (m , 4H), 9.70 (s, 2H), 10.7 (s, 2H)
¹³ C-NMR (400 MHz, DMSO-d ₆ , δ): 36.14, 121.00, 121.36, 122.35, 122.76, 124.40, 129.24, 130.18, 135.49, 135.73, 136.98, 140.14, 153.58, 162.27, 164.96

(Example 9-2: Preparation of photoresponsive ionic compound 3-2)
In 20 mL of dimethylformamide, 0.2 g (0.36 mmol) of the compound represented by the formula (2) obtained in Example 2 and 1.0 g (3.7 mmol) of triethylene glycol mono-2-bromoethyl methyl ether were added. , And stirred at 100 ° C. for 72 hours. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. Acetone was added to the concentrate, and the resulting precipitate was suction filtered and washed with acetone to obtain 0.29 g of an orange powder (yield 73%). ^{From the 1} H-NMR spectrum, it was confirmed that this powder was an ionic compound represented by the following formula (9-2).
¹ H-NMR (400MHz, D ₂ O, δ): 3.18 (s, 6H), 3.42-3.56 (m, 24H), 3.77 (br, 4H), 4.28 (br, 4H), 7.38 (m, 4H) , 7.53-7.64 (m, 16H), 9.11 (s, 2H)

(Example 10: Preparation of photoresponsive ionic compound 4)
In 10 mL of dimethylformamide, 0.1 g (0.2 mmol) of the compound represented by the formula (1) obtained in Example 1 and 1.0 g (7.9 mmol) of benzyl chloride were stirred at 80 ° C. for 24 hours. . The reaction solution was concentrated under reduced pressure, and the precipitate obtained by dropwise addition to acetone was suction filtered to obtain 0.13 g of an orange powder (yield 81%). ^{From 1} H-NMR and ¹³ C-NMR spectra, it was confirmed that this powder was an ionic compound represented by the following formula (10).
¹ H-NMR (400MHz, DMSO-d _6, δ): 1.44 (m, 4H), 1.75 (br, 4H), 2.07 (br, 4H), 3.19 (br, 8H), 4.63 (s, 4H), 7.56 (m, 10H), 7.86-7.98 (m, 8H), 8.08 (m, 4H), 8.22 (m, 4H), 10.8 (s, 2H)
¹³ C-NMR (400 MHz, DMSO-d ₆ , δ): 19.18, 22.11, 51.43, 55.37, 120.01, 120.26, 122.66, 127.75, 128.94, 129.23, 130.19, 131.91, 133.42, 133.88, 140.79, 146.30, 153.45

(Example 10-2: Preparation of photoresponsive ionic compound 4-2)
In 20 mL of dimethylformamide, 0.32 g (0.52 mmol) of the compound represented by the formula (1) obtained in Example 1 and 1.5 g (9.6 mmol) of propyl iodide were stirred at 80 ° C. for 48 hours. did. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. A precipitate formed by adding acetone to the concentrate was suction filtered and washed with acetone to obtain 0.42 g of an orange powder (yield 85%). ^{From the 1} H-NMR spectrum, it was confirmed that this powder was an ionic compound represented by the following formula (10-2).
^{1 H-NMR (400MHz, DMSO} -d 6, δ): 1.44 (m, 4H), 1.75 (br, 4H), 2.07 (br, 4H), 3.19 (br, 8H), 4.63 (s, 4H), 7.56 (m, 10H), 7.86-7.98 (m, 8H), 8.08 (m, 4H), 8.22 (m, 4H), 10.8 (s, 2H)

(Example 11: Preparation of photoresponsive ionic compound 5)
In 10 mL of dimethylformamide, 0.1 g (0.2 mmol) of the compound represented by the formula (3) obtained in Example 3 and 4.0 g (25 mmol) of ethyl iodide were stirred at 50 ° C. for 6 hours. The reaction solution was cooled to room temperature, and the resulting precipitate was filtered with suction and washed with acetone to obtain 0.1 g of an orange powder (yield 60%). ^{From the 1} H-NMR spectrum, it was confirmed that this powder was an ionic compound represented by the following formula (11).
¹ H-NMR (400MHz, DMSO-d ₆ , δ): 1.43 (t, 6H), 2.12 (m, 4H), 3.37 (m, 4H), 4.15-4.27 (m, 8H), 7.81-7.83 (m , 4H), 8.01 (d, 4H), 8.07 (d, 4H), 8.74 (m, 2H), 8.21 (s, 2H)

(Example 12: Preparation of photoresponsive ionic compound 6)
Instead of the compound represented by the formula (3), the same amount of the compound represented by the formula (4) obtained in Example 4 was used as in Example 11, except that the orange powder 0 0.1 g was obtained (yield 66%). ^{From 1} H-NMR spectrum, it was confirmed that this powder was a compound represented by the following formula (12).
¹ H-NMR (400MHz, DMSO-d ₅ , δ): 1.47 (t, 6H), 3.17 (m, 4H), 3.68 (m, 4H), 4.52 (m, 4H), 7.94 (m, 4H), 8.02-8.12 (m, 8H), 8.93 (d, 4H) 9.23 (t, 2H)

(Example 13: Preparation of photoresponsive ionic compound 7)
In 20 mL of distilled water, 0.07 g (0.09 mmol) of the compound represented by the formula (12) obtained in Example 12 and 0.1 g (0.6 mmol) of silver acetate were stirred at 40 ° C. for 24 hours. . The reaction solution was naturally filtered, and the filtrate was evaporated to dryness. The residue was dissolved in methanol and naturally filtered, and the filtrate was evaporated to dryness to obtain 0.05 g of a red-orange viscous solid (yield 92%). ^{From the 1} H-NMR spectrum, it was confirmed that the viscous solid was a compound represented by the following formula (13).
¹ H-NMR (400MHz, DMSO-d ₅ , δ): 1.49 (t, 6H), 1.60 (s, 6H), 3.20 (m, 4H), 3.70 (m, 4H), 4.56 (m, 4H), 7.95 (m, 4H), 8.01-8.10 (m, 8H), 8.98 (d, 4H) 9.36 (t, 2H)

(Example 14: Preparation of photoresponsive ionic compound 8)
0.58 g (6 mmol) of 3-aminopyridine was dissolved in 15 mL of dehydrated methylene chloride. A solution prepared by dissolving 0.93 g (3 mmol) of azobenzene-4,4′-dicarbonyl dichloride and 0.67 g (6.6 mmol) of triethylamine in 35 mL of dehydrated methylene chloride was added dropwise with stirring. Thereafter, the mixture was stirred at room temperature overnight (about 16 hours). The precipitate was filtered off, washed with methanol, and then vacuum dried to obtain 0.92 g of orange powder (yield 73%). ^{From 1} H-NMR and ¹³ C-NMR spectra, it was confirmed that this powder was a compound represented by the following formula (14).
¹ H-NMR (400MHz, DMSO-d ₆ , δ): 7.43 (dd, J = 4.6Hz, 2H), 8.15 (d, J = 8.3Hz, 4H), 8.23 (d, J = 8.5Hz, 4H) , 8.35 (dd, J = 4.6Hz, 2H), 8.96 (d, J = 2.5Hz, 2H), 10.7 (s, 2H)
¹³ C-NMR (100 MHz, DMSO-d ₆ , δ): 122.73, 123.57, 127.45, 129.20, 130.33, 135.63, 136.85, 142.05, 144.78, 153.55, 165.02

Thereafter, in 40 mL of dimethylformamide, 0.22 g (0.53 mmol) of the compound represented by the formula (14) obtained above and 1.33 g (10.6 mmol) of benzyl chloride were stirred at 80 ° C. for 48 hours. . After cooling the reaction solution to room temperature, the precipitate was filtered off to obtain 0.168 g of orange powder (yield 47%). ^{From 1} H-NMR and ¹³ C-NMR spectra, it was confirmed that this powder was an ionic compound represented by the following formula (15).
^{1 H-NMR (400MHz, DMSO} -d 6, δ): 5.94 (s, 4H), 7.46-7.58 (m, 10H), 8.12 (d, J = 8.6Hz, 4H), 8.21 (dd, J = 8.6 Hz, 5.9Hz, 2H), 8.30 (d, J = 8.5Hz, 4H), 8.82 (d, J = 9.9Hz, 2H), 9.16 (d, J = 5.9Hz, 2H), 9.71 (s, 2H) , 11.59 (s, 2H)
¹³ C-NMR (100 MHz, DMSO-d ₆ , δ): 65.23, 103.72, 122.99, 156.64, 127.49, 128.48, 128.98, 129.33, 129.73, 130.28, 132.61, 132.80, 134.12, 135.18

(Example 15: Preparation of photoresponsive ionic compound 9)
In 40 mL of dimethylformamide, 0.22 g (0.53 mmol) of the compound represented by the formula (14) obtained in Example 14 and 1.1 g (12.1 mmol) of 3-chloro-2-methyl-1-propene. Was stirred at 60 ° C. for 72 hours. In addition, 1.1 g (12.1 mmol) of 3-chloro-2-methyl-1-propene was added every 24 hours from the start of the reaction. After cooling the reaction solution to room temperature, the precipitate was filtered off to obtain 0.177 g of orange powder (yield 55%). ^{From the 1} H-NMR spectrum, it was confirmed that this powder was an ionic compound represented by the following formula (16).
¹ H-NMR (400MHz, DMSO-d ₆ , δ): 1.75 (s, 6H), 5.01 (s, 2H), 5.21 (s, 2H), 5.31 (s, 4H), 8.14 (d, J = 8.6 Hz, 2H), 8.22 (dd, J = 5.9Hz, 2H), 8.33 (d, J = 8.6Hz, 2H), 8.82 (d, J = 6Hz, 2H), 8.87 (d, J = 8.9Hz, 2H ), 9.60 (s, 2H), 11.7 (s, 2H)

(Example 16: Preparation of photoresponsive ionic compound 10)
1.20 g of compound was obtained in the same manner as in Example 14 except that 4-aminopyridine having the same substance amount was used instead of 3-aminopyridine (yield 95%). This compound has impurities removed by stirring in methanol. ^{From 1} H-NMR and ¹³ C-NMR spectra, it was confirmed that this compound was represented by the following formula (17).
¹ H-NMR (400MHz, DMSO-d ₆ , δ): 7.82 (dd, J = 4.8Hz, 4H), 8.10 (d, J = 8.6Hz, 4H), 8.22 (d, J = 8.5Hz, 4H) , 8.51 (dd, J = 4.7Hz, 4H), 10.79 (s, 2H)
¹³ C-NMR (100 MHz, DMSO-d ₆ , δ): 114.06, 122.75, 122.79, 129.31, 129.36, 135.13, 150.36

Thereafter, in place of the compound represented by the formula (14), the product 0 was obtained in the same manner as in Example 14 except that the same amount of the compound represented by the formula (17) was used. Obtained .148 g (yield 40%). ^{From the 1} H-NMR and ¹³ C-NMR spectra, it was confirmed that this product was an ionic compound represented by the following formula (18).
¹ H-NMR (400MHz, DMSO-d ₆ , δ): 5.74 (s, 4H), 7.43-7.50 (m, 10H), 8.13 (d, J = 8.6Hz, 4H), 8.32 (d, J = 8.6 Hz, 4H), 8.44 (d, J = 7.4Hz, 4H), 8.99 (d, J = 7.3Hz, 4H), 12.0 (s, 2H)
¹³ C-NMR (100 MHz, D ₂ O, δ): 100.75, 122.89, 128.49, 129.19, 131.64, 136.60, 145.21, 145.39, 156.51, 156.99, 158.34, 160.10, 164.95

(Example 17: Preparation of photoresponsive ionic compound 11)
Product 0 was obtained in the same manner as in Example 15 except that instead of the compound represented by Formula (14), the same amount of the compound represented by Formula (17) obtained in Example 16 was used. 0.201 g was obtained (62% yield). ^{From the 1} H-NMR spectrum, it was confirmed that this product was an ionic compound represented by the following formula (19).
¹ H-NMR (400MHz, DMSO-d ₆ , δ): 1.37 (s, 6H), 4.86 (s, 2H), 5.10 (s, 4H), 5.14 (s, 2H), 8.14 (d, J = 8.6 Hz, 4H), 8.34 (d, J = 7.4Hz, 4H), 8.46 (d, J = 7.4Hz, 4H), 8.82 (d, J = 7.4Hz, 4H), 12.0 (s, 2H)

(Example 18: Preparation of photoresponsive ionic compound 12)
0.58 g of dark red powder was obtained in the same manner as in Example 1 except that 4- (4-pyridylmethyl) aniline having the same amount of material was used instead of 4- (piperidin-1-ylmethyl) aniline. (Rate 36%). From ¹ H-NMR spectrum, it was confirmed that this compound is represented by the following formula (20).
¹ H-NMR (400MHz, DMSO-d ₆ , δ): 3.94 (s, 4H), 7.24 (m, 8H), 7.96 (m, 4H), 8.15 (m, 8H), 8.44 (m, 4H), 10.4 (s, 2H)

Thereafter, in 30 mL of dimethylformamide, 0.2 g (0.3 mmol) of the compound represented by the formula (20) obtained above and 1.5 g (16.6 mmol) of 3-chloro-2-methyl 1-propene were obtained. The mixture was stirred at 60 ° C. for 72 hours. The reaction solution was dried under reduced pressure, redissolved in ethanol, and naturally filtered. The filtrate was distilled off and concentrated under reduced pressure. This was added dropwise to acetone, and the resulting precipitate was filtered with suction to obtain 0.03 g of an orange powder (yield 11%). ^{From 1} H-NMR and ¹³ C-NMR spectra, it was confirmed that this powder was an ionic compound represented by the following formula (21).
¹ H-NMR (400MHz, DMSO-d ₆ , δ): 1.74 (s, 6H), 5.00 (s, 2H), 5.19 (s, 2H), 5.34 (s, 4H), 7.94 (d, 4H), 8.09 (d, 4H), 8.13 (d, 4H), 8.26 (d, 4H), 8.41 (d, 4H), 9.24 (d, 4H), 11.1 (s, 2H)
¹³ C-NMR (400 MHz, DMSO-d ₆ , δ): 28.64, 47.21, 58.94, 114.18, 120.92, 122.64, 127.27, 129.09, 129.40, 131.49, 133.17, 141.35, 145.16, 148.31, 157.02, 162.53, 168.14

(Example 18-2: Preparation of photoresponsive ionic compound 13)
In 50 mL of dimethylformamide, 0.25 g (0.45 mmol) of the compound represented by the formula (6-2) obtained in Example 6-2 and 2 g (12.8 mmol) of ethyl iodide were mixed at 60 ° C. for 48 hours. Stir for hours. After cooling the reaction solution to room temperature, acetone was added and the resulting precipitate was filtered with suction to obtain 0.3 g of a yellow powder (yield 77%). ^{From the 1} H-NMR spectrum, it was confirmed that this powder was an ionic compound represented by the following formula (22).
¹ H-NMR (400MHz, DMSO-d ₆ , δ): 1.29 (t, J = 8Hz, 6H), 3.08 (m, 16H), 3.42 (m, 4H), 3.51 (m, 4H), 7.35 (d , J = 12Hz, 4H), 7.45 (d, J = 12Hz, 4H), 7.14 (d, J = 8Hz, 4H), 7.36 (d, J = 8Hz, 4H)

Examples 19 to 38: Preparation and evaluation of dispersion (Example 19: SWCNT dispersion 1 by HiPCO method)
A single-walled carbon nanotube (hereinafter referred to as a single-walled carbon nanotube) prepared by dissolving 1.05 mg of the ionic compound (formula (7)) obtained in Example 7 in 3 mL of pure water and a HIGH-Pressure carbon monoxide (HiPCO) method. Single-wall carbon nanotubes may be described as “SWCNT”). This mixed solution was placed in a vial and subjected to ultrasonic treatment (80 W, 35 kHz) for 1 hour using an ultrasonic cleaning device (SHARP, UT-105).

Using a refrigerated centrifuge (Eppendorf, Centrifuge 5417R, FA45-24-11), the resulting mixture was centrifuged at room temperature (22 ° C.) for 3 hours at a rotational speed of 16400 rpm (28500 g). Thereafter, the supernatant was collected to obtain a dispersion in which SWCNTs were stably dispersed. The absorbance of the obtained SWCNT dispersion was measured using a UV-vis-NIR spectrophotometer (JASCO, V-670). This visible-near infrared (Vis-NIR) absorption spectrum is shown in FIG. 1 as a solid line (original). This Vis-NIR absorption spectrum is similar to the Vis-NIR absorption spectrum of SWCNT dispersions synthesized by the HiPCO method reported so far, and the ionic compound represented by formula (7) allows It was confirmed that the bundles of the above were unpacked and isolated.

1 mL of the obtained SWCNT dispersion was dispensed into a glass sample tube. While stirring the SWCNT dispersion at a rotation speed of 500 rpm, ultraviolet light (UV light) having a wavelength of 365 nm was applied to the SWCNT dispersion using an ultraviolet LED (HOYA CANDEO OPTRONICS, EXECURE H-1VC II) with an intensity of 250 mW / cm ^2. For 10 minutes. Images of the SWCNT dispersion before UV light irradiation (original) and the SWCNT aggregate after UV light irradiation are shown in FIG. As shown in FIG. 2 (a), the SWCNT aggregate after the UV light irradiation resulted in black precipitation of SWCNT.

Next, the SWCNT aggregate after the UV light irradiation was centrifuged at a rotational speed of 16400 rpm (28500 g) for 5 minutes. An image of the SWCNT aggregate after the centrifugation is shown in FIG. Thereafter, the supernatant was separated from the SWCNT aggregate and the absorbance was measured using a UV-vis-NIR spectrophotometer. This Vis-NIR absorption spectrum is shown by a dotted line (after UV irradiation) in FIG. Aggregation of SWCNT due to a change in solubility of SWCNT in pure water was also confirmed in the Vis-NIR absorption spectrum. That is, in the Vis-NIR absorption spectrum of the supernatant of the SWCNT aggregate after UV light irradiation, the sharp absorption peak appearing at 600-1600 nm characteristic of the Vis-NIR absorption spectrum of SWCNT synthesized by the HiPCO method has disappeared. . It is thought that the structure of the dispersant was changed by UV light irradiation and desorbed from the surface of the SWCNT, and the dispersibility of SWCNT in water was extremely reduced.

(Example 20: SWCNT dispersion 2 by HiPCO method)
The supernatant of the SWCNT dispersion before UV light irradiation in the same manner as in Example 19, except that the amounts of the ionic compound (formula (7)) and SWCNT obtained in Example 7 were changed to 10.0 mg, respectively. The absorbance was measured. The Vis-NIR absorption spectrum is shown in FIG.

(Example 21: SWCNT dispersion 3 by HiPCO method)
Example 19 is the same as Example 19 except that 3.0 mg of the ionic compound (formula (8)) obtained in Example 8 was used instead of the ionic compound (formula (7)) obtained in Example 7. Similarly, the absorbance of the supernatant of the SWCNT dispersion before UV light irradiation was measured. The Vis-NIR absorption spectrum is shown in FIG.

(Example 22: SWCNT dispersion 4 by HiPCO method)
Example 19 is the same as Example 19 except that 3.0 mg of the ionic compound (formula (10)) obtained in Example 10 was used instead of the ionic compound (formula (7)) obtained in Example 7. Similarly, the absorbance of the supernatant of the SWCNT dispersion before UV light irradiation was measured. The Vis-NIR absorption spectrum is shown in FIG.

(Example 23: SWCNT dispersion 5 by HiPCO method)
A solution prepared by dissolving 10.04 mg of the ionic compound (formula (15)) obtained in Example 14 in 20 mL of pure water and 6.99 mg of SWCNT synthesized by the HiPCO method were mixed. This mixed solution was placed in a vial and sonicated (80 W, 35 kHz) for 1 hour using an ultrasonic cleaning device. Then, this mixed solution is put into a plastic wide-mouth bottle with a capacity of 50 mL, and subjected to ultrasonic irradiation (20 W, 19.9 kHz) for 4 hours using an ultrasonic homogenizer (BRANSON, Advanced Digital Sonifier 250D), and a black SWCNT uniform dispersion liquid Got.

Using a refrigerated centrifuge, the obtained dispersion was centrifuged at room temperature (22 ° C.) for 3 hours at a rotation speed of 16400 rpm (28500 g). Thereafter, the supernatant was collected to obtain a SWCNT dispersion. The absorbance of the obtained SWCNT dispersion was measured using a UV-vis-NIR spectrophotometer. The Vis-NIR absorption spectrum is shown in FIG.

(Example 24: SWCNT dispersion 6 by HiPCO method)
Instead of the ionic compound obtained in Example 14 (Formula (15)), the same weight of the ionic compound obtained in Example 15 (Formula (16)) was used. Similarly, the absorbance of the supernatant of the SWCNT dispersion was measured. The Vis-NIR absorption spectrum is shown in FIG.

(Example 25: SWCNT dispersion 7 by HiPCO method)
Instead of the ionic compound obtained in Example 14 (Formula (15)), the same weight of the ionic compound obtained in Example 16 (Formula (18)) was used. Similarly, the absorbance of the supernatant of the SWCNT dispersion was measured. The Vis-NIR absorption spectrum is shown in FIG.

(Example 26: SWCNT dispersion 8 by HiPCO method)
Instead of the ionic compound obtained in Example 14 (Formula (15)), the same weight of the ionic compound obtained in Example 17 (Formula (19)) was used. Similarly, the absorbance of the supernatant of the SWCNT dispersion was measured. The Vis-NIR absorption spectrum is shown in FIG.

(Example 27: SWCNT dispersion 9 by HiPCO method)
Example 19 is the same as Example 19 except that 3.0 mg of the ionic compound (formula (21)) obtained in Example 18 was used instead of the ionic compound obtained in Example 7 (formula (7)). Similarly, the absorbance of the supernatant of the SWCNT dispersion before UV light irradiation was measured. This Vis-NIR absorption spectrum is shown in FIG.

(Example 28: SWCNT dispersion 10 by HiPCO method)
Instead of the ionic compound (formula (7)) obtained in Example 7, 1.0 mg of the ionic compound (formula (9)) obtained in Example 9 was used, and in place of pure water The absorbance of the supernatant of the SWCNT dispersion before UV light irradiation was measured in the same manner as in Example 19 except that propylene carbonate was used. The Vis-NIR absorption spectrum is shown in FIG.

1 mL of the obtained SWCNT dispersion was dispensed into a glass sample tube. While stirring the SWCNT dispersion at a rotation speed 500 rpm, using an ultraviolet LED, and irradiated with a wavelength of 365nm UV light at an intensity 250 mW / cm ² 20 min the SWCNT dispersion. Next, the SWCNT aggregate obtained after the UV light irradiation was centrifuged at a rotational speed of 16400 rpm (28500 g) for 5 minutes.

The supernatant was collected from the SWCNT aggregate after centrifugation and the absorbance was measured using a UV-vis-NIR spectrophotometer. This Vis-NIR absorption spectrum is shown by a solid line (after UV irradiation) in FIG. Similar to Example 19, the sharp absorption peak appearing at 600-1600 nm characteristic of the Vis-NIR absorption spectrum of SWCNT synthesized by the HiPCO method has disappeared, and SWCNT is aggregated in propylene carbonate. confirmed.

The light having a wavelength of 436 nm extracted from a high-pressure mercury lamp (USHIO) using a filter was irradiated for 20 minutes to the aggregate liquid in which the aggregation of SWCNTs occurred. Then, this aggregated liquid was subjected to ultrasonic treatment (80 W, 35 kHz) for 10 minutes using an ultrasonic cleaning device to re-disperse SWCNT. The supernatant was separated from the re-dispersed SWCNT dispersion and the absorbance was measured. This Vis-NIR absorption spectrum is shown by a dotted line (after Vis irradiation) in FIG. In the SWCNT dispersion of this example, SWCNTs aggregated by ultraviolet light irradiation for a short time of 20 minutes, whereas in the dispersion containing the azobenzene type dispersant described in Patent Document 2, the length of 3 to 15 hours was increased. SWCNTs are aggregated by irradiation with ultraviolet light for a period of time.

Next, the re-dispersed SWCNT dispersion was irradiated with ultraviolet light to agglomerate SWCNTs, and the SWCNT agglomerated liquid in which SWCNTs were aggregated was irradiated with visible light to re-disperse SWCNTs. FIG. 13 shows the change in absorbance when the supernatant of the SWCNT dispersion and SWCNT aggregate is irradiated with light having a wavelength of 1155 nm in this repeating step.

As shown in FIG. 13, it was confirmed that when the SWCNT dispersion liquid was irradiated with ultraviolet light, SWCNTs aggregated, and when the SWCNT aggregation liquid in which SWCNTs aggregated was irradiated with visible light, SWCNTs were dispersed. The isomer produced when the dispersant of the present invention is irradiated with ultraviolet light is chemically stable. For this reason, when the SWCNT dispersion containing the dispersant of the present invention is irradiated with ultraviolet light, the efficiency of desorbing the dispersant from SWCNT is high. On the other hand, with the azobenzene-type dispersant described in Patent Document 2, the isomer produced by ultraviolet light irradiation is not chemically stable, and thus immediately returns to the state before isomerization at room temperature. For this reason, the azobenzene type dispersant described in Patent Document 2 has a low desorption efficiency of the dispersant, and cannot be returned to the azobenzene type dispersant in the state before isomerization by irradiation with visible light.

(Example 29: SWCNT dispersion 11 by HiPCO method)
Instead of the ionic compound (formula (7)) obtained in Example 7, 1.51 mg of the ionic compound (formula (9)) obtained in Example 9 was used, and instead of pure water The absorbance of the supernatant of the SWCNT dispersion before UV light irradiation was measured in the same manner as in Example 19 except that propylene carbonate was used. This Vis-NIR absorption spectrum is shown in FIG. 14 by a solid line (original).

While agitating the SWCNT dispersion at a rotation speed of 500 rpm, the SWCNT dispersion was irradiated with UV light having a wavelength of 365 nm at an intensity of 150 mW / cm ² for 10 minutes using an ultraviolet LED. Next, the SWCNT dispersion after UV light irradiation was centrifuged at a rotational speed of 16400 rpm (28500 g) for 10 minutes. The supernatant was separated from the SWCNT dispersion after centrifugation, and the absorbance was measured using a UV-vis-NIR spectrophotometer. This Vis-NIR absorption spectrum is shown by a dotted line (after UV irradiation) in FIG.

Next, the supernatant was separated from the SWCNT dispersion after the UV light irradiation, and irradiated with light having a wavelength of 436 nm extracted from the high pressure mercury lamp using a filter for 20 minutes. Then, this supernatant was added to 1.01 mg of SWCNT synthesized by the HiPCO method. This mixed solution was subjected to ultrasonic treatment (80 W, 35 kHz) for 1 hour using an ultrasonic cleaning device. The obtained mixture was centrifuged at room temperature (22 ° C.) for 3 hours at a rotation speed of 16400 rpm (28500 g) using a cooling centrifuge. Thereafter, the supernatant was separated and the absorbance was measured using a UV-vis-NIR spectrophotometer. The Vis-NIR absorption spectrum is shown in FIG. 14 with a broken line (a dispersion obtained by reusing the collected supernatant).

(Example 29-2: SWCNT dispersion 12 by HiPCO method)
Except for using 3.0 mg of the ionic compound (formula (9-2)) obtained in Example 9-2 instead of the ionic compound (formula (7)) obtained in Example 7, In the same manner as in Example 19, the absorbance of the supernatant of the SWCNT dispersion before UV light irradiation was measured. This Vis-NIR absorption spectrum is shown in FIG. 14-2.

(Example 29-3: SWCNT dispersion 13 by HiPCO method)
Instead of the ionic compound (formula (7)) obtained in Example 7, 3.0 mg of the ionic compound (formula (10-2)) obtained in Example 10-2 was used. The absorbance of the supernatant of the SWCNT dispersion before UV light irradiation was measured in the same manner as in Example 19 except that propylene carbonate was used instead of water. This Vis-NIR absorption spectrum is shown in FIG. 14-3.

(Example 30: SWCNT dispersion by SG method)
A solution obtained by dissolving 12.1 mg of the ionic compound (formula (7)) obtained in Example 7 in 3 mL of pure water was mixed with 6.0 mg of SWCNT synthesized by the super growth (SG) method. This mixed solution was put into a vial and subjected to ultrasonic treatment (80 W, 35 kHz) for 1 hour using an ultrasonic cleaning device to obtain a dispersion in which SWCNTs were stably dispersed. The obtained dispersion was diluted 20 times with pure water, and the absorbance was measured using a UV-vis-NIR spectrophotometer. The UV-vis-NIR absorption spectrum is shown by a solid line (original) in FIG.

Next, 1 mL of this dispersion is dispensed into a glass cell, and UV light having a wavelength of 365 nm is irradiated to the dispersion at an intensity of 450 mW / cm ² for 20 minutes using an ultraviolet LED while stirring at a rotation speed of 500 rpm. did. In the dispersion after UV light irradiation, black aggregates of SWCNTs were formed. The mixed solution in which the aggregate was formed was centrifuged at a rotational speed of 16400 rpm (28500 g) for 5 minutes. Thereafter, the supernatant was separated and the absorbance was measured using a UV-vis-NIR spectrophotometer. This UV-vis-NIR absorption spectrum is shown by a dotted line (after UV irradiation) in FIG. It was confirmed that the absorption spectrum derived from SWCNT synthesized by the SG method was reduced by UV light irradiation.

(Example 31: SWCNT dispersion by eDIPS method)
A solution obtained by dissolving 3.0 mg of the ionic compound (formula (7)) obtained in Example 7 in 3 mL of pure water and 1.0 mg of SWCNT synthesized by the enhanced Direct Injection Pyrolytic Synthesis method (eDIPS) method were mixed. . This mixed solution was put into a vial and subjected to ultrasonic treatment (80 W, 35 kHz) for 1 hour using an ultrasonic cleaning device to obtain a dispersion in which SWCNTs were stably dispersed. The absorbance of this dispersion was measured using a UV-vis-NIR spectrophotometer. This UV-vis-NIR absorption spectrum is shown in FIG. 16 by a solid line (original).

Next, 1 mL of this dispersion is dispensed into a glass cell, and UV light having a wavelength of 365 nm is irradiated to the dispersion at an intensity of 450 mW / cm ² for 20 minutes using an ultraviolet LED while stirring at a rotation speed of 500 rpm. did. In the dispersion after UV light irradiation, black aggregates of SWCNTs were formed. The mixed solution in which the aggregate was formed was centrifuged at a rotational speed of 16400 rpm (28500 g) for 5 minutes. Thereafter, the supernatant was separated and the absorbance was measured using a UV-vis-NIR spectrophotometer. This UV-vis-NIR absorption spectrum is shown by a dotted line (after UV irradiation) in FIG. It was confirmed that the absorption spectrum derived from SWCNT synthesized by the eDIPS method was reduced by UV light irradiation.

(Example 32: MWCNT dispersion)
A solution obtained by dissolving 3.0 mg of the ionic compound (formula (7)) obtained in Example 7 in 3 mL of pure water and 1.0 mg of multi-walled carbon nanotube (MWCNT) (Nanocyl, NC-7000) were mixed. . This mixed solution was put into a vial and subjected to ultrasonic treatment (80 W, 35 kHz) for 1 hour using an ultrasonic cleaning device to obtain a dispersion in which MWCNTs were stably dispersed. The obtained dispersion was diluted twice with pure water, and the absorbance was measured using a UV-vis-NIR spectrophotometer. This UV-vis-NIR absorption spectrum is shown by a solid line (original) in FIG.

Next, 1 mL of this dispersion is dispensed into a glass cell, and UV light having a wavelength of 365 nm is irradiated to the dispersion at an intensity of 450 mW / cm ² for 20 minutes using an ultraviolet LED while stirring at a rotation speed of 500 rpm. did. In the dispersion after UV light irradiation, black aggregates of MWCNTs were formed. The mixed solution in which the aggregate was formed was centrifuged at a rotational speed of 16400 rpm (28500 g) for 5 minutes. Thereafter, the supernatant was separated and the absorbance was measured using a UV-vis-NIR spectrophotometer. This UV-vis-NIR absorption spectrum is shown by a dotted line (after UV irradiation) in FIG. It was confirmed that the absorption spectrum derived from MWCNT decreased by UV light irradiation.

(Example 33: Carbon black dispersion 1)
A solution obtained by dissolving 3.05 mg of the ionic compound (formula (7)) obtained in Example 7 in 3 mL of pure water and 1.03 mg of carbon black (Mitsubishi Chemical, CB-2600) were mixed. This mixed solution was put into a vial and subjected to ultrasonic treatment (80 W, 35 kHz) for 1 hour using an ultrasonic cleaning device to obtain a dispersion in which carbon black was stably dispersed. An image of this dispersion is shown in FIG. 18 (with a dispersant). As a comparison, an image of a mixture of carbon black and pure water is also shown in FIG. 18 (no dispersant). It was confirmed that carbon black was well dispersed in pure water by using a dispersant.

Further, the absorbance of this dispersion containing the dispersant was measured using a UV-vis-NIR spectrophotometer. This UV-vis-NIR absorption spectrum is shown by a solid line (with a dispersant) in FIG. As a comparison, FIG. 19 shows a UV-vis-NIR absorption spectrum of a mixture of carbon black and pure water with a dotted line (without a dispersant).

(Example 34: Carbon black dispersion liquid 2)
A carbon black dispersion was prepared in the same manner as in Example 33 except that the amount of carbon black was changed to 60 mg and the amount of the ionic compound (formula (7)) was changed to 10.5 mg. This dispersion was diluted 40 times with pure water, 1 mL was taken and transferred to a glass sample tube. An image of this dispersion is shown in FIG. 20 (original). Then, while stirring the sample tube at a rotation speed of 500 rpm, the dispersion liquid was irradiated with UV light having a wavelength of 365 nm at an intensity of 450 mW / cm ² for 20 minutes using an ultraviolet LED. An image of the dispersion which was allowed to stand for 12 hours after UV light irradiation is also shown in FIG. 20 (after UV light irradiation). It was confirmed that carbon black aggregates and precipitates when irradiated with UV light.

Further, the absorbance of the dispersion before and after UV light irradiation was measured using a UV-vis-NIR spectrophotometer. These UV-vis-NIR absorption spectra are shown in FIG. 21 by a solid line (original) and a dotted line (after UV light irradiation), respectively.

(Example 34-2: Carbon black dispersion 3)
A solution prepared by dissolving 45.1 mg of the ionic compound (formula (7)) obtained in Example 7 in 2.4 mL of pure water and 600 mg of carbon black (Mitsubishi Chemical, CB-4000B) were mixed. This mixed solution was put into a vial and subjected to ultrasonic treatment (80 W, 37 kHz) for 1 hour using an ultrasonic cleaning device to obtain a dispersion in which carbon black was stably dispersed. When the viscosity of this dispersion was measured using a tuning fork vibration viscometer (SV-1A, manufactured by AND), it was 3.38 mPa · s at 26 ° C. It was confirmed that carbon black was well dispersed even in a carbon black dispersion having a high concentration, and a low viscosity dispersion was obtained.

Example 34-3: Carbon Black Dispersion 4
A solution obtained by dissolving 30.2 mg of the ionic compound (formula (9)) obtained in Example 9 in 2.7 mL of propylene carbonate and 300 mg of carbon black (Mitsubishi Chemical, CB-4000B) were mixed. This mixed solution was put into a vial and subjected to ultrasonic treatment (80 W, 37 kHz) for 1 hour using an ultrasonic cleaning device to obtain a dispersion in which carbon black was stably dispersed. When the viscosity of this dispersion was measured using a tuning fork vibration viscometer, it was 120 mPa · s at 26 ° C. It was confirmed that carbon black was well dispersed even in a carbon black dispersion having a high concentration, and a low viscosity dispersion was obtained.

(Example 34-4: Carbon black dispersion 5)
Example 34-2 except that 3.7 mL of N-methylpyrrolidone was used instead of 2.7 mL of propylene carbonate, and carbon black was changed to “Ketjen Black EC300J” manufactured by Lion Specialty Chemicals. Thus, a high-viscosity paste in which carbon black was dispersed was obtained.

(Example 35: Graphene nanoplatelet dispersion)
Except that the amount of the ionic compound (formula (7)) was 3.03 mg and that 1.05 mg of graphene nanoplatelets (XG SCIENCES, xGnP-C-300) was used instead of carbon black. A graphene nanoplatelet dispersion was prepared in the same manner as in Example 33. An image of this dispersion is shown in FIG. 22 (with a dispersant). As a comparison, an image of a mixed solution of graphene nanoplatelets and pure water is also shown in FIG. 22 (no dispersant). It was confirmed that the graphene nanoplatelets were well dispersed in pure water by using the dispersant.

Further, the absorbance of this dispersion containing the dispersant was measured using a UV-vis-NIR spectrophotometer. This UV-vis-NIR absorption spectrum is shown by a solid line (with a dispersant) in FIG. As a comparison, FIG. 23 shows a UV-vis-NIR absorption spectrum of a mixed solution of graphene nanoplatelets and pure water as a dotted line (without a dispersant).

(Example 36: Copper phthalocyanine dispersion)
A solution obtained by dissolving 10.5 mg of the ionic compound (formula (7)) obtained in Example 7 in 3 mL of pure water and 311.5 mg of copper phthalocyanine (Tokyo Kasei) were mixed. This mixed solution was put into a vial and subjected to ultrasonic treatment (80 W, 35 kHz) for 20 minutes using an ultrasonic cleaning device to obtain a dispersion in which copper phthalocyanine was stably dispersed. An image of this dispersion is shown in FIG. 24 (with dispersant). As a comparison, an image of a mixed solution of copper phthalocyanine and pure water is also shown in FIG. 24 (no dispersant). It was confirmed that copper phthalocyanine was well dispersed in pure water by using a dispersant.

Also, an image when a copper phthalocyanine dispersion containing a dispersant is dropped onto a slide glass (Matsunami Glass) and spread is shown in FIG. 25 (with a dispersant). As a comparison, an image when a liquid mixture of copper phthalocyanine and pure water is dropped onto a slide glass and spread is also shown in FIG. 25 (no dispersant). By using the dispersant, the copper phthalocyanine dispersion showed good film forming properties.

(Example 37: Iron (III) oxide dispersion)
A solution obtained by dissolving 5.02 mg of the ionic compound (formula (7)) obtained in Example 7 in 3 mL of pure water and iron oxide (III) (Fe ₂ O ₃ ) (Wako Pure Chemical Co., Ltd., Cosmetic Grade) 5 0.01 mg was mixed. This mixed solution was put into a vial and subjected to ultrasonic treatment (80 W, 35 kHz) for 1 hour using an ultrasonic cleaning device to obtain a dispersion liquid in which iron (III) oxide was dispersed. An image of this dispersion is shown in FIG. 26 (with a dispersant). As a comparison, an image of a mixed solution of iron (III) oxide and pure water is also shown in FIG. 26 (no dispersant). It was confirmed that the use of the dispersant improved the dispersibility of iron (III) oxide in pure water.

Further, the absorbance of this dispersion containing the dispersant was measured using a UV-vis-NIR spectrophotometer. This UV-vis-NIR absorption spectrum is shown by a solid line (with a dispersant) in FIG. As a comparison, FIG. 27 shows a UV-vis-NIR absorption spectrum of a mixed solution of iron (III) oxide and pure water as a dotted line (without a dispersant).

(Example 38: Coronene dispersion)
A solution obtained by dissolving 3.12 mg of the ionic compound (formula (7)) obtained in Example 7 in 3 mL of pure water and 1.16 mg of coronene (Tokyo Kasei) were mixed. This mixed solution was put into a vial and subjected to ultrasonic treatment (80 W, 35 kHz) for 1 hour using an ultrasonic cleaning device to obtain a dispersion in which coronene was dispersed. An image of this dispersion is shown in FIG. 28 (with a dispersant). As a comparison, an image of a mixed solution of coronene and pure water is also shown in FIG. 28 (no dispersant). It was confirmed that the dispersibility of coronene in pure water was improved by using the dispersant.

Further, the absorbance of this dispersion containing the dispersant was measured using a UV-vis-NIR spectrophotometer. This UV-vis-NIR absorption spectrum is shown by a solid line (with a dispersant) in FIG. As a comparison, FIG. 29 shows a UV-vis-NIR absorption spectrum of a mixed solution of coronene and pure water as a dotted line (without a dispersant).

The ionic compound of the present invention can be used for nanocarbon material dispersants, nanocarbon material inks, nanocarbon material thin film processing, and the like.

Claims

An ionic compound represented by the following general formula (I).

(In the formula, X is a kind selected from amide bonds and ester bonds shown below.

A is a substituent having a cation moiety represented by the following.

However, n is a number from 1 to 10, R 1 is hydrogen, an alkyl group, a phenyl group, a polyethylene glycol group, or an allyl group, and R 2 and R 3 are independently hydrogen or an alkyl group. B represents an anion, and m is a number such that mB becomes -2 valent. )
The ionic compound according to claim 1, which is a kind selected from substances represented by the following chemical formulas:
A dispersant for dispersing a dispersoid in a dispersion medium containing at least one of water and a polar organic solvent,
A dispersant comprising the ionic compound according to claim 1 as an active ingredient.
The dispersant according to claim 3, wherein the dispersoid is at least one selected from nanocarbon materials, hydrophobic fine particles, and hydrophobic molecules.
The dispersant according to claim 4, wherein the dispersoid is at least one selected from single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon black, graphene, phthalocyanine, metal phthalocyanine, coronene, and iron oxide fine particles.
With dispersoids,
A dispersion medium containing at least one of water and a polar organic solvent;
A dispersant according to any one of claims 3 to 5;
A dispersion having
The dispersion according to claim 6, wherein the dispersoid is at least one selected from nanocarbon materials, hydrophobic fine particles, and hydrophobic molecules.
The dispersion according to claim 7, wherein the dispersoid is at least one selected from single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon black, graphene, phthalocyanine, metal phthalocyanine, coronene, and iron oxide fine particles.
A mixing step of mixing a dispersoid, a dispersion medium containing at least one of water and a polar organic solvent, and a dispersant according to any one of claims 3 to 5 to obtain a mixed liquid;
A dispersion step of oscillating the mixed liquid with ultrasonic waves and dispersing the dispersoid in the dispersion medium;
A method for producing a dispersion having
The method for producing a dispersion according to claim 9, wherein the dispersoid is at least one selected from the nanocarbon material, hydrophobic fine particles, and hydrophobic molecules.
The method for producing a dispersion according to claim 10, wherein the dispersoid is at least one selected from single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon black, graphene, phthalocyanine, metal phthalocyanine, coronene, and iron oxide fine particles.
The dispersion according to any one of claims 6 to 8 is irradiated with light having a predetermined wavelength of 250 to 450 nm to desorb the dispersant from the dispersoid, and disperse the dispersoid in the dispersion medium. A method for producing an agglomerated liquid by aggregating to obtain an aggregated liquid.
The dispersion according to any one of claims 6 to 8 is irradiated with light having a predetermined wavelength of 250 to 450 nm to desorb the dispersant from the dispersoid, and the dispersoid is dispersed in the dispersion medium. An aggregating step of aggregating to obtain an aggregated liquid;
The aggregate liquid is irradiated with light having a predetermined wavelength of 380 to 500 nm different from the wavelength of light used when the dispersant is desorbed from the dispersoid in the aggregation step, and the dispersion medium is dispersed in the dispersion medium. A dispersion step of dispersing the quality to obtain a dispersion;
A method for producing a dispersion having
The dispersion according to any one of claims 6 to 8 is irradiated with light having a predetermined wavelength of 250 to 450 nm to desorb the dispersant from the dispersoid, and the dispersoid is dispersed in the dispersion medium. An aggregating step of aggregating to obtain an aggregated liquid;
A recovery step of recovering a solution containing at least a part of the dispersant and at least a part of the dispersion medium from the aggregate liquid;
After mixing the other dispersoid and the solution, a dispersion step of vibrating the obtained mixture with ultrasonic waves to disperse the dispersoid in the dispersion medium;
A method for producing a dispersion having