WO2006112162A1

WO2006112162A1 - Gel-form composition and process for producing the same

Info

Publication number: WO2006112162A1
Application number: PCT/JP2006/303952
Authority: WO
Inventors: Gen Masuda; Yasuharu Kato
Original assignee: Nisshinbo Industries, Inc.
Priority date: 2005-03-31
Filing date: 2006-03-02
Publication date: 2006-10-26
Also published as: JP2006282418A

Abstract

A gel-form composition characterized by comprising carbon nanotubes and a neutralization-salt type ionic liquid obtained by the neutralization reaction of an acid with a base. This gel-form composition is excellent in carbon nanotube dispersibility and environmental friendliness and can be obtained at a relatively low cost. In particular, using benzoic acid or a derivative thereof as the acid constituting the neutralization-salt type ionic liquid gives a gel-form composition having excellent carbon nanotube dispersibility.

Description

Specification

Gel composition and method for producing the same

Technical field

[0001] The present invention relates to a gel composition and a method for producing the same, and more specifically to a gel composition comprising carbon nanotubes and a neutralized salt type ionic liquid, and a method for producing the same.

Background art

[0002] Carbon nanotubes have various electrical properties ranging from metallic properties to semiconducting properties, and are attracting attention as new additives that can improve the physical properties of materials due to their mechanical strength properties. Take a bath.

On the other hand, carbon nanotubes exist in the form of a large bundle that is not as long as a single tube, and thus it has been pointed out that it has the disadvantage of poor processability and is difficult to put into practical use.

[0003] As a method for improving the processability of carbon nanotubes, (1) a method of chemically treating carbon nanotubes to obtain a dispersion (see Patent Document 1), (2) affinity liquid without chemically modifying carbon nanotubes (3) A method of coating carbon nanotubes with a conjugated polymer and dispersing them in a resin (see Patent document 3), (4) Carbon nanotubes in an organic solvent (5) a method for obtaining a gel composition comprising carbon nanotubes and an ionic liquid (see Patent Document 5), (6) using an ionic liquid having a polymerizable group A method of dispersing carbon nanotubes in a polymer (see Patent Document 6) has been reported.

[0004] However, the above-described method (1) for increasing affinity by chemical treatment requires a separate process for chemically treating carbon nanotubes, resulting in complicated processes and increased costs, and chemical modification. Therefore, the problem that the characteristics of the carbon nanotube are impaired is pointed out. The method (2) for dispersing without chemical treatment requires the use of a special dispersion medium with a complicated structure, which is also disadvantageous in terms of cost.

Using the ultrasonic irradiation and stirring described in (3) and (4) above, the organic solvent or conjugated polymer is separated. The dispersion method may cause the carbon nanotubes to re-aggregate when applied to a substrate or the like where the dispersion of the carbon nanotubes becomes insufficient and tends to occur.

In the case of the gel composition (the carbon nanotubes are evenly dispersed in the ionic liquid) or polymer using the ionic liquids (5) and (6) above, the ionic liquid to be used has a high purity. In addition, it is difficult to obtain a product. In addition, many ionic liquids are expensive because they have fluorine atoms in the structure, and there are concerns about environmental impact. Furthermore, when a gel composition is used, there is a problem that time is required for gelling.

Patent Document 1: Japanese Patent Application Laid-Open No. 2004-216516

Patent Document 2: Japanese Patent Laid-Open No. 2003-238126

Patent Document 3: Japanese Patent Laid-Open No. 2002-244490

Patent Document 4: Japanese Patent Laid-Open No. 2002-255528

Patent Document 5: Japanese Patent Application Laid-Open No. 2004-255481

Patent Document 6: Japanese Unexamined Patent Application Publication No. 2004-142972

Disclosure of the invention

Problems to be solved by the invention

[0006] The present invention has been made in view of such circumstances, and is a gel-like composition that is excellent in dispersibility of carbon nanotubes, is excellent in environmental adaptability, and can be obtained relatively inexpensively. And it aims at providing the simple manufacturing method.

Means for solving the problem

[0007] As a result of intensive studies to achieve the above object, the present inventor has obtained a neutralization reaction of an acid, preferably a benzoic acid, and a base as a gelling medium for carbon nanotubes. The inventors have found that a gel-like composition in which carbon nanotubes are well dispersed can be obtained easily and quickly by using a Japanese salt type ionic liquid, and completed the present invention.

That is, the present invention

1. a gel composition comprising carbon nanotubes and a neutralized salt-type ion liquid obtained by a neutralization reaction of an acid and a base,

2. The neutralized salt type ionic liquid contains benzoic acid or a derivative thereof as an anion component. 1 gel-like composition characterized in that

3. Gelatin composition according to 2, characterized by being represented by the following formula (1):

[Chemical 1]

{Wherein Ri to R ⁵ may be the same as or different from each other, a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 6 carbon atoms [this alkyl group is a bur group, a aryl group, a pro It may be substituted with a pargyl group, an attalyloyl group, a methacryloyl group or an epoxy group. ], — (CH) —OR ′ group, — (CH) —SR ′ group, — (CH) — OCO—R ′ group

2 n 2 n 2 n

,-(CH) -COO-R 'group, (CH) -NHCO-R' group, (CH) — CONH

2 n 2 n 2 n

-R 'group,-(CH) -NHCONH-R' group, CO- group (wherein

2 n

Represents a branched alkyl group having 1 to 6 carbon atoms (this alkyl group may be substituted with a buyl group, a allyl group, a propargyl group, an attalyloyl group, a methacryloyl group or an epoxy group), and n is 1. Indicates an integer of ~ 6. ] Represents a bur group, a allyl group, a propargyl group, an attalyl group, a methacryloyl group, or an epoxy group. }

4. The liquid of any one of 1 to 3, characterized in that the base is an amine, an amidine or a guanidine,

5. The gel composition according to any one of 1 to 4, wherein the neutralized salt type ionic liquid has a polymerizable group in at least one of a cation component and an anion component;

6. The gel-like composition according to 5, wherein the neutralized salt type ionic liquid has a polymerizable group in an anion component;

7. The gel composition according to any one of 1 to 6, wherein the carbon nanotube is a single-walled carbon nanotube,

8. A carbon nanotube-containing polymer obtained by polymerizing the neutralized salt type ionic liquid in the gel composition of 5 or 6,

9. Neutralized salt form obtained by neutralization of carbon nanotubes with acid and base A method for producing a gel-like composition comprising applying a shearing force to a mixture obtained by mixing an on-liquid,

10. The method for producing a gel-like composition according to 9, wherein the mixture is prepared by directly adding a carbon nanotube to a blend obtained by blending the acid and the base.

11. The method for producing a gel composition according to 9 or 10, wherein after applying the shearing force, the excess neutralized salt is removed by centrifugation.

I will provide a.

The invention's effect

[0008] According to the present invention, a neutralized salt type ionic liquid is used as a gelling (dispersing) medium for carbon nanotubes, so that a gel-like composition can be obtained at a lower cost and more easily than conventional methods. be able to. In this case, the gel-like composition can be easily produced by simply mixing an acid and a base and carbon nanotubes and applying a shearing force, and a quaternary salt type ionic liquid is used as a gelling medium. Compared to the case, gelation speed is faster!

In addition, various acids and bases that do not contain halogen atoms can be used. Compared to quaternary salt type ionic liquids, various non-halogen carbon nanotube-dispersed gel compositions can be easily obtained, and environmental load countermeasures are possible. And the point is also excellent.

Furthermore, by using benzoic acid as an acid component constituting the ionic liquid, a gel-like composition that is superior in dispersibility of carbon nanotubes can be obtained.

In addition, a carbon nanotube-containing polymer can be easily obtained by using a neutralized salt type ionic liquid having a polymerizable group. This polymer is superior in electrical properties such as electrical conductivity compared to a polymer obtained using a quaternary salt type ionic liquid having a polymerizable group.

BEST MODE FOR CARRYING OUT THE INVENTION

[0009] Hereinafter, the present invention will be described in more detail.

The gel composition according to the present invention comprises carbon nanotubes and a neutralized salt type ionic liquid obtained by a neutralization reaction of an acid and a base.

Here, the carbon nanotube is a carbon-based material that has the shape force of a dullafen sheet rolled into a cylindrical shape. Single-walled carbon nanotubes and double-walled carbon nanotubes are determined from the number of peripheral walls. They can be broadly classified into tubes and multi-walled carbon nanotubes, and any of them can be used in the gel composition of the present invention. In the present invention, single-walled carbon nanotubes are particularly suitable.

The neutralized salt type ionic liquid is a liquid salt obtained by a neutralization reaction between an acid and a base. The ionic liquid is not particularly limited as long as it is a liquid at 100 ° C or lower, but it is preferably a liquid at 50 ° C or lower, more preferably 30 ° C or lower, in view of handling at around room temperature. It is desirable that there be.

[0010] Examples of the acid constituting the neutralized salt type ionic liquid include carboxylic acid such as trifluoroacetic acid, benzoic acid, propionic acid, formic acid, and derivatives thereof, sulfonic acid such as methanesulfonic acid, and derivatives thereof, HC1 , H SO, HNO, HBF, HPF, (CF SO) NH, etc.

2 4 3 4 6 3 2 2

Of these, benzoic acid and its derivatives, propionic acid, formic acid, methanesulfonic acid, H 2 SO, and HNO, which do not contain halogen atoms, are suitable in view of obtaining a gel composition having a low environmental impact. .

2 4 3

[0011] In particular, benzoic acid or a derivative thereof is suitable, and by using these, a gel composition in which carbon nanotubes are more dispersed (large volume) can be obtained.

As such benzoic acid or a derivative thereof, for example, those represented by the following formula (1) can be suitably used without particular limitation.

[0012] [Chemical 2]

2 n 2 n 2 n

,-(CH) -COO-R 'group, (CH) -NHCO-R' group, (CH) — CONH

2 n 2 n 2 n

-R 'group,-(CH) -NHCONH-R' group, CO- group (wherein

2 n Represents a branched alkyl group having 1 to 6 carbon atoms (this alkyl group may be substituted with a buyl group, a allyl group, a propargyl group, an attalyloyl group, a methacryloyl group or an epoxy group), and n is 1. Indicates an integer of ~ 6. ], A bur group, a allyl group, a propargyl group, an attalyl group, a methacryloyl group, or an epoxy group. }

[0013] Here, specific examples of the linear or branched alkyl group having 1 to 6 carbon atoms include a methyl group, an ethinole group, an n-propinole group, an i-propinole group, an n-butinole group, an s-butinole group, an i-butinore group. Group, t-butinole group, n-pentinole group, i-pentinole group, neo pentinole group, t-pentinole group, 1 methylbutyl group, 2-methylbutyl group, 1-ethylpropyl group, n-hexyl group, i-hexyl group, Examples thereof include 1-methylpentyl group, 1,3 dimethylbutoxy group, 1-ethylbutyl group, 2-ethylbutyl group and the like.

n is a force of 1 to 6 Since a low molecular weight tends to become an ionic liquid, a force of 1 to 4 is preferable, and 1 to 2 is more preferable.

[0014] Specific examples of the-(CH) —OR 'group include: -CH OCH,-(CH) OCH,-(CH

2 n 2 3 2 2 3 2

) OCH, 1 CH OC H, 1 (CH) OC H, 1 (CH) OC H, 1 CH OC H, 1 (

3 3 2 2 5 2 2 2 5 2 3 2 5 2 3 7

CH) OC H, One (CH) OC H, One CH OC H, One (CH) OC H, One (CH) OC

2 2 3 7 2 3 3 7 2 4 9 2 2 4 9 2 3 4

H, 1 CH OC H, 1 (CH 3) OC H, 1 (CH 2) OC H and the like.

9 2 5 11 2 2 5 11 2 3 5 11

-(CH) — Examples of SR 'groups include CH SCH,-(CH) SCH,-(CH)

2 n 2 3 2 2 3 2

SCH, one CH SC H, one (CH) SC H, one (CH) SC H, one CH SC H, one (C

3 3 2 2 5 2 2 2 5 2 3 2 5 2 3 7

H) SC H, one (CH) SC H, CH SC H, one (CH) SC H, one (CH) SC H

2 2 3 7 2 3 3 7 2 4 9 2 2 4 9 2 3 4 9

, -CH SC H,-(CH) SC H,-(CH) SC H, and the like.

2 5 11 2 2 5 11 2 3 5 11

[0015] Specific examples of the-(CH) -OCOR 'group include:-CH OCOCH,-(CH) OCOC

2 n 2 3 2 2

H, One (CH) OCOCH, -CH OCOC H, One (CH) OCOC H, One (CH) OC

3 2 3 3 2 2 5 2 2 2 5 2 3

OC H, -CH OCOC H, one (CH) OCOC H, one (CH) OCOC H, one CH O

2 5 2 3 7 2 2 3 7 2 3 3 7 2

COC H, one (CH) OCOC H, one (CH) OCOC H, one CH OCOC H, one (C

4 9 2 2 4 9 2 3 4 9 2 5 11

H) OCOC H, and one (CH 3) OCOC H.

2 2 5 11 2 3 5 11

Specific examples of-(CH) -COOR 'groups are-CH COOCH,-(CH) COOC

2 n 2 3 2 2

H, One (CH) COOCH, -CH COOC H, One (CH) COOC H, One (CH) CO

3 2 3 3 2 2 5 2 2 2 5 2 3

OC H, 1 CH COOC H, 1 (CH) COOC H, 1 (CH) COOC H, 1 CH C

2 5 2 3 7 2 2 3 7 2 3 3 7 2 OOC H, one (CH) COOC H, one (CH) COOC H, one CH COOC H, one (C

4 9 2 2 4 9 2 3 4 9 2 5 11

H) COOCH, (CH) COOCH and the like.

2 2 5 11 2 3 5 11

[0016] Specific examples of the-(CH) -NHCOR 'group include CH NHCOCH and-(CH) NH

2 n 2 3 2 2

COCH, one (CH) NHCOCH, one CH NHCOC H, one (CH) NHCOC H, one

3 2 3 3 2 2 5 2 2 2 5

(CH) NHCOC H,-CH NHCOC H,-(CH) NHCOC H,-(CH) NH

2 3 2 5 2 3 7 2 2 3 7 2 3

COC H, one CH NHCOC H, one (CH) NHCOC H, one (CH) NHCOC H,

3 7 2 4 9 2 2 4 9 2 3 4 9

— CH NHCOC H,-(CH) NHCOC H,-(CH) NHCOC H etc.

2 5 11 2 2 5 11 2 3 5 11

It is.

-(CH) — CONHR 'Specific examples of groups include: -CH CONHCH,-(CH) CO

2 n 2 3 2 2

NHCH, one (CH) CONHCH, one-CH CONHC H, one (CH) CONHC H, one

3 2 3 3 2 2 5 2 2 2 5

(CH) CONHC H, 1 CH CONHC H, 1 (CH) CONHC H, 1 (CH) CO

2 3 2 5 2 3 7 2 2 3 7 2 3

NHC H, one CH CONHC H, one (CH) CONHC H, one (CH) CONHC H,

3 7 2 4 9 2 2 4 9 2 3 4 9

— CH CONHC H,-(CH) CONHC H,-(CH) CONHC H etc.

2 5 11 2 2 5 11 2 3 5 11

It is.

[0017] Specific examples of the-(CH) -NHCONHR 'group include CH NHCONHCH,-(C

2 n 2 3

H) NHCONHCH, I (CH) NHCONHCH, I CH NHCONHC H, I (C

2 2 3 2 3 3 2 2 5

H) NHCONHC H, I (CH) NHCONHC H, I CH NHCONHC H, I (C

2 2 2 5 2 3 2 5 2 3 7

H) NHCONHC H, I (CH) NHCONHC H, I CH NHCONHC H, I (C

2 2 3 7 2 3 3 7 2 4 9

H) NHCONHC H, one (CH) NHCONHC H, one CH NHCONHC H, - (

2 2 4 9 2 3 4 9 2 5 11

CH 2) NHCONHC H,-(CH 2) NHCONHC H and the like.

2 2 5 11 2 3 5 11

— Specific examples of the COR ′ group include —COCH, —COC H, —COC H, —COC H

3 2 5 3 7 4 9

, -COC H and the like.

5 11

[0018] Among these, Ri to R ⁵ are represented by a hydrogen atom, a methyl group, an ethyl group, and n-propylene because they are easier to synthesize, more easily available, and more easily have a low molecular weight. And an alkoxyalkyl group having a total carbon number of less than 3 are preferred. Preferred examples of the benzoic acid of the present invention include those represented by the following formulas (2) to (6), but are not limited thereto.

[0019] [Chemical 3]

On the other hand, the base is not particularly limited, but amines, amidines, and guanidines are preferable.

Examples of amines include primary amines, secondary amines, and tertiary amines. For example, ammonia, dimethylamine, jetylamine, triethylamine, dimethylethylamine, 2-methoxyethylamine, jetyl ( 2-methoxyethyl) amine, pyridine, piperidine, pyrrolidine, carbazole, indole, cyclohexylamine, aminohexanol, 2- (methylamino) ethanol, aline, hexamethylenediamine, dimethylallylamine Min and so on.

[0021] Examples of amidines include imidazole, N-methylimidazole, 2-methylimidazole and the like.

Examples of guanidines include 1,1,3,3-tetramethyldardine and 1,3-diphenyldazine.

Specific examples of the base preferably used in the present invention include those represented by the following formulas (7) to (20).

[0022] [Chemical 4]

p (8) (9) (11)

(12) (13) (14)

(15) (16) (17) (18)

(19) (20)

[0023] In addition, the acid component and the Z or base component described above may have a polymerizable group therein. The gel composition obtained using the neutralized salt type ionic liquid having a polymerizable group can be easily polymerized by polymerizing the polymerizable group present therein. Here, examples of the polymerizable group include a photopolymerizable functional group, a thermopolymerizable functional group, and a polyaddition functional group that are activated by light irradiation, heating, a polymerization initiator, a catalyst, and the like, and specific examples thereof. Examples of such a force include, but are not limited to, a vinyl group, an aryl group, a propargyl group, an attalyloyl group, a methacryloyl group, an epoxy group, and an isocyanate group.

In the present invention, when a neutralized salt type ionic liquid having a polymerizable group as an acid component is used, the resulting polymer skeleton can be composed of the acid component. In this case, the above-described benzoic acid or derivative thereof is used. Those having a polymerizable group are preferred. As the polymerizable group, Ri to R ⁵ in the formula (1) described above is preferably a polymerizable group such as a bur group, a allyl group, a propargyl group, an attalyloyl group, a methacryloyl group, and an epoxy group. A vinyl group, an talyloyl group and a methacryloyl group are preferred. Specific examples of the acid having a polymerizable group include a force S such as those represented by the following formulas (21) to (24). Specific examples of the base having a polymerizable group include the following formulas (25) to (30 ) And so on.

[Chemical 5]

[0027] Specific examples of the neutralized salt type ionic liquid preferably used in the gel composition of the present invention include

And those represented by the following formulas (31) to (41).

[0028] [Chemical 7]

N- (40)

[0029] The neutralized salt type ionic liquid described above can be obtained by a known acid-base neutralization method. For example, an acid and a base are mixed at a molar ratio of 1: 1 under cooling such as ice cooling. After mixing, the temperature can be raised to an appropriate temperature and stirred for 1 to 24 hours.

[0030] The method for producing the gel composition of the present invention is not particularly limited, but a carbon nanotube and a neutralized salt type ionic liquid obtained by neutralization reaction of acid and base are mixed. A method of applying a shearing force to the obtained mixture is preferably used.

At this time, the mixture can be prepared by neutralizing an acid and a base, and preparing a neutralized salt type ionic liquid and isolating it, and then adding carbon nanotubes. Directly (without isolating or purifying ionic liquids) A method of covering single-bonn nanotubes can also be used. Furthermore, an acid or base and carbon nanotubes are mixed, and then mixed into the mixture by a method of adding a base or acid thereto.

[0031] As a technique for applying a shearing force, a known shearing force applying means force can be appropriately selected and used. Specific examples include a method of manually or automatically kneading in a mortar, a method using a ball mill, a roller mill, a vibration mill, a kneader type kneader, and the like.

The time for applying the shearing force is not particularly limited, and may be an appropriate time for obtaining a gel composition. In the present invention, it is usually 1 to: LO minutes, and in some cases, 1 to 5 minutes. A gel composition can be obtained in a short time.

[0032] Through the above steps, a black gel composition is obtained. The obtained composition can be used for various purposes as it is, but if necessary, the excess neutralized salt type ionic liquid may be removed by centrifugation. In addition, the specific method and conditions of centrifugation are arbitrary force. Usually, the conditions of 1000-15000 rpm and 5-30 minutes are adopted. At this time, when an ionic liquid containing the above-described benzoic acid or a derivative thereof as an acid component is used as a gelling medium, the amount of surplus ionic liquid is reduced as compared with the case where other neutralized salt type ionic liquids are used. In other words, a gel-like composition obtained using an ionic liquid containing benzoic acid or a derivative thereof as a constituent component has a larger gel volume than when other ionic liquids are used. Accordingly, it can be said that a certain amount of carbon nanotubes are contained in a gel having a larger volume, and a gel-like composition having excellent dispersibility is generated.

[0033] The mixing ratio of the carbon nanotube and the neutralized salt type ionic liquid is not particularly limited, but is usually carbon nanotube: neutralized salt type ion liquid = 1: 60 to 1: 200 (mass) Ratio).

In addition, when using a neutralized salt type ionic liquid containing benzoic acid or a derivative thereof as an acid component and preparing a gel composition with a single bon nanotube: neutralized salt type ionic liquid = 1: 100 (mass ratio), The excess ionic liquid produced by centrifugation is usually 25% by mass or less of the ionic liquid used. [0034] The gel-like composition obtained using the neutralized salt type ionic liquid having a polymerizable group is polymerized in the gel-like composition by a conventionally known means such as heating, ultraviolet ray irradiation, electron beam irradiation and the like. The group can be reacted to polymerize. In this case, a polymerization initiator may be added to the gel composition before the polymerization reaction. The blending may be performed when preparing a mixture of carbon nanotubes and ionic liquid, which may be performed after the gel composition. In addition, what is necessary is just to select and use suitably from a well-known various thing as a polymerization initiator.

[0035] The carbon nanotube-containing polymer thus obtained preferably has a low volume resistivity and exhibits excellent electrical conductivity. Specifically, the volume resistivity is preferably 5. Ω · m or less. 2. Ω ·· πι or less is more preferable. The electrical conductivity is preferably 2 × 10— ^ Ζπι or more, and more preferably 5 × 10— ^ Ζπι or more. These physical properties are values measured by the two-terminal method using 4339B HIGH RESISTANCE METER / 16008B RESISTIVITY CELL (manufactured by HEWLETT PACKARD) as a measuring device under the conditions of an applied voltage of 3V and 25 ° C.

Since the carbon nanotube-containing polymer of the present invention uses a neutralized salt type ionic liquid as a gelling agent !, it is compared with a polymer using a conventionally known quaternary salt type ionic liquid as a gelling agent. Excellent electrical characteristics such as electrical conductivity.

Example

Hereinafter, the ability to more specifically describe the present invention with reference to examples and comparative examples The present invention is not limited to the following examples.

[0037] [1] Production of gel composition

[Example 1]

Benzoic acid (manufactured by Kanto Chemical Co., Inc.) was cooled to 1-methylimidazole (manufactured by Kanto Chemical Co., Ltd.) with an ice bath (molar ratio 1: 1). After 15 minutes, the ice bath was removed and the mixture was stirred at room temperature to obtain a neutralized salt type ionic liquid (31) represented by the following formula. The target product was a liquid at room temperature (25 ° C).

1H-NMR (CDCl) δ: 3.72 (s, 3H), 6.90 (d, lH), 7.16 (s, lH), 7.44 (t, 2H), 7.54 (m, lH), 7

Three

.78 (d, lH), 8.12, (d, 2H), 14.31 (br, lH).

[0038] [Chemical 8]

[0039] Neutralized salt type ionic liquid obtained (31) (not isolated / purified) 100 parts by mass and single-walled carbon nanotube (HiPco: Carbon Nanotechnologies) (hereinafter referred to as SWC NT) 1 When mixed with 0 parts by mass in a mortar and kneaded manually using a pestle until gelled for 5 minutes, a black paste was obtained (note that the kneaded product did not sag from the pestle. A gel (same below). When this paste-like material was centrifuged (12000 rpm, 30 minutes), it was separated into a black gel-like composition and a neutralized salt type ionic liquid, and the excess neutral salt type ionic liquid was removed. A gel composition was obtained. The excess ionic liquid was 25% by mass with respect to the ionic liquid used.

[0040] [Example 2]

A neutralized salt type ionic liquid (33) of the following formula was obtained in the same manner as in Example 1 except that triethylamine (Kanto Chemical Co., Ltd.) was used instead of 1-methylimidazole. The target product was a liquid at room temperature (25 ° C).

1H-NMR (CDCl) δ: 1.28 (t, 9H), 3.08 (q, 6H), 7.34-7.44 (m, 3H), 8.07 (d, 2H), 11.95 (b

Three

r, lH).

A gel composition was obtained in the same manner as in Example 1 except that this ionic liquid (33) was used. In addition, the surplus ionic liquid was 20 mass% with respect to the used ionic liquid.

[0041] [Chemical 9]

[Example 3]

Example 1 except that pyrrolidine (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 1-methylimidazole, and m-toluic acid (manufactured by Kanto Igaku) was used instead of benzoic acid. Thus, a neutralized salt type ionic liquid (35) represented by the following formula was obtained. The target product was a liquid at room temperature (25 ° C).

lH-NMR (CDCl) δ: 1.94 (t, 4H), 2.38 (s, 3H), 3.27 (t, 4H), 7.20-7.28 (m, 2H), 7.78 (d, l H), 7.82 (s, lH), 10.81 (s, 2H).

A gel composition was obtained in the same manner as in Example 1 except that this ionic liquid (35) was used. In addition, the surplus ionic liquid was 10 mass% with respect to the used ionic liquid.

[0043] [Chemical 10]

[0044] [Example 4]

Jetylamine (Kanto Chemical Co., Ltd.) 100ml and 2-methoxyethyl chloride (Kanto Chemical Co., Ltd.) 85ml were mixed, and the resulting mixed solution was placed in an autoclave at 100 ° C. For 24 hours. At this time, the internal pressure was 1.3 kgfZcm ² . After 24 hours, 200 ml of an aqueous solution in which 56 g of potassium hydroxide (made by Katayama Chemical Co., Ltd.) was dissolved was added to the mixture of the precipitated crystal and the reaction solution, and the organic layer separated into two layers was separated into a separating funnel. The liquid was separated. Further, 100 ml of methylene chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added and extracted twice. The separated organic layers were combined, washed with saturated brine, dried by adding potassium carbonate (Wako Pure Chemical Industries, Ltd.), and filtered under reduced pressure. The solvent of the obtained organic layer was distilled off with a rotary evaporator, and the residue was subjected to atmospheric distillation to obtain 18.9 g of 2-methoxyethyldecylamine, a fraction having a boiling point of around 135 ° C. .

[0045] Instead of 1-methylimidazole, the 2-methoxyethyldeethylamine obtained above was used, except that p-vinylbenzoic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of benzoic acid. In the same manner as in Example 1, a neutralized salt type ionic liquid (39) represented by the following formula was obtained. The target product was liquid at room temperature (25 ° C).

1H—NMR (CDCl) δ: 1.27 (t, 6H), 3.18 (q, 4H), 3.25 (dd, 2H), 3.32 (s, 3H), 3.78 (dd, 2H),

Three

5.30 (d, lH), 5.82 (d, lH), 6.76 (dd, lH), 7.45 (d, 2H), 8.04 (d, 2H), 13.75 (bs, lH).

A gel composition was obtained in the same manner as in Example 1 except that this ionic liquid (39) was used. In addition, the surplus ionic liquid was 2 mass% with respect to the used ionic liquid.

[0046] [Chemical 11]

[ετ ^] [oeoo]. , O / ₀ W Kuzu

• (HI

^S ) ZVS '(HS'Jq) 0S'9' (ΗΖ ') ζτ'(HZ'WZ'(H6)8S'I — OS'I: 9 (OS 顺-HI

. ^; 继

) & m) One, ^^ -i

[9th zone] [6 rinse]

[Zl ^ [8 rinse]. , O / ₀ w kudzu _ζ

(H2'sq) es-8 HV ^{S (} \) Z £ 'HZ'W £'(HS'Jq) 86 '(HS's) ZS "2: 9 (OSW I) 顺 -HI z tm eyes (): # Be ns a ^

m

,

) 峯阖) One ^

[9p} »] [00]

ZS6C0C / 900Zdf / X3d 91 OAV [0051] [Example 7]

The following formula was used in the same manner as in Example 1, except that 2-methoxyethyldetilamine was used instead of 1-methylimidazole and methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of benzoic acid. The ionic liquid (36) shown in 3 was obtained. The target product was a liquid at room temperature (25 ° C).

1H-NMR (CDCl) δ: 1.34 (t, 6H), 2.81 (s, 3H), 3.22 (q, 4H), 3.28 (dd, 2H), 3.38 (s, 3H),

Three

3.84 (dd, 2H), 10.52 (bs, lH).

A gel composition was obtained in the same manner as in Example 1 except that this ionic liquid (36) was used and kneaded in a mortar for 8 minutes. In addition, the surplus ionic liquid was 33 mass% with respect to the used ionic liquid.

[0052] [Chemical 14]

[0053] [Example 8]

Instead of 1-methylimidazole, 2-jetylaminoethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 1, 1, 1-trifluoro-N-[((trifluoromethyl) sulfonyl) instead of benzoic acid A neutralized salt ionic liquid (40) represented by the following formula was obtained in the same manner as in Example 1 except that methanesulfonimide (manufactured by Kanto Chemical Co., Ltd.) was used. The target product was a liquid at room temperature (25 ° C).

1H—NMR (CDCl 3) δ: 1.41 (t, 6H), 1.96 (s, 3H), 3.33 (q, 4H), 3.51 (t, 2H), 4.54 (t, 2H) 5.7

Three

2 (s, lH), 6.17 (s, lH), 7.72 (br, lH).

A gel composition was obtained in the same manner as in Example 1 except that this ionic liquid (40) was used and kneaded in a mortar for 8 minutes. The surplus ionic liquid was 3% by mass with respect to the ionic liquid used.

[0054] [Chemical 15] (40)

[0055] [Comparative Example 1]

Example 1 except that quaternary salt-type ionic liquid 1-ethyl 3-methylimidazolium tetrafluoroborate (EMIBF4) (Kanto Yigaku Co., Ltd.) was used and kneaded in a mortar for 20 minutes. In the same manner as above, a gel composition was obtained. The excess ionic liquid was 42% by mass with respect to the ionic liquid used.

[0056] [Comparative Example 2]

Example 1 except that quaternary salt-type ionic liquid 1-butyl-3-methylimidazole hexafluorophosphate (BMIPF6) (Kanto Yigaku Co., Ltd.) was used and kneaded in a mortar for 10 minutes. A gel composition was obtained. The surplus ionic liquid was 25% by mass with respect to the ionic liquid used.

[0057] [Comparative Example 3]

Using a quaternary salt-type ionic liquid, N, N-jetyl-N-methyl-N- (2-methoxyethyl) ammotetrafluoroborate (DEMEBF4) (Kantoi Chemical Co., Ltd.) in a mortar A gel-like composition was obtained in the same manner as in Example 1 except that the mixture was kneaded for 1 minute. The surplus ionic liquid was 30% by mass with respect to the ionic liquid used.

[0058] [Comparative Example 4]

Using a quaternary salt type ionic liquid, N, N-jetyl-N-methyl-N- (2-methoxyethyl) ammo-umbis (trifluoromethylsulfurimide) (DEMETFSI) (Kanto Chemical Co., Ltd.) A gel composition was obtained in the same manner as in Example 1 except that the mixture was kneaded for 15 minutes. The excess ionic liquid was 35% by mass with respect to the used ionic liquid.

[0059] [Comparative Example 5]

2-methylaminoethyl methacrylate (made by Wako Pure Chemical Industries, Ltd.) 12.04 g is dissolved in 30 ml of tetrahydrofuran (Wako Pure Chemical Industries, Ltd.). (Manufactured by Kogyo Co., Ltd.) 4. 86 ml was collected. After 30 minutes, the ice bath was removed and the mixture was stirred overnight at room temperature. The solvent of this reaction solution was distilled off under reduced pressure, and the resulting solid content was recrystallized with ethanol (manufactured by Wako Pure Chemical Industries, Ltd.)-Tetrahydrofuran system to give 17-jetylmethylaminoethyl iodine salt of methacrylate. 22g was obtained. [0060] Subsequently, 17.22 g of methacrylic acid 2 jetylmethylaminoethyl iodine salt was dissolved in 50 mL of ion-exchanged water. To this was added 15.42 g of trifluoromethanesulfonic acid imidolithium (manufactured by Kishida Chemical Co., Ltd.), and after complete dissolution, the mixture was stirred overnight at room temperature. The organic layer separated into two layers was separated and washed three times with water to remove impurities in the organic layer.

The organic layer after washing was decompressed with a vacuum pump, and water was sufficiently distilled off to obtain a quaternary salt type ionic liquid (42) represented by the following formula.

1H-NMR (CDCl) δ: 1.40 (t, 6H), 1.95 (s, 3H), 3.10 (s, 3H), 3.45 (q, 4H), 3.68 (dd, 2H),

Three

4.58 (dd, 2H), 5.72 (s, lH), 6.12 (s, lH).

A gel composition was obtained in the same manner as in Example 1 except that this quaternary salt type ionic liquid (42) was used and kneaded in a mortar for 10 minutes. The excess ionic liquid was 5% by mass with respect to the ionic liquid used.

[0061] [Chemical 16]

[0062] [2] Preparation of carbon nanotube-containing polymer

[Example 9]

Polymerizable group-containing neutralized salt type ionic liquid (39) 2 parts by mass of 2, 2 dimethoxy-2-phenylacetophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization initiator is dissolved in 100 parts by mass Then, after adding 3.8 parts by mass of SWCNT to this, and applying a shearing force in the same manner as in Example 1, a black paste was obtained. This is sandwiched between polyethylene terephthalate sheets (Therapeutic, Toray Film Co., Ltd., 100 / zm), and UV irradiation is performed for 15 minutes. As a result, a neutralized salt type ionic liquid ZSWCNT composite film containing a polymerizable group was produced.

[Example 10]

A polymerizable group-containing neutralized salt ion / SWCNT composite film was prepared in the same manner as in Example 9 except that the polymerizable group-containing neutralized salt type ionic liquid (40) was used. [Comparative Example 6]

A polymerizable group-containing quaternary salt type ion, SWCNT composite film was prepared in the same manner as in Example 9 except that the polymerizable group-containing quaternary salt type ionic liquid (42) was used.

[0064] The films obtained in Examples 9 and 10 and Comparative Example 6 were measured for volume resistivity and electrical conductivity by the two-terminal method under conditions of an applied voltage of 3V and 25 ° C (measurement apparatus: H EWLETT PACKARD 4339B HIGH RESISTANCE METER / 16 008B RESISTIVITY CELL). The results are shown in Table 1.

As shown in Table 1 below, by using a neutralizing salt type ionic liquid containing a polymerizable group, a film with higher electrical conductivity can be obtained than when a quaternary salt type ionic liquid is used. That's right.

[0065] [Table 1]

[0066] As described above, by using a neutralized salt ionic liquid that can be synthesized inexpensively and easily as a gelling agent V, a gel-like composition in which carbon nanotubes are dispersed can be obtained quickly and easily. did it. Further, by using a neutralized salt type ionic liquid containing no halogen atom, a gel-like composition having high environmental adaptability with non-halogen could be obtained. Further, by using a neutralized salt type ionic liquid having a polymerizable group, a polymer composite material having excellent electrical characteristics derived from carbon nanotubes could be obtained.

Claims

The scope of the claims

[1] A gel-like composition comprising carbon nanotubes and a neutralized salt-type ionic liquid obtained by an acid and base neutralization reaction.

[2] The gel composition according to claim 1, wherein the neutralized salt type ionic liquid comprises benzoic acid or a derivative thereof as an anion component.

[3] The benzoic acid or derivative thereof is represented by the following formula (1):

^2. The gel composition according to 2.

[Chemical 1]

2 n 2 n 2 n

,-(CH) -COO-R 'group, (CH) -NHCO-R' group, (CH) — CONH

2 n 2 n 2 n

-R 'group,-(CH) -NHCONH-R' group, CO- group (wherein

2 n

Is a branched alkyl group having 1 to 6 carbon atoms (this alkyl group may be substituted with a buyl group, a allyl group, a propargyl group, an attalyloyl group, a methacryloyl group or an epoxy group

. N represents an integer of 1 to 6. ] Represents a bur group, a allyl group, a propargyl group, an attalyl group, a methacryloyl group, or an epoxy group. }

[4] The ionic liquid according to any one of claims 1 to 3, wherein the base is an amine, an amidine, or a guanidine.

[5] The gel composition according to any one of claims 1 to 4, wherein the neutralized salt type ionic liquid has a polymerizable group in at least one of a cation component and a cation component.

[6] The gel composition according to claim 5, wherein the neutralized salt type ionic liquid has a polymerizable group in an anion component.

[7] The gel-like composition according to claims 1 to 6, wherein the carbon nanotube is a single-walled carbon nanotube, and the displacement force is 1.

[8] A carbon nanotube-containing polymer obtained by polymerizing the neutralized salt type ionic liquid in the gel composition according to claim 5 or 6.

[9] A method for producing a gel composition, comprising applying a shearing force to a mixture obtained by mixing carbon nanotubes and a neutralized salt-type liquid obtained by a neutralization reaction of an acid and a base.

10. The method for producing a gel composition according to claim 9, wherein the mixture is prepared by directly adding carbon nanotubes to a blend obtained by blending the acid and base.

11. The method for producing a gel composition according to claim 9 or 10, wherein after applying the shearing force, the excess neutralized salt is removed by centrifugation.