JP4425083B2 - Polymer-modified nanoscale carbon tube and method for producing the same - Google Patents

Description

  The present invention relates to a nanoscale carbon tube surface-modified with a polymer, a polymer-nanoscale carbon tube composite material, and a method for producing the same. Furthermore, the present invention also relates to a compound used in the method for producing the composite material.

  Conventionally, it has been reported that a carbon nanotube is used as a conductive filler for the purpose of forming an antistatic film (see, for example, Patent Document 1). However, carbon nanotubes with a graphite structure are inferior in affinity with solvents and resins, and when there are defects in the graphite structure, the shape is bent, and a cocoon-like aggregate in which a plurality of twisted CNTs are intertwined It has become. For this reason, it is difficult to unravel and disperse carbon nanotubes in a solvent or resin.

  When carbon nanotubes are aggregated when forming a conductive network in a resin using carbon nanotubes as a conductive filler in order to impart antistatic properties to the resin molded body, the conductive fillers that are originally required It is necessary to use a larger amount than the amount. Even if the aggregates of carbon nanotubes are unwound and dispersed, the individual carbon nanotubes are bent so that a large amount of carbon nanotubes must be used to form a conductive network compared to a linear shape. There is.

  For this reason, in order to improve the compatibility of the carbon nanotube with a medium such as a solvent or a resin, the surface of the carbon nanotube is modified with an organic substance. For example, it has been proposed to covalently bond an organic compound to the surface of a carbon nanotube. Examples of such an organic compound include carbenes (Non-Patent Document 1), azides (or nitrenes) (Non-Patent Document 2), azomethine ylides. (Non-Patent Document 3), diazoniums (Non-Patent Document 4) or fluorine compounds (Non-Patent Document 5) have been reported. However, since these techniques are only modified with a low molecular weight compound or a compound in the oligomer region, the effect of improving the compatibility with a medium such as a resin is not always satisfactory.

  In addition, a technique has been reported in which polystyrene is directly bonded to the side surface of carbon nanotubes by conducting living anionic polymerization of styrene in the presence of single-walled carbon nanotubes (Non-Patent Document 6). However, living anionic polymerization is complicated to operate and difficult to industrialize.

On the other hand, a method of modifying carbon nanotubes with a polymer using the ATRP (Atom Transfer Radical Polymerization) method, which is a radical type living polymerization method that can manage the reaction more easily than living anionic polymerization, is known. (Non-patent document 7). However, in this method, the process of introducing the initiator to the surface of the single-walled carbon nanotube is extremely complicated. More specifically, in this Non-Patent Document 7, the surface of the carbon nanotube is treated with a strong acid (60% nitric acid) that may cause damage to the surface of the carbon nanotube to form a carboxyl group, which is further reacted with thionyl chloride to react with the acid. After the chloride is obtained, a diol compound (ethylene glycol) that serves as a bridge for introducing the initiator is bonded under conditions that do not cause cross-linking of the carbon nanotubes, and 2-bromo-2-methylpropionyl bromide that serves as the initiator. To form a starting point. Living radical polymerization of methyl methacrylate and the like is performed through this starting point. As a result, the surface of the carbon nanotube and the polymer chain are bonded through a linking group having a structure of —COO—CH ₂ CH ₂ —O—CO—C (CH ₃ ) ₂ —. As described above, when the ATRP method, which is a radical type living polymerization method, is used in accordance with the method described in Non-Patent Document 7, the introduction method of the initiator (starting point) is complicated, which is a major obstacle in terms of industrial production and costs. It is thought that it becomes.

  Further, by treating the carbon nanotube with a strong acid, a functional group such as a carboxyl group is formed at both ends of the carbon nanotube, and by reacting this carboxyl group with a compound having an amino group, carbon is bonded via an amide bond. A technique for modifying both ends of a nanotube has also been reported (Non-patent Document 8). However, in this method, since it is essential to treat the carbon nanotube with a strong acid, there is a problem that the structure of the carbon nanotube itself is likely to be damaged by the strong acid.

In addition, a compound (PtBA-) obtained by preparing poly (t-butyl acrylate) in advance by the ATRP method, which is a living radical polymerization method, azide the growth terminal, and adding this to fullerene (C ₆₀ ). C ₆₀ ) and a compound (PAA-C ₆₀ ) obtained by hydrolyzing the poly (t-butyl acrylate) moiety of the compound and converting it to polyacrylic acid are known (Non-patent Document 9). However, there is no description as to whether the same method can be applied to carbon nanotubes that are longer in size than fullerenes and have low reactivity on the side surfaces.

As described above, there are many reports on improving the dispersibility of carbon nanotubes, but carbon nanotubes capable of high concentration dispersion in a medium (organic solvent, resin, etc.), which are of interest from an industrial viewpoint, and their At present, an industrially advantageous production method has not yet been developed.
JP 2002-67209 A (Claim 1) C. Haddon, et al., Science 28295 (1998) A. Hirsch, et al., Angew. Chem. Int. Ed., 40 (2), 4002 (2001) M., Prato, et al., JACS 124, 760 (2002) JM Tour, et al., Mancomolecules 35, 8825 (2002) RE Smally, et al., J. Phys. Chem. B, 1052525 (2001) PM, Ajaya, et al., JACS. 125, 9258 (2003) Deyue Yan, et al., J. Am. Chem. Soc., 126, 412 (2004) MA Hamon, et al., Adv. Mater. 11, 834 (1999) C. Wang, et al., Macromolecules 36, 6060 (2003)

  The present invention is capable of damaging the structure of carbon nanotubes, such as carbon nanotubes that can be dispersed at high concentration in organic media such as organic solvents and resins, and carbon nanotubes that can be dispersed at high concentration in such organic media. The main object is to provide a method which is advantageous and industrially advantageous.

  In light of the problems of the prior art, the present inventors have conducted extensive research to achieve the above object, and have obtained the following knowledge.

  (1) An azide compound having a specific structure reacts with carbon nanotubes and is covalently bonded to the surface (side surface and both ends).

  (2) Thus, the azide compound having a specific structure covalently bonded to the surface of the carbon nanotubes functions as an initiation point (initiator) for living radical polymerization.

  (3) Therefore, at the starting point, at least one monomer selected from the group consisting of (meth) acrylates and styrenes is graft-polymerized by a living radical polymerization method, whereby a polymer or copolymer containing the monomer is carbonized. The surface (side and both ends) of the nanotubes can be modified.

  (4) The reaction of the carbon nanotubes with the azide compound and the graft polymerization reaction by the living radical polymerization method on the product of the reaction do not substantially damage the structure of the carbon nanotubes.

  (5) The living radical polymerization method is more suitable for industrial applications than the living anion polymerization, and is advantageous in terms of industrial implementation.

  The present invention has been completed based on the above findings, and has been completed. The present invention provides the following polymer-modified nanoscale carbon tube, polymer-nanoscale carbon tube composite material, and production method thereof. The present invention also provides an azide compound used in the production method.

  Item 1 The following general formula (1a)

［式中、
R¹は、水素原子又は炭素数１〜４のアルキル基を示し、
R²は、式（ｐ）

[Where:
R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R ² is the formula (p)

で表される基を示すか、又は、一般式（ｑ）

Or a group represented by the general formula (q)

（式中、ｍは０又は１〜４の整数を示す。）で表される基を示し、
R³は、（メタ）アクリレート及びスチレン類からなる群から選ばれる少なくとも１種のモノマーの重合体を示す。］
で表される少なくとも１種の修飾基が、ナノスケールカーボンチューブの表面（側面及び両端）に結合していることを特徴とするポリマー修飾ナノスケールカーボンチューブ。

(Wherein m represents an integer of 0 or 1 to 4),
R ³ represents a polymer of at least one monomer selected from the group consisting of (meth) acrylates and styrenes. ]
A polymer-modified nanoscale carbon tube, wherein at least one modification group represented by the formula (1) is bonded to the surface (side surface and both ends) of the nanoscale carbon tube.

Item 2 The polymer-modified nanoscale carbon tube according to Item 1, wherein R ² is a group represented by the formula (p).

Item 3 Nanoscale carbon tube
(i) single-walled carbon nanotubes,
(ii) amorphous nanoscale carbon tube,
(iii) a carbon tube selected from the group consisting of nano flake carbon tubes and nested multi-walled carbon nanotubes, or
(iv) An iron-carbon composite comprising the carbon tube of the above (iii) and iron carbide or iron, in which 10 to 90% of the space in the tube of the carbon tube is filled with iron carbide or iron. Item 2. The polymer-modified nanoscale carbon tube according to Item 1, which is a polymer-modified nanoscale carbon tube according to Item 1.

  Item 4 (a) On the surface (side surface and both ends) of the nanoscale carbon tube, (b) the following general formula (1b)

［式中、
R¹は、水素原子又は炭素数１〜４のアルキル基を示し、
R²は、式（ｐ）

[Where:
R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R ² is the formula (p)

で表される基を示すか、又は、一般式（ｑ）

Or a group represented by the general formula (q)

（式中、ｍは０又は１〜４の整数を示す。）で表される基を示す。］
で表される少なくとも１種の連結基がその窒素原子で結合しており、上記一般式(1b)で表される連結基の基R¹、基R²及びメチル基が結合している炭素原子に、（メタ）アクリレート類及びスチレン類からなる群から選ばれる少なくとも１種のモノマーがリビングラジカル重合法によりグラフト重合されていることを特徴とするポリマー−ナノスケールカーボンチューブ複合材料。（即ち、前記一般式(1a)で表される少なくとも１種の修飾基が、ナノスケールカーボンチューブの表面（側面及び両端）に結合していることを特徴とするポリマー修飾ナノスケールカーボンチューブ複合材料）。

(Wherein m represents an integer of 0 or 1 to 4). ]
A carbon atom to which at least one linking group represented by general formula (1b) is bonded by the nitrogen atom, and the linking group R ¹ , R ² and methyl group of the general formula (1b) are bonded to each other. A polymer-nanoscale carbon tube composite material, wherein at least one monomer selected from the group consisting of (meth) acrylates and styrenes is graft-polymerized by a living radical polymerization method. (In other words, at least one modifying group represented by the general formula (1a) is bonded to the surface (side surface and both ends) of the nanoscale carbon tube, a polymer-modified nanoscale carbon tube composite material ).

Item 5 The polymer-nanoscale carbon tube composite material according to Item 4, wherein R ² is a group represented by the formula (p).

Item 6 Nanoscale carbon tube
(i) single-walled carbon nanotubes,
(ii) amorphous nanoscale carbon tube,
(iii) a carbon tube selected from the group consisting of nano flake carbon tubes and nested multi-walled carbon nanotubes, or
(iv) An iron-carbon composite comprising the carbon tube of the above (iii) and iron carbide or iron, in which 10 to 90% of the space in the tube of the carbon tube is filled with iron carbide or iron. Item 5. The polymer-nanoscale carbon tube composite material according to Item 4.

  Item 7 Nanoscale carbon tube and general formula (1)

［式中、
Ｘは、ハロゲン原子を示し、
R¹は、水素原子又は炭素数１〜４のアルキル基を示し、
R²は、式（ｐ）

[Where:
X represents a halogen atom,
R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R ² is the formula (p)

で表される基を示すか、又は、一般式（ｑ）

Or a group represented by the general formula (q)

（式中、ｍは０又は１〜４の整数を示す。）で表される基を示す。］
で表されるアジド化合物の少なくとも１種とを反応させ、得られた反応生成物に、（メタ）アクリレート及びスチレン類からなる群から選ばれる少なくとも１種のモノマーをリビングラジカル重合法でグラフト重合させることを特徴とするポリマー−ナノスケールカーボンチューブ複合材料の製造方法。

(Wherein m represents an integer of 0 or 1 to 4). ]
And at least one monomer selected from the group consisting of (meth) acrylates and styrenes is graft-polymerized by a living radical polymerization method to the obtained reaction product. A method for producing a polymer-nanoscale carbon tube composite material.

Item 8 The method according to Item 7, wherein R ² is a group represented by the formula (p).

Item 9 Nanoscale carbon tube
(i) single-walled carbon nanotubes,
(ii) amorphous nanoscale carbon tube,
(iii) a carbon tube selected from the group consisting of nano flake carbon tubes and nested multi-walled carbon nanotubes, or
(iv) An iron-carbon composite comprising the carbon tube of the above (iii) and iron carbide or iron, in which 10 to 90% of the space in the tube of the carbon tube is filled with iron carbide or iron. Item 8. The manufacturing method according to Item 7.

  Item 10 The production method according to Item 7, wherein the living radical polymerization method is an ATRP (Atom Transfer Radical Polymerization) method.

  Item 11 Living radical polymerization is carried out using a catalyst selected from cuprous chloride (CuCl) and cuprous bromide (CuBr) and 2,2′-bipyridyl, 4,4′-di-tert-butyl-2,2 '-Bipyridyl, 4,4'-diheptyl-2,2'-bipyridyl, 4,4'-di (1-butyl-pentyl) -2,2'-bipyridyl, 4,4'-ditridecyl-2,2' -Bipyridyl, 1,1,4,7,10,10-hexamethyltriethylenetetramine and the following formula (3)

で表される化合物からなる群から選ばれる少なくとも１種の配位子の存在下で、又は、NiBr₂(P(n-C₄H₉)₃)₂の存在下で行う項７〜１０のいずれかに記載の製造方法。

Any one of Items 7 to 10 performed in the presence of at least one ligand selected from the group consisting of compounds represented by: or in the presence of NiBr ₂ (P (nC ₄ H ₉ ) ₃ ) ₂ . The manufacturing method as described in.

  Item 12 A polymer-nanoscale carbon tube composite material obtained by the production method according to any one of Items 7 to 11.

  Item 13 General formula (1)

［式中、
Ｘは、ハロゲン原子を示し、
R¹は、水素原子又は炭素数１〜４のアルキル基を示し、
R²は、式（ｐ）

[Where:
X represents a halogen atom,
R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R ² is the formula (p)

で表される基を示すか、又は、一般式（ｑ）

Or a group represented by the general formula (q)

（式中、ｍは０又は１〜４の整数を示す。）で表される基を示す。］
で表されるアジド化合物。

(Wherein m represents an integer of 0 or 1 to 4). ]
The azide compound represented by these.

  According to the present invention, the following remarkable effects are achieved.

  The polymer-modified nanoscale carbon tube and polymer-nanoscale carbon tube composite material of the present invention has an affinity for a medium such as a solvent or a resin because the surface (side surface and both ends) of the nanoscale carbon tube is modified with a polymer. It has improved dramatically, has the advantage that uniform dispersion in these media is very easy and that the nanoscale carbon tubes are substantially free of precipitation and phase separation in the media.

  This can also be confirmed from a centrifugation experiment of the polymer-modified nanoscale carbon tube dispersion obtained in the examples described later.

  Therefore, the polymer-modified nanoscale carbon tube of the present invention can be easily and uniformly dispersed in a resin or a mixture of a resin and a solvent, and the resulting dispersion can be used in various fields, for example, an electromagnetic shielding film, Suitable for use in fields such as paints and antistatic materials.

  The production method of the present invention does not substantially damage the structure of the nanoscale carbon tube, and is advantageous in terms of industrial implementation as compared with the conventional method using living anionic polymerization.

  Further, the azide compound represented by the general formula (1) of the present invention reacts with the surface of the nanoscale carbon tube without substantially damaging the structure of the nanoscale carbon tube, binds to the surface, and Acts as an initiator for radical polymerization.

Nanoscale carbon tube In the present invention, various types of nanoscale carbon tubes modified with a polymer can be used.

(i) single-walled carbon nanotubes,
(ii) amorphous nanoscale carbon tube,
(iii) a carbon tube selected from the group consisting of nano flake carbon tubes and nested multi-walled carbon nanotubes, or
(iv) An iron-carbon composite comprising the carbon tube of the above (iii) and iron carbide or iron, in which 10 to 90% of the space in the tube of the carbon tube is filled with iron carbide or iron.

  Among these, the amorphous nanoscale carbon tube, the nano flake carbon tube, and the iron-carbon composite are particularly preferable because of good dispersion in the solvent and the resin. The reason why these tubes are well dispersed in solvents and resins has not been fully elucidated, but because the carbon network surface of the outermost layer of these tubes is discontinuous, the affinity with solvents, resins, etc. It is assumed that it is higher. Furthermore, when the surface of the nanoscale carbon tube is modified with a polymer according to the present invention, the compatibility with a medium such as a resin or a solvent is further improved.

< Carbon nanotube >
A carbon nanotube is a hollow carbon material in which a graphite sheet (that is, a carbon atom plane or graphene sheet of a graphite structure) is closed like a tube, its diameter is nanometer scale, and the wall structure has a graphite structure. . Among the carbon nanotubes, one with a single graphite sheet whose wall structure is closed in a tube shape is called a single-walled carbon nanotube, and a plurality of graphite sheets are each closed in a tube shape and are nested. It is called a multi-walled carbon nanotube with a nested structure. In the present invention, both single-walled carbon nanotubes and multi-walled carbon nanotubes can be used.

  The single-walled carbon nanotube that can be used in the present invention preferably has a diameter of about 0.4 to 10 nm and a length of about 1 to 500 μm, and more preferably has a diameter of about 0.7 to 5 nm and a length of about 1 to 100 μm. In particular, those having a diameter of about 0.7 to 2 nm and a length of about 1 to 20 μm are preferable.

  The multi-walled carbon nanotube that can be used in the present invention preferably has a diameter of about 1 to 100 nm and a length of about 1 to 500 μm, and further has a diameter of about 1 to 50 nm and a length of about 1 to 100 μm. Particularly preferred are those having a diameter of about 1 to 40 nm and a length of about 1 to 20 μm.

< Amorphous nanoscale carbon tube >
The amorphous nanoscale carbon tube is described in WO 00/40509 (Patent No. 3355442), has a main skeleton made of carbon, has a diameter of 0.1 to 1000 nm, and has an amorphous structure. The carbon tube has a linear shape, and in the X-ray diffraction method (incident X-ray: CuKα), the plane interval (d002) of the carbon mesh plane (002) measured by the diffractometer method is 3.54 mm. In particular, it is 3.7 mm or more, the diffraction angle (2θ) is 25.1 degrees or less, particularly 24.1 degrees or less, and the half-value width of 2θ band is 3.2 degrees or more, particularly 7.0 degrees or more. It is characterized by.

  The amorphous nanoscale carbon tube is a thermally decomposable resin having a decomposition temperature of 200 to 900 ° C. in the presence of a catalyst made of at least one metal chloride such as magnesium, iron, cobalt, nickel, etc. It can be obtained by subjecting tetrafluoroethylene, polyvinylidene chloride, polyvinylidene fluoride, polyvinyl alcohol or the like to excitation treatment.

  The shape of the thermally decomposable resin as a starting material may be any shape such as a film shape, a sheet shape, a powder shape, or a lump shape. For example, when obtaining a carbon material in which a thin amorphous nanoscale carbon tube is formed on a substrate, excitation treatment may be performed under appropriate conditions with a thermally decomposable resin applied or placed on the substrate. .

  As the excitation treatment, for example, heating is performed in an inert atmosphere, preferably in a temperature range of about 450 to 1800 ° C. and at or above the thermal decomposition temperature of the raw material, and in a temperature range of about room temperature to 3000 ° C. and the thermal decomposition temperature of the raw material. Examples of the processing such as the above plasma processing can be given.

  The amorphous nanoscale carbon tube used in the present invention is a nanoscale carbon nanotube having an amorphous structure (amorphous structure), has a hollow linear shape, and the pores are highly controlled. The shape is mainly a cylinder, a quadrangular prism, etc., and at least one of the tips often has no cap (open). When the tip is closed, the shape is often flat.

  The outer diameter of the amorphous nanoscale carbon tube is usually in the range of about 1 to 1000 nm, preferably in the range of about 1 to 200 nm, and more preferably in the range of about 1 to 100 nm. The aspect ratio (tube length / diameter) is 2 times or more, preferably 5 times or more.

  Here, “amorphous structure” means a carbonaceous structure consisting of an irregular carbon network plane, not a graphite structure consisting of a continuous carbon layer of regularly arranged carbon atoms. The graphene sheets are irregularly arranged, and the atomic arrangement is irregular. From an image obtained by a transmission electron microscope, which is a typical analysis technique, the nanoscale carbon tube having an amorphous structure according to the present invention has a spread in the plane direction of the carbon network plane that is one time larger than the diameter of the amorphous nanoscale carbon tube. small. As described above, the amorphous nanoscale carbon tube has an amorphous structure in which a large number of fine graphene sheets (carbon network surface) are irregularly distributed instead of a graphite structure, so that the outermost layer is formed. The carbon mesh surface is not continuous over the entire length in the tube longitudinal direction but is discontinuous. In particular, the length of the carbon network surface constituting the outermost layer is less than 20 nm, particularly less than 5 nm.

Amorphous carbon generally does not exhibit X-ray diffraction, but exhibits broad reflection. In the graphitic structure, the carbon mesh planes are regularly stacked, so the carbon mesh plane spacing (d ₀₀₂ ) is narrowed, and the broad reflection shifts to the high angle side (2θ) and becomes gradually sharper (in the 2θ band). It becomes observable as d ₀₀₂ diffraction lines (d ₀₀₂ = 3.354 mm when they are regularly stacked due to the graphite positional relationship).

In contrast, an amorphous structure generally does not exhibit X-ray diffraction as described above, but partially exhibits very weak coherent scattering. The theoretical crystallographic properties of the amorphous nanoscale carbon tube according to the present invention measured by the diffractometer method in the X-ray diffraction method (incident X-ray = CuKα) are defined as follows: carbon network plane The interval (d ₀₀₂ ) is 3.54 mm or more, more preferably 3.7 mm or more; the diffraction angle (2θ) is 25.1 degrees or less, more preferably 24.1 degrees or less; the half width of the 2θ band Is 3.2 degrees or more, more preferably 7.0 degrees or more.

Typically, the amorphous nanoscale carbon tube used in the present invention has a diffraction angle (2θ) by X-ray diffraction in the range of 18.9 to 22.6 degrees, and the carbon network plane spacing (d ₀₀₂ ) is 3.9 to 4.7 mm. The full width at half maximum of the 2θ band is in the range of 7.6 to 8.2 degrees.

The phrase “linear”, which is one term representing the shape of the amorphous nanoscale carbon tube of the present invention, is defined as follows. That is, when the length of the amorphous nanoscale carbon tube image obtained by a transmission electron microscope is L and the length when the amorphous nanoscale carbon tube is extended is L ₀ , L / L ₀ is 0.9 or more. It shall mean shape characteristics.

  The tube wall portion of such an amorphous nanoscale carbon tube has an amorphous structure composed of a plurality of fine carbon network planes (graphene sheets) oriented in all directions, and the active point is determined by the carbon plane spacing of these carbon network planes. It has the advantage that it is excellent in affinity with the solvent and resin which are media.

< Iron-carbon composite >
The iron-carbon composite used in the present invention is described in Japanese Patent Application Laid-Open No. 2002-338220, and (a) a carbon tube selected from the group consisting of a nano flake carbon tube and a multi-layer carbon nanotube with a nested structure. And (b) iron carbide or iron, and 10 to 90% of the space in the tube of the carbon tube (a) is filled with the iron carbide or iron (b). That is, 100% of the space in the tube is not completely filled, and the metal or alloy is filled in the range of 10 to 90% of the space in the tube (that is, partially). It is characterized in that it is filled). The wall portion is a patchwork-like or machete-like (so-called paper mache-like) nano-flake carbon tube.

  In the claims and the specification of the present application, the “nano flake carbon tube” is composed of a plurality of (usually many) flake-like graphite sheets assembled into a patchwork shape or a paper mache shape. This refers to a carbon tube made of an aggregate of graphite sheets.

Such iron-carbon composites are
(1) Ratio when the pressure is adjusted to 10 ⁻⁵ Pa to 200 kPa in an inert gas atmosphere, the oxygen concentration in the reactor is A (liter), and the oxygen amount is B (Ncc). Heating the iron halide to 600 to 900 ° C. in a reaction furnace adjusted to a concentration at which B / A is 1 × 10 ⁻¹⁰ to 1 × 10 ⁻¹ , and
(2) It is manufactured by a manufacturing method including a step of introducing an inert gas into the reaction furnace, introducing a pyrolytic carbon source at a pressure of 10 ⁻⁵ Pa to 200 kPa, and performing a heat treatment at 600 to 900 ° C. The

  Here, “Ncc”, which is a unit of the oxygen amount B, means a volume (cc) when converted to a standard state of gas at 25 ° C.

  The iron-carbon composite is composed of (a) a carbon tube selected from the group consisting of nano flake carbon tubes and nested multi-walled carbon nanotubes, and (b) iron carbide or iron. The space portion (that is, the space surrounded by the tube wall) is not completely filled, but a part of the space portion, more specifically, about 10 to 90%, particularly about 30 to 80%. Preferably, about 40 to 70% is filled with iron carbide or iron.

  In the iron-carbon composite used in the present invention, as described in JP-A No. 2002-338220, the carbon portion is produced at a specific rate after performing the production steps (1) and (2). When cooled, it becomes a nano flake carbon tube, and after performing the manufacturing steps (1) and (2), heat treatment is performed in an inert gas, and cooling is performed at a specific cooling rate, thereby forming a multi-walled carbon nanotube with a nested structure. .

<(A-1) Nano flake carbon tube>
The nano-flake carbon tube of the present invention and the iron-carbon composite made of iron carbide or iron are typically cylindrical, but such a cylindrical iron-carbon composite (Japanese Patent Laid-Open No. 2002-338220). A transmission electron microscope (TEM) photograph of a cross section perpendicular to the longitudinal direction of that obtained in Example 1 is shown in FIG. 3, and a side TEM photograph is shown in FIG.

  FIG. 4 (a-1) shows a schematic diagram of a TEM image of such a columnar nanoflake carbon tube. In (a-1) of FIG. 4, 100 schematically shows a TEM image in the longitudinal direction of the nano flake carbon tube, and 200 indicates a TEM image in a cross section substantially perpendicular to the longitudinal direction of the nano flake carbon tube. This is shown schematically.

  The nanoflake carbon tube constituting the iron-carbon composite used in the present invention typically has a hollow cylindrical shape, and when the cross section is observed by TEM, arc-shaped graphene sheet images are concentrically assembled. Each graphene sheet image forms a discontinuous ring, and when the longitudinal direction is observed with TEM, the substantially straight graphene sheet images are arranged in multiple layers almost parallel to the longitudinal direction. The individual graphene sheet images are not continuous over the entire length in the longitudinal direction, but are discontinuous.

  More specifically, the nanoflake carbon tube constituting the iron-carbon composite used in the present invention is perpendicular to the longitudinal direction, as is apparent from 200 in FIGS. 3 and 4 (a-1). When the cross section is observed by TEM, many arc-shaped graphene sheet images are concentrically (multi-layered tube shape), but each graphene sheet image is completely closed as shown in 210 and 214, for example. It does not form a continuous ring, but forms a discontinuous ring that is interrupted. Some graphene sheet images may be branched as indicated by 211. At the discontinuity point, a plurality of arc-shaped TEM images constituting one discontinuous ring may have a partially disturbed layer structure as indicated by 222 in FIG. As shown by 223, there may be a space between adjacent graphene sheet images, but a large number of arc-shaped graphene sheet images observed by TEM form a multilayer tube structure as a whole. Yes.

  Further, as is clear from 100 of FIGS. 1 and 4 (a-1), when the longitudinal direction of the nanoflake carbon tube is observed by TEM, a large number of substantially straight graphene sheet images are used in the present invention. Although it is arranged in multiple layers substantially parallel to the longitudinal direction of the iron-carbon composite, the individual graphene sheet images 110 are not continuous over the entire length in the longitudinal direction of the iron-carbon composite, and are discontinuous in the middle. It has become. Some graphene sheet images may be branched as indicated by reference numeral 111 in FIG. Further, at the discontinuous points, among the TEM images arranged in a layered manner, the TEM image of one discontinuous layer is at least partly adjacent to the adjacent graphene sheet image as indicated by 112 in FIG. In some cases, they may overlap each other, or as shown at 113, they may be slightly apart from the adjacent graphene sheet images, but a large number of substantially linear TEM images form a multilayer structure as a whole.

  The structure of the nanoflake carbon tube of the present invention is greatly different from the conventional multi-walled carbon nanotube. That is, as shown by 400 in FIG. 4A-2, the multi-walled carbon nanotube with a nested structure has a cross-sectional TEM image perpendicular to its longitudinal direction. As shown by 300 in FIG. 4 (a-2), the straight graphene sheet images 310 and the like continuous over the entire length in the longitudinal direction are arranged in parallel. Structure (concentric cylindrical or nested structure).

  Although the details have not been fully elucidated yet, the nano-flake carbon tube constituting the iron-carbon composite used in the present invention has a large number of flake-like graphene sheets overlapped in a patchwork or tension form. It seems to form a tube as a whole.

  Such a nano-flake carbon tube of the present invention and an iron-carbon composite made of iron carbide or iron encapsulated in the inner space of the tube are nested multi-walled carbon nanotubes as described in Japanese Patent No. 2546114. The structure of the carbon tube is greatly different from that of the composite in which the metal is included in the inner space of the tube.

  In the case of TEM observation of the nano-flake carbon tube constituting the iron-carbon composite used in the present invention, each graphene sheet image relates to a number of substantially linear graphene sheet images oriented in the longitudinal direction. The length is usually about 2 to 500 nm, particularly about 10 to 100 nm. That is, as indicated by 100 in FIG. 4 (a-1), a large number of TEM images of the substantially linear graphene sheet indicated by 110 are collected to constitute a TEM image of the wall portion of the nanoflake carbon tube. The length of each substantially linear graphene sheet image is usually about 2 to 500 nm, particularly about 10 to 100 nm.

  Thus, in the iron-carbon composite, the outermost layer of the nanoflake carbon tube constituting the wall portion is formed of a discontinuous graphene sheet that is not continuous over the entire length in the tube longitudinal direction. The length of the outer carbon net surface is usually about 2 to 500 nm, particularly about 10 to 100 nm.

  As described above, the carbon portion of the wall portion of the nano-flake carbon tube constituting the iron-carbon composite used in the present invention has a tube shape in which a large number of flake-like graphene sheets are oriented in the longitudinal direction. However, when measured by the X-ray diffraction method, the average distance (d002) between the carbon network surfaces has a graphite structure of 0.34 nm or less.

  Moreover, the thickness of the wall part which consists of a nano flake carbon tube of the iron-carbon composite used by this invention is 49 nm or less, Especially about 0.1-20 nm, Preferably it is about 1-10 nm, Comprising: Over the full length, And substantially uniform.

<(A-2) Nested multi-walled carbon nanotubes>
As described above, after performing steps (1) and (2), as described in JP-A-2002-338220, by performing a heat treatment in an inert gas and cooling at a specific cooling rate, The carbon tube constituting the obtained iron-carbon composite becomes a multi-walled carbon nanotube with a nested structure.

  The nested multi-walled carbon nanotube thus obtained is a concentric tube whose cross section perpendicular to the longitudinal direction forms a substantially perfect circle as indicated by reference numeral 400 in FIG. There is a structure (concentric cylindrical or nested structure) in which continuous graphene sheet images are arranged in parallel over the entire length in the longitudinal direction.

  The carbon portion of the wall portion of the multi-walled carbon nanotube of the nested structure constituting the iron-carbon composite used in the present invention has an average distance (d002) between carbon network surfaces of 0, as measured by X-ray diffraction. It has a graphite structure of 34 nm or less.

  Further, the thickness of the wall portion composed of the multi-walled carbon nanotube of the iron-carbon composite nested structure used in the present invention is 49 nm or less, particularly about 0.1 to 20 nm, preferably about 1 to 10 nm. Substantially uniform.

<(B) Iron carbide or iron contained>
In the present specification, the filling ratio (10 to 90%) with iron carbide or iron in the space portion in the carbon tube selected from the group consisting of the nano flake carbon tube and the nested multi-walled carbon nanotube was obtained by the present invention. The portion filled with iron carbide or iron with respect to the area of the image of the space portion of each carbon tube (that is, the space surrounded by the tube wall of the carbon tube) when the iron-carbon composite is observed with a transmission electron microscope Is the ratio of the area of the image.

  The filling form of iron carbide or iron includes a form in which the space in the carbon tube is continuously filled and a form in which the space in the carbon tube is filled intermittently. Filled. Therefore, the iron-carbon composite used in the present invention should also be referred to as a metal-encapsulated carbon composite, an iron compound-encapsulated carbon composite, iron carbide, or an iron-encapsulated carbon composite.

  In addition, the iron carbide or iron included in the iron-carbon composite used in the present invention is oriented in the longitudinal direction of the carbon tube, has high crystallinity, and is in a range where iron carbide or iron is filled. The ratio of the area of the crystalline iron carbide or iron TEM image to the area of the TEM image (hereinafter referred to as “crystallization rate”) is generally about 90 to 100%, particularly about 95 to 100%.

  The high crystallinity of the iron carbide or iron contained is apparent from the fact that the TEM images of the inclusions are arranged in a lattice form when observed from the side of the iron-carbon composite of the present invention, It is clear from the fact that a clear diffraction pattern can be obtained in electron beam diffraction.

  Moreover, it can be easily confirmed by an electron microscope and EDX (energy dispersive X-ray detector) that iron carbide or iron is included in the iron-carbon composite used in the present invention.

<Overall shape of iron-carbon composite>
The iron-carbon composite used in the present invention is less curved, straight, and has a uniform thickness over the entire length of the wall, so it is homogeneous over the entire length. It has a shape. The shape is columnar and mainly cylindrical.

  The outer diameter of the iron-carbon composite according to the present invention is usually about 1 to 100 nm, particularly about 1 to 50 nm, preferably about 1 to 30 nm, more preferably about 10 to 30 nm. It is in. The aspect ratio (L / D) of the tube length (L) to the outer diameter (D) is about 5 to 10,000, and particularly about 10 to 1,000.

  The term “linear”, which is one term representing the shape of the iron-carbon composite used in the present invention, is defined as follows. That is, when the carbonaceous material containing the iron-carbon composite used in the present invention is observed in a range of 200 to 2000 nm square by a transmission electron microscope, the length of the image is W, and the image is linearly extended. In this case, the shape characteristic means that the ratio W / Wo is 0.8 or more, particularly 0.9 or more.

  The iron-carbon composite used in the present invention has the following properties when viewed as a bulk material. That is, in the present invention, iron- or iron carbide is filled in a range of 10 to 90% of the space in the tube of the carbon tube selected from the nano flake carbon tube and the nested multi-walled carbon nanotube as described above. The carbon composite is not a minute amount that can be barely observed by microscopic observation, but is a bulk material containing a large number of the iron-carbon composite, and is a carbonaceous material containing iron-carbon composite, or iron carbide or iron. It can be obtained in large quantities in the form of a material that should be referred to as an encapsulated carbonaceous material.

  FIG. 2 shows an electron micrograph of the carbonaceous material of the present invention comprising the nanoflake carbon tube produced in Example 1 of JP-A-2002-338220 and iron carbide filled in the space in the tube.

  As can be seen from FIG. 2, in the carbonaceous material containing the iron-carbon composite used in the present invention, basically, in almost all (particularly 99% or more) carbon tubes, the space portion (that is, In general, iron carbide or iron is filled in a range of 10 to 90% of the space surrounded by the tube wall of the carbon tube, and there is usually substantially no carbon tube in which the space is not filled. However, in some cases, a small amount of carbon tubes not filled with iron carbide or iron may be mixed.

  Further, in the carbonaceous material of the present invention, an iron-carbon composite in which 10 to 90% of the space in the carbon tube as described above is filled with iron or iron carbide is a main constituent component. In addition to the iron-carbonaceous composite, soot may be contained. In such a case, components other than the iron-carbonaceous composite of the present invention are removed to improve the purity of the iron-carbonaceous composite in the carbonaceous material of the present invention, which is substantially used in the present invention. A carbonaceous material consisting only of an iron-carbon composite can also be obtained.

  In addition, unlike materials that could only be confirmed in microscopic amounts by conventional microscopic observation, the carbonaceous material containing the iron-carbon composite used in the present invention can be synthesized in large quantities, and its weight can easily be increased to 1 mg or more. can do. The material of the present invention can be produced infinitely by scaling up or repeating the process of the present invention described later.

The carbonaceous material of the present invention is attributed to iron or iron carbide contained in powder X-ray diffraction measurement in which X-rays of CuKα are irradiated with an irradiation area of 25 mm ² or more with respect to 1 mg of the carbonaceous material. The integrated intensity of the peak showing the strongest integrated intensity among the peaks of ° <2θ <50 ° is Ia, and 26 ° <2θ <27 ° attributed to the average distance (d002) between the carbon network surfaces of the carbon tubes. When the integrated intensity Ib of the peak is set, the ratio R (= Ia / Ib) of Ia to Ib is preferably about 0.35 to 5, particularly about 0.5 to 4, more preferably 1 to 3. Degree.

In this specification, the ratio of Ia / Ib is referred to as an R value. This R value peaks as an average value of the entire carbonaceous material when the carbonaceous material containing the iron-carbon composite used in the present invention is observed in an X-ray diffraction method with an X-ray irradiation area of 25 mm ² or more. Since the strength is observed, not the inclusion rate or filling rate in one iron-carbon composite that can be measured by TEM analysis, but the entire carbonaceous material as an aggregate of iron-carbon composites, It shows the average value of iron filling rate or inclusion rate.

  In addition, the average filling rate as a whole carbonaceous material containing a large number of the present invention iron-carbon composites is observed by TEM, and a plurality of iron carbides in a plurality of iron-carbon composites observed in each field of view. It can also be obtained by measuring the average filling rate of iron and calculating the average value of the average filling rates of a plurality of visual fields. When measured by such a method, the average filling rate of iron carbide or iron as a whole carbonaceous material comprising the iron-carbon composite used in the present invention is about 10 to 90%, particularly about 40 to 70%.

< Nano flake carbon tube >
By treating the iron-carbon composite in which the iron or iron carbide is partially encapsulated in the inner space of the nano flake carbon tube with acid, the encapsulated iron or iron carbide is dissolved and removed, and the inner space of the tube A hollow nanoflake carbon tube in which no iron or iron carbide is present can be obtained.

  Examples of the acid used for the acid treatment include hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, and the like, and the concentration is preferably about 0.1N. As the acid treatment method, various methods can be used. For example, 1 g of iron-encapsulated nanoflake carbon tube is dispersed in 100 ml of 0.1N hydrochloric acid, and stirred at room temperature for 6 hours. After separation by filtration, a hollow nanoflake carbon tube can be obtained by performing the same treatment twice with 100 ml of 0.1N hydrochloric acid twice.

  The basic structure of the nano flake carbon tube is not particularly changed by this acid treatment. Therefore, even in a hollow nanoflake carbon tube in which iron or iron carbide does not exist in the inner space of the tube, the length of the carbon network surface constituting the outermost surface is 500 nm or less, particularly 2 to 500 nm, particularly 10 to 10. 100 nm.

Azide Compound The azide compound used in the present invention is a compound represented by the following general formula (1).

［式中、
Xはハロゲン原子を示し、
R¹は、水素原子又は炭素数１〜４のアルキル基を示し、
R²は、下記の式（ｐ）で表されるカルボニル基又は下記一般式（ｑ）で表される基を示す。

[Where:
X represents a halogen atom,
R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R ² represents a carbonyl group represented by the following formula (p) or a group represented by the following general formula (q).

（一般式（ｑ）において、ｍは０又は１〜４の整数を示す。）］。

(In general formula (q), m represents 0 or an integer of 1 to 4.)].

In the general formula (1), the alkyl group represented by R ¹ is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, particularly a linear or branched alkyl group having 1 to 3 carbon atoms. However, a methyl group, an ethyl group or the like is preferable.

  In the general formula (1), the halogen atom represented by X is preferably a chlorine atom or a bromine atom, and more preferably a bromine atom.

The compound represented by the general formula (1) can generally be produced, for example, according to the method shown in the following reaction process formula 1.
Reaction process formula 1

上記反応工程式１において、Ｘ、R¹及びR²は前記に同じであり、Yはハロゲン原子（塩素原子、臭素原子）を示す。

In the above reaction process formula 1, X, R ¹ and R ² are the same as above, and Y represents a halogen atom (chlorine atom, bromine atom).

  The reaction of the above reaction process formula 1 will be described in more detail. First, the carboxylic acid derivative represented by the general formula (s1) and the halogenating agent are reacted in a suitable solvent in the presence of a base. The carboxylic acid derivative represented by the general formula (s1) is a known compound or can be easily produced by a known method. Examples of the halogenating agent include ethyl chlorocarbonate. Examples of the solvent include organic solvents such as acetone. Examples of the base include amines such as triethylamine. It is preferable to use an equimolar amount or more, particularly about 1 to 3 moles of the halogenating agent with respect to 1 mole of the carboxylic acid derivative represented by the general formula (s1). The base is preferably used in an amount of at least equimolar, particularly about 1 to 3 moles per mole of the halogenating agent. The reaction between the carboxylic acid derivative represented by the general formula (s1) and the halogenating agent is usually preferably performed at about −10 ° C. to room temperature. Thus, an acid halide (intermediate) represented by the general formula (s2) is obtained.

  Next, sodium azide is reacted with the acid halide represented by the general formula (s2) thus obtained in a suitable solvent. Examples of the solvent include water. The amount of sodium azide used is preferably equimolar or more, particularly about 1 to 3 moles per mole of the acid halide represented by the general formula (s2). This reaction is preferably performed at a temperature of about 0 to 50 ° C., particularly near room temperature. In this way, the target azide compound represented by the general formula (1) is obtained.

  The obtained crude azide compound represented by the general formula (1) can be purified by a generally known purification means, for example, a solvent extraction method, a recrystallization method or the like, if necessary.

  The azide compound represented by the general formula (1) may be used singly or in combination of two or more.

Monomer In the present invention, as the monomer polymerized by the living radical polymerization method, for example, (meth) acrylates and styrenes are preferable.

  In the present description and claims, the term “(meth) acrylate” shall refer to acrylate and / or methacrylate. Similarly, the term “(meth) acrylic acid” refers to acrylic acid and / or methacrylic acid.

  Examples of the (meth) acrylates include (C1-C12) alkyl esters of (meth) acrylic acid, hydroxy lower (C1-C3) alkyl esters, aralkyl esters (particularly benzyl esters), and C 1-4 perfluoroalkyls. Esters can be used. Among these, methyl methacrylate, benzyl methacrylate, t-butyl acrylate, N, N-dimethylacrylamide, 2-hydroxyethyl acrylate, and 2-hydroxyethyl methacrylate can be exemplified.

  In addition to styrene, examples of styrenes include those represented by the following general formula (M1) or (M2).

［一般式（M1）において、R^aは、CF₃、Ｆ、Ｂｒ、Ｃｌ、CH₃、i-C₄H₉、Si(CH₃)₃、CH₂Cl、−O−(C＝O)−CH₃、−CH₂−O−CH₃、−CH₂−O−(C＝O)−CH₃、−SO₃C₂H₅を示す。］

[In General Formula (M1), ^Ra is CF ₃ , F, Br, Cl, CH ₃ , iC ₄ H ₉ , Si (CH ₃ ) ₃ , CH ₂ Cl, —O— (C═O) —CH _{3, -CH 2 -O-CH 3} , -CH 2 -O- (C = O) -CH 3, showing a -SO ₃ C ₂ H _5. ]

［一般式（M2）において、R^bは、CF₃又はCH₃を示す。］
これらモノマーは、１種単独で使用してもよく、また、２種以上を併用してもよい。これら一般式（M1）及び一般式（M2）で表されるモノマーは、いずれも公知のモノマーである。これらモノマーのうちでも、スチレン、スチレンスルホン酸エチル等を使用するのが好ましい。

[In General Formula (M2), R ^b represents CF ₃ or CH ₃ . ]
These monomers may be used individually by 1 type, and may use 2 or more types together. The monomers represented by these general formulas (M1) and (M2) are both known monomers. Among these monomers, it is preferable to use styrene, ethyl styrenesulfonate, or the like.

Production Method of Polymer-Modified Nanoscale Carbon Tube of the Present Invention The polymer-modified nanoscale carbon tube of the present invention is produced by, for example, the surface (side surface and both ends) of the nanoscale carbon tube by an azide compound represented by the general formula (1). Can be produced by a method comprising a step of modifying the monomer (first step) and a step of graft polymerization of the monomer by a living radical polymerization method (second step).

<First step: Modification step with azide compound>
First, as a first step, a nanoscale carbon tube is reacted with an azide compound represented by the general formula (1). The amount of the azide compound used can be appropriately selected from a wide range, but generally it is preferably about 5 to 5000 parts by weight, particularly about 50 to 500 parts by weight, per 100 parts by weight of the nanoscale carbon tube.

  The reaction is preferably carried out in an inert solvent. Examples of the inert solvent include solvents that dissolve the azide compound and that do not substantially react with the nanoscale carbon tube. Examples thereof include dimethylformamide (DMF), dimethylacetamide, and N-methylpyrrolidone. it can. The amount of the solvent used can be appropriately selected from a wide range, but is usually about 1000 to 1,000,000 parts by weight, particularly about 10,000 to 200,000 parts by weight per 100 parts by weight of the nanoscale carbon tube. preferable.

  In the reaction, the nanoscale carbon tube is dispersed in the solvent. The dispersion may be performed using a known dispersion device such as an ultrasonic homogenizer. Next, the azide compound represented by the general formula (1) is added and reacted.

  The reaction is preferably performed in the absence of oxygen, and is preferably performed in an inert gas atmosphere such as argon or nitrogen. Moreover, it is preferable to deoxygenate also about the dissolved oxygen in the said solvent, for example, it is advantageous to deoxygenate beforehand, for example by blowing the said inert gas in a solvent.

  The reaction temperature can be appropriately selected from a wide range, but in general, it is preferably about 80 to 150 ° C, particularly preferably about 100 to 130 ° C. The reaction time varies depending on the reaction temperature, the amount of azide compound used, etc., but is generally about 30 minutes to 200 hours.

  By the above reaction, the general formula (1c)

［式中、X、R¹及びR²は、一般式（１）におけると同じ意味を有する。］
で表される基がその窒素原子で結合する。上記一般式(1c)で表される基は、その窒素原子とナノスケールカーボンチューブ表面の炭素原子との間で化学結合（共有結合）を形成して、ナノスケールカーボンチューブ表面に結合している。

[Wherein X, R ¹ and R ² have the same meaning as in general formula (1). ]
The group represented by this is bonded by the nitrogen atom. The group represented by the general formula (1c) is bonded to the nanoscale carbon tube surface by forming a chemical bond (covalent bond) between the nitrogen atom and the carbon atom on the nanoscale carbon tube surface. .

  The amount of the group represented by the general formula (1c) bonded to the nanoscale carbon tube surface generally increases as the amount of the azide compound represented by the general formula (1) increases. Therefore, by adjusting the amount of the azide compound represented by the general formula (1), the amount of the group represented by the general formula (1c) bonded to the nanoscale carbon tube surface can be adjusted.

  In this way, a reaction mixture containing the nanoscale carbon tube to which the group represented by the general formula (1c) is bonded is obtained, and the reaction mixture including the nanoscale carbon tube to which the linking group is bonded is continued as it is in the living radical polymerization step. In addition, the nanoscale carbon tube to which the linking group is bonded may be isolated by a known isolation method and then used in the subsequent living radical polymerization step.

<Second step: Living radical polymerization step>
As described above, the group represented by the general formula (1c) functions as an initiation point (initiator) for living radical polymerization, and the polymer is grown by living radical polymerization to grow the polymer. be able to.

  Therefore, the corresponding polymer can be graft-polymerized by conducting a living radical polymerization reaction of the monomer on the nanoscale carbon tube modified with the azide compound obtained in the first step.

  As the living radical polymerization reaction, an atom transfer radical polymerization (ATRP) method can be used. The ATRP method is a polymerization method capable of producing a polymer having a narrow molecular weight distribution, and is industrially advantageous as compared with the living anion polymerization method. For example, in living anionic polymerization, it is important to prevent contamination of impurities such as trace amounts of water, and the operation is complicated for the management. On the other hand, the ATRP method has the convenience that a good reaction can be continued to the extent that a normal deoxygenation operation is performed, and is also advantageous for scale-up as an industrial production method.

  In general, in the ATRP method, the monomer is subjected to living radical polymerization in the presence of an initiator and a catalyst, if necessary, using a solvent. When the ATRP method is used as a polymerization method of the polymer of the present invention, a nanoscale carbon tube surface-modified with at least one azide compound represented by the general formula (1), that is, represented by the general formula (1c) A nanoscale carbon tube with a group attached to the side and both ends serves as an initiator. As a result, the living radical polymerization proceeds with the group represented by the general formula (1c) bonded to the surface of the nanoscale carbon tube as an initiation point (initiator), and the resulting polymer causes the side surface of the nanoscale carbon tube and Both ends can be modified.

Moreover, as a catalyst, the catalyst of a general ATRP method can be used, for example, chlorides and bromides, such as transition metals, especially copper, nickel, iron, ruthenium, etc. are preferable. However, monovalent ions are used for copper, and divalent ions are used for nickel, iron, and ruthenium. These metal catalysts are usually used as an organometallic complex or in combination with a bipyridyl or amine compound as a ligand. Among these catalysts, cuprous chloride (CuCl), cuprous bromide (CuBr), and NiBr ₂ (P (nC ₄ H ₉ ) ₃ ) ₂ are preferable.

  Moreover, as a representative example of the above ligand, 2,2′-bipyridyl, 4,4′-di-tert-butyl-2,2′-bipyridyl, 4,4′-diheptyl-2,2′-bipyridyl 4,4′-di (1-butyl-pentyl) -2,2′-bipyridyl, 4,4′-ditridecyl-2,2′-bipyridyl, 1,1,4,7,10,10-hexamethyl Examples include triethylenetetramine, compound (3) (that is, a compound represented by the following formula (3)), and the like. When a ruthenium 2+ complex is used, a Lewis acid such as triisopropoxyaluminum is preferably used in combination. Among these, a copper-based catalyst selected from the group consisting of cuprous bromide and cuprous chloride and 2,2′-bipyridyl or 1,1,4,7,10,10-hexamethyltriethylenetetramine are used. A combined catalyst is particularly preferred.

特に、本発明では、上記ＡＴＲＰ法によるリビングラジカル重合を、塩化第一銅（CuCl）及び臭化第一銅（CuBr）から選択される触媒及び２，２'−ビピリジル、４，４'−ジ−tert−ブチル−２，２'−ビピリジル、４，４'−ジヘプチル−２，２'−ビピリジル、４，４'−ジ（１−ブチル−ペンチル）−２，２'−ビピリジル、４，４'−ジトリデシル−２，２'−ビピリジル、１，１，４，７，１０,１０−ヘキサメチルトリエチレンテトラミン及び上記化合物（３）からなる群から選ばれる少なくとも１種の配位子の存在下で、又は、NiBr₂(P(n-C₄H₉)₃)₂の存在下で行うのが好ましい。

In particular, in the present invention, the living radical polymerization by the ATRP method is performed using a catalyst selected from cuprous chloride (CuCl) and cuprous bromide (CuBr), and 2,2′-bipyridyl, 4,4′-di -Tert-butyl-2,2'-bipyridyl, 4,4'-diheptyl-2,2'-bipyridyl, 4,4'-di (1-butyl-pentyl) -2,2'-bipyridyl, 4,4 In the presence of at least one ligand selected from the group consisting of '-ditridecyl-2,2'-bipyridyl, 1,1,4,7,10,10-hexamethyltriethylenetetramine and the above compound (3) Or in the presence of NiBr ₂ (P (nC ₄ H ₉ ) ₃ ) ₂ .

  In the living radical polymerization step, which is the second step of the present invention, polymerization can be carried out without solvent, but a solvent can also be used as necessary. Although the kind of solvent is not specifically limited, what melt | dissolves a raw material monomer and a catalyst (or catalyst system which consists of a catalyst and a ligand) can be used from a wide range. Among them, those that do not promote a stop reaction such as chain transfer and disproportionation are preferable. As such a solvent, for example, toluene, tetrahydrofuran (THF), methanol, water, ethyl carbonate and the like can be used. Furthermore, other solvents that act as chain transfer agents in normal radical polymerization, such as chloroform, can also be used.

  In the present invention, the living radical polymerization reaction is carried out by using the monomer, catalyst (or catalyst and ligand) on the reaction mixture in the first step or on the nanoscale carbon tube to which the group represented by the general formula (1c) is bonded. And a solvent system as necessary.

  The amount of the monomer used may be selected as appropriate, but in general, it is in large excess with respect to 1 part by weight of the nanoscale carbon tube, for example, about 10 to 10,000 parts by weight, preferably about 100 to 1000 parts by weight Good results are then obtained.

  Moreover, although the usage-amount of a catalyst can be suitably selected from a wide range, generally it is large excess with respect to 1 weight part of nanoscale carbon tubes, for example, about 10-1000 weight part, especially about 50-200 weight part. It is preferable to do this.

  When a catalyst system comprising a catalyst and a ligand is used, generally, about 0.1 to 10 parts by weight, particularly about 0.5 to 3 parts by weight of the ligand is used with respect to 1 part by weight of the catalyst. Is preferred.

  When the solvent is used, the amount of the solvent used can be appropriately selected from a wide range, but generally it is preferably about 0 to 10 parts by weight, particularly preferably about 0 to 3 parts by weight with respect to 1 part by weight of the monomer. .

  The reaction system is preferably carried out in the absence of oxygen, and is preferably carried out in an inert gas atmosphere such as argon, nitrogen and helium. Moreover, it is preferable to deoxygenate also about the dissolved oxygen in the said solvent, for example, it is advantageous to deoxygenate beforehand, for example by blowing the said inert gas in a solvent.

  The polymerization reaction temperature can be appropriately selected from a wide range, but is generally about 15 to 90 ° C, particularly preferably about 20 to 60 ° C, from the viewpoint of suppressing the spontaneous reaction of the monomer. There is an example in which polymerization proceeds easily using water as a solvent even at a low temperature of about room temperature. The reaction time required for the living polymerization of the present invention is generally about 0.5 to 72 hours, although it depends on other polymerization conditions.

  Further, when two or more kinds of monomers are polymerized simultaneously, a random copolymer can be produced, and when polymerized sequentially, a block copolymer that has been difficult to synthesize by a normal radical polymerization method can be produced. For example, when an acrylate (A) is polymerized first, and then a monomer (B) other than the above is polymerized, an AB type consisting of a polymer block A and a polymer block B is obtained. Block copolymers can be produced. When the monomer A is polymerized again following the polymerization of the monomer B, an ABA type block copolymer can be produced. Further, when the monomers A and B are polymerized in the reverse order, a B-A-B type block copolymer can be produced. As said other monomer (B), the said styrene can be illustrated, for example.

  Thus, on the side and both ends of the nanoscale carbon tube, the general formula (1a)

［式中、R¹及びR²は、一般式（１）におけると同じ意味を有し、R³は、（メタ）アクリレート及びスチレン類からなる群から選ばれる少なくとも１種のモノマーのリビングラジカル重合体を示す。］
で表される修飾基が結合した本発明のポリマー修飾ナノスケールカーボンチューブないしポリマー−ナノスケールカーボンチューブ複合材料を含有する反応混合物を得る。

[Wherein R ¹ and R ² have the same meaning as in general formula (1), and R ³ represents the living radical weight of at least one monomer selected from the group consisting of (meth) acrylates and styrenes. Indicates coalescence. ]
A reaction mixture containing the polymer-modified nanoscale carbon tube or polymer-nanoscale carbon tube composite material of the present invention to which a modifying group represented by formula (1) is bonded is obtained.

  Various methods can be used to isolate the polymer-modified nanoscale carbon tube or polymer-nanoscale carbon tube composite material of the present invention from the reaction mixture thus obtained. For example, a solvent capable of dissolving the used monomer, for example, an organic solvent such as toluene, xylene, dimethylformamide, N-methylpyrrolidone and the like is added to the reaction mixture to dilute, and the diluted solution may be filtered. If necessary, this dilution and filtration operation may be repeated. In the present invention, the catalyst, unreacted monomer, reaction solvent, ligand, etc. can be removed by filtering with a filter having a pore size sufficiently small with respect to the size of the nanoscale carbon tube. The desired product can be isolated.

Polymer-modified nanoscale carbon tube or polymer-nanoscale carbon tube composite material of the present invention The polymer-modified nanoscale carbon tube of the present invention is modified on the side and both ends of the nanoscale carbon tube by the general formula (1a). It is characterized in that the groups are bonded.

  In the polymer-modified nanoscale carbon tube of the present invention, the amount of the modifying group represented by the general formula (1a) bonded to the surface of the nanoscale carbon tube is 5 to 50 of the polymer-modified nanoscale carbon tube of the present invention. % By weight, in particular 10 to 40% by weight.

R ³ in the general formula (1a) represents a group (polymer chain) obtained by living radical polymerization of at least one monomer selected from the group consisting of (meth) acrylates and styrenes. That is, R ³ is a group composed of a polymer chain in which the monomer is grown by the living radical polymerization. Examples of such polymer chains are at least one polymer or copolymer selected from the group consisting of the (meth) acrylates and styrenes. Specifically, homopolymers and copolymers of acrylates, homopolymers of styrenes And a copolymer, a random copolymer of acrylates and styrene, a block copolymer composed of a block composed of acrylates and a block composed of styrenes, and the like.

In the present invention, the nitrogen atom of the linking group represented by the general formula (1b) is bonded to the side surface and both ends of the nanoscale carbon tube, and the linking group represented by the general formula (1b) At least one monomer selected from the group consisting of (meth) acrylates and styrenes is graft-polymerized by a living radical polymerization method to the carbon atom to which the group R ¹ , the group R ² and the methyl group are bonded. A polymer-nanoscale carbon tube composite material is provided.

  In the polymer-nanoscale carbon tube composite material of the present invention, the linking group represented by the general formula (1b) bonded to the nanoscale carbon tube surface is graft-polymerized by a living radical polymerization method starting from the linking group. The total amount of the polymer comprising at least one monomer selected from the group consisting of (meth) acrylates and styrenes is 5 to 50% by weight of the polymer-nanoscale carbon tube composite material of the present invention, particularly 10 to 10%. 40% by weight.

  In the polymer-modified nanoscale carbon tube and polymer-nanoscale carbon tube composite material of the present invention, a polymer grown on the nanoscale carbon tube by the living radical polymerization method is a linking group represented by the general formula (1b). It is a novel material that is clearly different from the composite material described in Non-Patent Document 6 in that it is bonded (graft polymerization) via a polymer.

  In addition, compared with the polymer-modified multi-walled carbon nanotube described in Non-Patent Document 7, the polymer-modified nanoscale carbon tube and the polymer-nanoscale carbon tube composite material of the present invention are completely different in the structure of the linking group.

  Further, the polymer-modified nanoscale carbon tube and polymer-nanoscale carbon tube composite material of the present invention are clearly different in the structure of the linking group even when compared with the material described in Non-Patent Document 8.

  The polymer-modified nanoscale carbon tube and polymer-nanoscale carbon tube composite material of the present invention has dramatically improved affinity for a medium such as a solvent and a resin, and uniform dispersion in these medium is extremely easy. In addition, there is an advantage that the nanoscale carbon tube is not substantially precipitated or phase-separated in the medium. Such excellent dispersibility or dispersion stability is an intrinsic property of the polymer-modified nanoscale carbon tube or polymer-nanoscale carbon tube composite material of the present invention.

  Reference examples (manufacturing examples of nanoscale carbon tubes), examples and comparative examples are shown below to further clarify the features of the present invention. However, the present invention is not limited to these examples. Absent.

Reference example 1
Production of amorphous nanoscale carbon nanotubes Amorphous nanoscale carbon nanotubes were prepared by the following method:
10 mg of anhydrous iron chloride powder (particle size of 500 μm or less) was uniformly sprinkled onto a 60 μm × 10 mm × 10 mm PTFE film, and then plasma-excited. Plasma excitation conditions were as follows:
Atmosphere: Argon (Ar)
Internal pressure: 0.01 torr
Input power: 300W
RF frequency: 13.56 MHz.

  After completion of the reaction, it was confirmed by a scanning electron microscope (SEM) and X-ray diffraction that an amorphous nanoscale carbon tube (outer diameter: 10-60 nm, length: 5-6 μm) was formed.

  The obtained amorphous nanoscale carbon tube has an X-ray diffraction angle (2θ) of 19.1 degrees, and the calculated carbon network plane spacing (d002) is 4.6 mm, and the half-width of the band of 2θ is 8 It was 1 degree.

Reference example 2
By using toluene as a raw material and ferric chloride as a catalyst and performing a reaction according to the method described in JP-A-2002-338220, iron carbide is partially included in the inner space of the nanoflake carbon tube. A carbonaceous material containing an iron-carbon composite was obtained.

  The obtained iron-carbon composite was highly linear with an outer diameter of 20 to 100 nm and a length of 1 to 10 microns from the result of SEM observation. Moreover, the thickness of the wall part which consists of carbon was 5-40 nm, and was substantially uniform over the full length. In TEM observation, the wall surface appears to be a patchwork shape (so-called paper mache shape or cord shape), not a nested shape or a scroll shape. It was confirmed that the nanoflake carbon tube had a graphite structure with an average distance (d002) between the mesh surfaces of 0.34 nm or less. Further, it was confirmed by X-ray diffraction and EDX that the iron-carbon composite of the present invention contained iron carbide.

  When the carbonaceous material containing many iron-carbon composites which comprise the obtained carbonaceous material of this invention was observed with the electron microscope (TEM), the space part (namely, nanoflake carbon tube of a nanoflake carbon tube) was observed. Iron-carbon composites having various filling rates in the range of 20 to 60% filling rate of iron carbide in the space surrounded by the tube wall were mixed.

  The average filling factor calculated by observing a plurality of fields of view of the TEM observation image of iron carbide into the space in the nano flake carbon tube of the large number of iron-carbon composites was 30%. The R value calculated from X-ray diffraction was 0.57.

Example 1
In a solution consisting of 10.9 g of 2-bromoisobutyric acid, 7.26 g of triethylamine and about 30 g of acetone, a solution prepared by dissolving 7.15 g of ethyl chlorocarbonate in about 30 g of acetone was added dropwise under ice cooling to react. An active intermediate (acid chloride) was obtained.

  Next, a solution obtained by dissolving 6.74 g of sodium azide in 30 g of water was dropped into the obtained reaction mixture at room temperature for about 30 minutes with stirring.

  Water and ethyl acetate were added to the reaction mixture containing the obtained azide compound, and the target product was extracted into an organic layer. The ethyl acetate layer was concentrated to about 20% of the total amount using a rotary evaporator, and this concentrated solution was used as it was in Example 2 below.

A part of the concentrated solution was sampled, and the structure of the product was analyzed by ¹ H-NMR, IR, and elemental analysis. ^{In 1} H-NMR, a singlet peak was observed at δ = 1.95 ppm. Further, in the IR analysis, absorption specific to the azide group was observed at 2100 cm ⁻¹ . From these analysis results, it was confirmed that the obtained azide compound was a compound in which R ¹ = methyl group, R ² = carbonyl group, and X = Br in the general formula (1).

Example 2
(1) First step: Modification step with an azide compound An iron-carbon composite (a nanoflake carbon tube partially encapsulating iron carbide) obtained in the same manner as in Reference Example 2 above in a 100 ml round bottom flask ) 35 mg and 23.2 g of dimethylformamide (DMF) were charged, and preliminary dispersion was performed using an ultrasonic homogenizer. Thereafter, argon gas was blown into the obtained dispersion to deoxygenate. The resulting dispersion was deoxygenated by blowing argon gas, and then the azide compound-containing concentrate obtained in Example 1 (containing 0.141 g of azide compound) was added, and the bath temperature was increased to 130 ° C. with stirring. The temperature rose. Stirring was carried out at the same temperature for 2 days.

  The resulting reaction mixture was filtered through a 0.2 μm PTFE filter and washed thoroughly with DMF.

(2) Second step: Living radical polymerization step (ATRP method)
A 100 ml round bottom flask was charged with the total amount of the azide compound-modified iron-carbon composite obtained in the first step and 20 g of styrene, and deoxygenated by blowing argon gas into the system, and immediately using NiBr ₂ as a nickel catalyst. (P (nC ₄ H ₉ ) ₃ ) _{2 (} 2.9 g) was added, the bath temperature was raised to 100 ° C., and the mixture was stirred at the same temperature for 4 hours.

  The obtained reaction mixture was diluted with a large amount of toluene, the diluted solution was filtered using a 0.2 μm PTFE filter, sufficiently washed with toluene, and dried at 60 ° C. for 1 day using a vacuum dryer. Thus, an iron-carbon composite modified with the azide compound obtained in Example 1 and further grafted with styrene by living radical polymerization was obtained.

  The thermal analysis result of the obtained polystyrene-modified iron-carbon composite is shown below. That is, the thermal analysis (TG-DTA) of the iron-carbon composite modified by graft polymerization of the polystyrene and the unmodified product (the iron-carbon composite itself used as a raw material in Example 2) was performed. The modification rate by the polymer (the proportion of the polymer present) was determined. In the thermal analysis, the weight decreased while the temperature was increased from room temperature to 900 ° C. at a temperature increase rate of 10 ° C./min was measured. The iron-carbon composite modified by graft polymerization of polystyrene lost about 70% by weight. On the other hand, the unmodified product lost about 55% in weight. From this result, it was found that the total amount of the linking group derived from the polystyrene and the azide compound bonded by graft polymerization was about 15% by weight of the total amount of the iron-carbon complex modified with polystyrene.

  Moreover, the obtained polystyrene-modified iron-carbon composite of the present invention was well dispersed in toluene and was excellent in dispersion stability (see Test Example 1 below).

Comparative Example 1
Nanoscale using the diazonium method (Non-Patent Document 4, JM Tour, et al., Mancomolecules 35, 8825 (2002)), which is a typical carbon nanotube chemical modification method in the prior art, as a raw material in Example 2. This was applied to a carbon tube (an iron-carbon composite, that is, a nanoflake carbon tube partially containing iron carbide). More details are as follows.

(1) Synthesis of p-aminobenzoic acid ester In a round bottom flask with a reflux tube (capacity 500 ml), 11.0 g of tert-butyl alcohol was added, and then about 200 g of dichloromethane and 12.8 g of pyridine were added and dissolved. To the resulting solution, 25 g of p-nitrobenzoic acid chloride was gradually added, and then the reaction was continued at a bath temperature of 60 ° C. for 1 day. The resulting reaction mixture was diluted with dichloromethane and then washed with pure water, dilute hydrochloric acid and a saturated aqueous sodium bicarbonate solution. Recrystallization was performed with hexane.

  After dissolving 18.32 g of the obtained purified product in about 400 mL of ethanol, 2 g of palladium-supported carbon was dispersed as a catalyst, and about 5.6 L of hydrogen was added. After reacting the calculated amount of hydrogen, the catalyst was removed and dried to obtain a crude product. Recrystallization was performed with hexane / ethyl acetate.

^{In 1} H-NMR, a signal derived from a tert-butyl group and a signal derived from an aromatic ring were measured, so that the product was confirmed to be tert-butyl p-aminobenzoate.

(2) Modification reaction Add 50 mg of the iron-carbon complex obtained in the same manner as in Reference Example 2 above to a mixed solvent of 75 mL of dichlorobenzene and 15 mL of tetrahydrofuran (THF) in a round bottom flask, and disperse with an ultrasonic homogenizer. Promoted. Then, argon gas was blown to deoxygenate, p-aminobenzoic acid tert-butyl ester 8.59 g and isoamyl nitrite 0.9 g were added, and the reaction was continued for about 2 days at a bath temperature of about 55-60 ° C. It was.

  After completion of the reaction, the product was collected by filtration with a 0.2 μ polytetrafluoroethylene (PTFE) filter, washed repeatedly with DMF, and dried to obtain a purified product.

Test example 1
Evaluation of dispersion stability in solvents
According to the method described in R. Yerushalmi-Rosen, et al., Nano Lett. 2 (1) 25 (2002), the modified iron-carbon composite (iron carbide) obtained in Example 2 and Comparative Example 1 was used. The dispersibility of toluene in the non-modified iron-carbon composite was evaluated.

  To 100 g of toluene, 0.2 g of the modified iron-carbon composite or unmodified iron-carbon composite obtained in Example 2 and Comparative Example 1 was added, and an ultrasonic homogenizer (ultrasonic irradiation condition: frequency = 20 kHz, 150 (Watt, irradiation time = 3 minutes). The resulting mixed solution was treated at 4,000 rpm (3130 g) for 20 minutes using a centrifuge. Then, the liquid mixture was taken out and the state was observed.

  When the modified or unmodified nanoscale carbon tube used for evaluation has excellent dispersibility in toluene, the mixed solution exhibits the black color of the nanoscale carbon tube even after the centrifugal separation treatment. On the other hand, when the dispersibility with respect to toluene is low, the amount of nanoscale carbon tubes in the supernatant liquid is small or absent after the centrifugation treatment.

  The dispersion obtained by dispersing the modified nanoscale carbon tube obtained in Example 2 in toluene maintains the original black color even after the centrifugal treatment, and the modified nanoscale carbon tube is contained in the dispersion. Was present in a large amount without substantial precipitation, and only a very small amount of precipitation was observed. Moreover, the dispersion liquid after centrifugation maintained the original black color even after being left for 3 months.

  On the other hand, in the dispersion obtained by dispersing the modified nanoscale carbon tube obtained in Comparative Example 1 in toluene, the supernatant is almost colorless and transparent after centrifugation, and a large amount of precipitate is observed at the bottom of the centrifuge beaker. From this, it was clear that there was almost no modified nanoscale carbon tube in the supernatant.

  Further, the unmodified nanoscale carbon tube (the iron-carbon composite itself used as a raw material in Example 2) was hardly present in the supernatant after the centrifugation treatment as in Comparative Example 1.

  As is clear from the above results, the polystyrene-modified iron-carbon composite of the present invention includes an iron-carbon composite modified by the method of Non-Patent Document 4 (Comparative Example 1) and an iron-carbon composite not modified with a polymer. It can be seen that the dispersibility and dispersion stability are far superior to the body itself.

It is an electron microscope (TEM) photograph of one iron-carbon complex which comprises the carbonaceous material obtained in Example 1 of Unexamined-Japanese-Patent No. 2002-338220. It is an electron microscope (TEM) photograph which shows the presence state of the iron-carbon composite in the carbonaceous material obtained in Example 1 of Unexamined-Japanese-Patent No. 2002-338220. It is the electron microscope (TEM) photograph which made one iron-carbon composite_body | complex obtained in Example 1 of Unexamined-Japanese-Patent No. 2002-338220 into the shape of a ring. In addition, the black triangle ((triangle | delta)) shown in the photograph of FIG. 3 has shown the EDX measurement point for a composition analysis. A schematic diagram of a TEM image of a carbon tube is shown, (a-1) is a schematic diagram of a TEM image of a cylindrical nanoflake carbon tube, and (a-2) is a TEM image of a nested multi-wall carbon nanotube. It is a schematic diagram.

Explanation of symbols

100 TEM image in the longitudinal direction of the nano flake carbon tube 110 Approximate linear graphene sheet image 200 TEM image in a cross section substantially perpendicular to the longitudinal direction of the nano flake carbon tube 210 Arc-shaped graphene sheet image 300 Longitudinal direction of the multi-layered carbon nanotube in a nested structure Straight graphene sheet image continuous over the entire length of 400 TEM image of a cross section perpendicular to the longitudinal direction of a nested multi-walled carbon nanotube

Claims (9)

The following general formula (1a)

[Where:
R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R ² is the formula (p)

Represents a group represented by
R ³ represents a polymer of at least one monomer selected from the group consisting of (meth) acrylates and styrenes. ]
A polymer-modified nanoscale carbon tube, wherein at least one modification group represented by the formula (1) is bonded to the side surface and both ends of the nanoscale carbon tube. Nanoscale carbon tube
(I) single-walled carbon nanotubes,
(Ii) amorphous nanoscale carbon tube,
(Iii) a carbon tube selected from the group consisting of nano-flake carbon tubes and nested multi-walled carbon nanotubes, or (iv) the carbon tube of (iii) above and iron carbide or iron, and the inner space of the carbon tube iron 10 to 90% of the section iron or iron carbide is filled - polymer-modified nanoscale carbon tubes according to claim 1 is a carbon composite. (A) On the side and both ends of the nanoscale carbon tube, (b) the following general formula (1b)

[Where:
R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R ² is the formula (p)

The group represented by these is shown. ]
A carbon atom to which at least one linking group represented by general formula (1b) is bonded to the group R ¹ , the group R ² and the methyl group. A polymer-nanoscale carbon tube composite material, wherein at least one monomer selected from the group consisting of (meth) acrylates and styrenes is graft-polymerized by a living radical polymerization method. Nanoscale carbon tube
(I) single-walled carbon nanotubes,
(Ii) amorphous nanoscale carbon tube,
(Iii) a carbon tube selected from the group consisting of nano-flake carbon tubes and nested multi-walled carbon nanotubes, or (iv) the carbon tube of (iii) above and iron carbide or iron, and the inner space of the carbon tube The polymer-nanoscale carbon tube composite material according to claim 3 , which is an iron-carbon composite in which iron carbide or iron is filled in a range of 10 to 90% of the part. Nanoscale carbon tube and general formula (1)

[Where:
X represents a halogen atom,
R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R ² is the formula (p)

The group represented by these is shown. ]
And at least one monomer selected from the group consisting of (meth) acrylates and styrenes is graft-polymerized by a living radical polymerization method to the obtained reaction product. A method for producing a polymer-nanoscale carbon tube composite material. Nanoscale carbon tube
(I) single-walled carbon nanotubes,
(Ii) amorphous nanoscale carbon tube,
(Iii) a carbon tube selected from the group consisting of nano-flake carbon tubes and nested multi-walled carbon nanotubes, or (iv) the carbon tube of (iii) above and iron carbide or iron, and the inner space of the carbon tube The manufacturing method according to claim 5 , which is an iron-carbon composite in which iron carbide or iron is filled in a range of 10 to 90% of the part. 6. The production method according to claim 5 , wherein the living radical polymerization method is an ATRP (Atom Transfer Radical Polymerization) method. Living radical polymerization is carried out using a catalyst selected from cuprous chloride (CuCl) and cuprous bromide (CuBr) and 2,2′-bipyridyl, 4,4′-di-tert-butyl-2,2′- Bipyridyl, 4,4′-diheptyl-2,2′-bipyridyl, 4,4′-di (1-butyl-pentyl) -2,2′-bipyridyl, 4,4′-ditridecyl-2,2′-bipyridyl 1,1,4,7,10,10-hexamethyltriethylenetetramine and the following formula (3)

At least one in the presence of a ligand selected from in represented by the group consisting of the compounds or any of the claims 5-7 carried out in the presence of _{NiBr 2 (P (nC 4 H} 9) 3) 2 The manufacturing method of crab. A polymer-nanoscale carbon tube composite material obtained by the production method according to any one of claims 5 to 8 .

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