KR20080096051A

KR20080096051A - Preparation methods for polymer composites containing carbon nanotubes

Info

Publication number: KR20080096051A
Application number: KR1020070040933A
Authority: KR
Inventors: 우성일; 조현용
Original assignee: 한국과학기술원
Priority date: 2007-04-26
Filing date: 2007-04-26
Publication date: 2008-10-30

Abstract

The present invention relates to a method for preparing a composite of carbon nanotubes and a polymer, and more particularly, the presence of an organoaluminum compound and an organic boron compound as a metal catalyst and a promoter supported on a surface of a carbon nanotube containing various functional groups. The present invention relates to a method for producing a polymer composite comprising carbon nanotubes by polymerization.

The present invention utilizes an in-situ polymerization method in which various types of metal catalysts are supported on a carbon nanotube including a functional group, and polymerized from a catalyst carrying a monomer. It is dispersed, and provides a polymer composite including carbon nanotubes with improved physical and mechanical properties compared to pure polymers.

Description

Preparation method for polymer composites containing carbon nanotubes {Preparation methods for polymer composites containing carbon nanotubes}

1 is a scanning electron micrograph of a carbon nanotube and polyethylene composite magnified 50,000 times.

2 is a scanning electron micrograph of a carbon nanotube and a polymethyl methacrylate composite magnified 50,000 times.

The present invention relates to a method for producing a composite of carbon nanotubes and polymers, and more particularly, to a metal catalyst and an organoaluminum or organic boron compound supported on a surface of a carbon nanotube an olefin monomer including a double bond between carbon and carbon. The present invention relates to a process for producing a composite of carbon nanotubes / polymer by polymerization in the presence.

Carbon nanotubes were first published in 1991 by Dr. Iijima of Japan. Carbon nanotubes have a graphite sheet that is rounded off while maintaining a nano-sized diameter to form a tube, and the diameter of the tube is nano-sized. Single-well carbon nanotubes (SWNTs), double-well carbon nanotubes (DWNTs) and multi-wall carbon nanotubes (SWNTs), depending on the number of curled nanotube walls nanotube, MWNT). These various carbon nanotubes have been found to have excellent physical properties such as thermal and electrical conductivity, strength, and the like. Accordingly, it can be utilized in various material fields requiring conductive materials and high strength. However, since the properties of the carbon nanotubes themselves are in a fine powder state, it is difficult to implement various characteristics of the carbon nanotubes with a single carbon nanotube alone. Therefore, various studies have been conducted to increase the utilization by forming a composite with other materials. A typical composite material with carbon nanotubes is a polymer composite.

Known methods for producing a composite of carbon nanotubes and polymers are known three methods.

(1) Solution blending (solution blending): The polymer is dissolved in a specific solvent, the carbon nanotubes are dispersed in a specific solvent and mixed. Thereafter, the solvent is removed to prepare a composite of carbon nanotubes and a polymer.

(2) Melting blending: After melting the polymer at high temperature, the carbon nanotubes are put together and mixed. After lowering the temperature to prepare a polymer composite.

(3) In-situ polymerization: Polymer composite is prepared by polymerizing monomer in a state in which monomer and carbon nanotube are mixed.

The solution mixing method and the melt mixing method are a composite of a polymer and carbon nanotubes, and the in-situ polymerization method has a feature of using a monomer, not a polymer, in preparation.

As a polymerization method of the carbon nanotubes and the polymer using the in-situ polymerization method, Zhu et al. Reported a method for producing a composite of carbon nanotubes of epoxy resin (Zhu, J .; Kim, J .; Peng, H .; Margrave, JL; Khabashesku, VN; Barrera, EV, Nano Letter, 2003, 3, 1107-1113). In 2005, Dubois et al. Treated the methyl aluminoxane on the surface of carbon nanotubes, and then reported the first results of polymerizing ethylene, a typical olefin monomer, using a metallocene catalyst (Bonduel, D .; Mainil, M .; Alexandre, M .; Monteverde, F .; Dubois, P., Chem. Commun., 2005, 781-783). In addition, in 2006, Park et al. Reported the results of physical adsorption of metallocene catalyst on the surface of carbon nanotubes and polymerization of ethylene (Park, S .; Yoon, SW; Lee, K.- B .; Kim, DJ; Jung, YH; Do, Y .; Paik, H .; Choi, IS, Macromol.Rapid Commun., 2006, 27, 47-50).

Patent Publication No. 2007-0026949 discloses that a monomer is formed by using a metal catalyst on the surface of a carbon nanotube having a functional group instead of a method of mixing a synthetic polymer with a carbon nanotube without a functional group by melting or solution mixing. Polymer polymerization was obtained by in-situ polymerization.

However, these shsanns and patents do not report on the improvement of the physical properties of carbon nanotubes and polymer composites in the above report where polyolefins are polymerized using in-situ polymerization.

The present invention is characterized in that the carbon nanotubes containing functional groups such as hydroxy groups and carboxylic acids on the surface of the metallocene or single active site metal catalyst, and then polymerize the polymers by in-situ polymerization to physical properties compared to pure polymers. It is an object of the present invention to manufacture a composite of the improved carbon nanotubes and a polymer and to provide a method of manufacturing the same.

The present invention in the production of carbon nanotubes and polymer composites,

The carbon nanotubes having functional groups on the surface thereof are supported on an organometallic catalyst and an organic solvent, thereby showing a method for producing a polymer composite including carbon nanotubes using an in-situ olefin polymerization method.

The monomer may be any one selected from methyl acrylate, methyl methacrylate or tert-butyl acrylate.

In the carbon nanotube having functional groups on the surface of the present invention, the functional groups are fluorine, chlorine, bromine, iodine, amine, hydroxy group, carboxylic acid, sulfonic acid, alkoxy, siloxy hydrocarbon, sulfoxy hydrocarbon, heterocyclic group, aliphatic hydrocarbon, alicyclic One or more selected from fluorine, chlorine, bromine, iodine, oxygen, sulfur or nitrogen is a substituted functional group instead of one or more carbons or hydrogens contained in hydrocarbons, aromatic hydrocarbons, alkyl substituted aromatic hydrocarbons.

The alkoxy group in the functional group on the surface of the carbon nanotube is at least one selected from methoxy, ethoxy, propoxy, butoxy, isopropoxy or phenoxy.

In the functional group on the surface of the carbon nanotube, an aliphatic hydrocarbon substituted with one or more selected from fluorine, chlorine, bromine, iodine, oxygen, sulfur or nitrogen in place of carbon hydrogen may be methyl, ethyl, propyl, butyl, iso-propyl or at least one selected from tert-butyl.

In the functional group on the surface of the carbon nanotube, at least one alicyclic hydrocarbon group substituted with fluorine, chlorine, bromine, iodine, oxygen, sulfur or nitrogen in place of carbon hydrogen is adamantyl, norbornyl, cyclopentyl or At least one selected from cyclohexyl.

In the functional group on the surface of the carbon nanotube, an aromatic hydrocarbon group substituted with at least one selected from fluorine, chlorine, bromine, iodine, oxygen, sulfur or nitrogen in place of carbon hydrogen may benzyl, tolyl, mesityl, 2,6-di At least one selected from isopropylphenyl or 2,4,6-trimethyl.

In the functional group on the surface of the carbon nanotube, a heterocyclic group substituted with at least one selected from fluorine, chlorine, bromine, iodine, oxygen, sulfur or nitrogen in place of carbon hydrogen may be selected from 2-pyridinyl or 2-pyrrolyl. 1 or more types.

Carbon nanotubes containing functional groups in the present invention is selected from single-well carbon nanotubes, double-well carbon nanotubes or multi-well carbon nanotubes. It is any 1 or more types.

In the present invention, the surface treatment of the carbon nanotube having a functional group may use an in-situ olefin polymerization method using a catalyst supported on a carbon nanotube using an organoaluminum compound or an organic boron compound.

The organoaluminum compound is methyl aluminoxane, trimethyl aluminum, triethyl aluminum, triiso-butyl aluminum, dimethyl chloro aluminum, di At least one selected from ethyl chloro aluminum, methyl dichloro aluminum, and ethyl dichloro aluminum.

The organic boron compound is triphenylboron, trispentafluoropheneyl boron, tris (3,5-di (trifluoromethyl) phenyl) boron (tris (3,5-) di (trifluoromethyl) phenyl) boron), tetraphenylborate salt or tetrakis (pentapluorophenyl) borate salt.

While using the organic aluminum compound or the organic boron compound in the above, the organic solvent is tetrahydrofuran (tetrahydrofuran), 1,2-dichlorobenzene (1,2-dichlorobenzene), toluene (n-hexane) , n-pentane, n-heptane, n-heptane, chlorobenzene, dichloromethane, chloroform, 1,2-dichloroethane 1 selected from 1,1,2,2-tetrachloroethane, N, N-dimethyl formamide or dimethyl solfoxided More than one species can be used.

In the present invention, the organometallic compound catalyst used in the preparation of a polymer composite including carbon nanotubes by in-situ polymerization of a monomer by supporting an organometallic catalyst on carbon nanotubes has a structure represented by the following formula (1): A method for producing a polymer composite including carbon nanotubes using an in-situ olefin polymerization method using a catalyst supported on carbon nanotubes using an organometallic compound catalyst is provided.

Formula (1)

In the formula (1), R1 is a C1 to C4 alkylene group, C1 to C5 linear, pulverized or cyclic alkylidene group; Silicone compound containing C1-C5 linear or crushed alkyl group; Or a compound comprising a germanium atom containing a C1 to C5 straight or crushed alkyl group; The ring of two CpR2n may or may not be connected.

In CpR2n, Cp can be a cyclopentadienyl group or a cyclopentadienyl group substituted with R2, and R2 is halogen including hydrogen, phosphorus, fluorine, chlorine, bromine and the like; Silicone compounds such as trimethylsilyl, triethylsilyl and triphenylsilyl; C1-C10 linear or pulverized alkyl group; C1-C10 linear alkyl group substituted by halogen, C1-C4 linear alkoxy group; And C1 to C4 linear or pulverized aryloxy group, wherein R2 may be the same or different, R3 is hydrogen, phosphorus, fluorine, chlorine or halogen selected from bromine, C1-20 linear or pulverized alkyl group It is a silicon compound containing; M is a transition metal compound of Groups 4, 5 and 6; In this case, when n is 0, it means that two cyclopentadienyl groups are not connected.In this case, R2 is substituted in Cp with 5, and when n is 1, two cyclopentadienyl groups are connected. In this case, four substituted forms of R2 in Cp. In the above R1, the alkylene group of C1 to C4 is selected from the group consisting of methylene group, ethylene group, propylene group and butylene group, and the linear, pulverized or cyclic alkylidene group of C1 to C5 is methylidene group, ethylidene group , Propylidene group, isopropylidene group, phenylmethylidene group and diphenylmethylidene group. In addition, the silicone compound containing a C1 to C5 linear or pulverized alkyl group is selected from the group consisting of dimethylsilylene group, diethylsilylene group, diisopropylsilylene group, diphenylsilylene group, methylethylsilylene group and methylphenylsilylene group The compound containing a zirconium atom containing a C1-C5 linear or crushed alkyl group is selected from the group consisting of an ethylene group, a dimethylsilylene group, and a methylphenylsilylene group.

In R2, C1 to C10 linear or pulverized alkyl group is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isobutyl, isopentyl and phenyl, and C1 to C10 substituted with halogen. Linear alkyl groups include chloromethyl, chloroethyl, chloropropyl, chlorobutyl, chloropentyl and the like, and C 1 to C 4 linear alkoxy groups include methoxy, ethoxy, propoxy and butoxy. In addition, C1-C4 linear or crushed aryloxy groups include phenoxy, methylphenoxy and pentamethylphenoxy. R3 is halogen including hydrogen, phosphorus, fluorine, chlorine, bromine and the like; Silicon-containing compounds such as trimethylsilyl, triethylsilyl and triphenylsilyl; And a C1-20 straight or branched alkyl group, wherein the alkyl group is methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, hexyl, heptyl, octyl nonyl, decyl and phenyl.

M is a Group 4 element consisting of titanium, zirconium and hafnium; A Group 5 element consisting of vanadium, niobium and tantalum; And a group 6 element composed of chromium, molybdenum and tungsten.

In the present invention, in the preparation of a polymer composite including carbon nanotubes by carrying out an organometallic catalyst on carbon nanotubes and in-situ polymerization of monomers, the organometallic compound catalyst used has a structure of formula (2) It includes a method for producing a polymer composite including carbon nanotubes using an in-situ polymerization method by a catalyst supported on carbon nanotubes using an organometallic compound catalyst.

Formula (2)

In the compound of formula (2), X is independently one selected from oxygen, nitrogen, phosphorus, sulfur and carbon. R1, R2, R3 are independently halogen, hydroxy, carboxylic acid, sulfonic acid, alkoxy, siloxy hydrocarbon, sulfoxy hydrocarbon, aliphatic hydrocarbon, cycloaliphatic hydrocarbon, aromatic hydrocarbon, alkyl substituted aromatic hydrocarbon, heterocyclic group and in the group It is any one or more selected from derivatives substituted with a hetero element instead of carbon or hydrogen, and R1, R2, R3 may be connected to each other to form a ring or may not be connected. R4, R5 are halogenated elements of fluorine, chlorine, bromine, iodine, alkoxy, siloxy hydrocarbons, aliphatic hydrocarbons, aromatic hydrocarbons, alkyl substituted aromatic hydrocarbons, heterocyclic groups and derivatives substituted with hetero elements in place of carbon, hydrogen in said groups It is any 1 type selected from any 1 or more types selected from among.

Examples of the alkoxy group in the compound of formula (2) are any one or more selected from methoxy, ethoxy, propoxy, butoxy, isopropoxy and phenoxy.

Examples of aliphatic hydrocarbons in the compound of formula (2) are any one or more selected from methyl, ethyl, propyl, butyl, iso-propyl, tert-butyl.

Examples of the alicyclic hydrocarbon group in the compound of formula (2) are any one or more selected from adamantyl, norbornyl, cyclopentyl, and cyclohexyl.

Examples of the aromatic hydrocarbon group in the compound of formula (2) are any one or more selected from phenyl, biphenyl, naphthyl, phenanthrenyl and anthracenyl.

Examples of the alkyl substituted aromatic hydrocarbon group in the compound of formula (2) are any one or more selected from benzyl, tolyl, mesityl, 2,6-diisopropylphenyl, 2,4,6-trimethyl.

Examples of the heterocyclic group in the compound of the formula (2) are any one or more selected from 2-pyridinyl and 2-pyrrolyl.

Suitable substituents for forming heterosubstituted derivatives in the compound of formula (2) are any one or more selected from chloro, bromo, fluorine, and iodo.

Examples of the anion X in the compound of formula (2) are any one or more selected from chloro, bromo, fluorine, iodo and methyl groups.

In the compound of Formula (2), M is a metal of Groups 8 to 10 of the periodic table, and as an example thereof, any one selected from nickel, cobalt, palladium, and iron.

In the present invention, the organometallic compound catalyst used in the preparation of a polymer composite including carbon nanotubes by in-situ polymerization of a monomer by supporting an organometallic catalyst on carbon nanotubes has a structure represented by the following formula (3): It includes a method for producing a polymer composite including carbon nanotubes using an in-situ polymerization method by a catalyst supported on carbon nanotubes using an organometallic compound catalyst.

Formula (3)

In the compound of the formula (3), X is independently one selected from oxygen, nitrogen, phosphorus, sulfur and carbon. R1, R2, R3 are independently halogen, hydroxy, carboxylic acid, sulfonic acid, alkoxy, siloxy hydrocarbon, sulfoxy hydrocarbon, aliphatic hydrocarbon, cycloaliphatic hydrocarbon, aromatic hydrocarbon, alkyl substituted aromatic hydrocarbon, heterocyclic group and in the group It is any one or more selected from derivatives substituted with a hetero element instead of carbon or hydrogen, and R1, R2, R3 may be connected to each other to form a ring or may not be connected.

Examples of the alkoxy group in the compound of formula (3) are any one or more selected from methoxy, ethoxy, propoxy, butoxy, isopropoxy or phenoxy.

Examples of aliphatic hydrocarbons in the compound of formula (3) are any one or more selected from methyl, ethyl, propyl, butyl, iso-propyl or tert-butyl.

Examples of the alicyclic hydrocarbon group in the compound of formula (3) are any one or more selected from adamantyl, norbornyl, cyclopentyl or cyclohexyl.

Examples of the aromatic hydrocarbon group in the compound of formula (3) are any one or more selected from phenyl, biphenyl, naphthyl, phenanthrenyl or anthracenyl.

Examples of the alkyl substituted aromatic hydrocarbon group in the compound of formula (3) are any one or more selected from benzyl, tolyl, mesityl, 2,6-diisopropylphenyl or 2,4,6-trimethyl.

Examples of the heterocyclic group in the compound of formula (3) are any one or more selected from 2-pyridinyl or 2-pyrrolyl.

Suitable substituents for forming a heterosubstituted derivative in the compound of formula (3) are any one or more selected from chloro, bromo, fluorine or iodo.

Examples of the anion X in the compound of formula (3) are any one or more selected from chloro, bromo, fluorine, iodo or methyl groups.

In the compound of Formula (3), M is a metal of Groups 8 to 10 of the periodic table, and is one selected from nickel, cobalt, palladium, or iron as an example thereof.

In the present invention, when using at least one organometallic compound selected from the above-mentioned organometallic compounds as a catalyst for supporting carbon nanotubes, the present invention is supported on carbon nanotubes using organoaluminum compounds or organic boron compounds used together. It includes a method for producing a polymer composite containing carbon nanotubes using the in-situ polymerization method by using the prepared catalyst.

In the present invention, in the preparation of carbon nanotubes and polymer composites using an in-situ polymerization method using a catalyst supported on carbon nanotubes, monomers as raw materials are acrylates and derivatives thereof, α-olefins and derivatives thereof, styrene and derivatives thereof. Butadiene and its derivatives, ε-carrolactam and its derivatives, or any one or more selected from hexamethylenediamine and its derivatives may be used.

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

Carbon nanotubes

Carbon nanotubes used in the present invention contain functional groups on the surface. The functional groups contained on the surface of the carbon nanotubes are fluorine, chlorine, bromine, iodine, amine, hydroxy group, carboxylic acid, sulfonic acid, alkoxy, siloxy hydrocarbon, sulfoxy hydrocarbon, heterocyclic group, aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic One or more selected from fluorine, chlorine, bromine, iodine, oxygen, sulfur, and nitrogen are substituted functional groups instead of one or more carbons or hydrogens contained in hydrocarbons, alkyl substituted aromatic hydrocarbons.

Examples of the alkoxy group in the functional group on the surface of the carbon nanotubes are any one or more selected from methoxy, ethoxy, propoxy, butoxy, isopropoxy and phenoxy.

Examples of aliphatic hydrocarbons substituted with one or more selected from fluorine, chlorine, bromine, iodine, oxygen, sulfur, and nitrogen instead of carbon hydrogen in the functional group on the surface of the carbon nanotubes are methyl, ethyl, propyl, butyl, iso-propyl , tert-butyl is any one or more selected from.

Examples of the alicyclic hydrocarbon group substituted with at least one selected from fluorine, chlorine, bromine, iodine, oxygen, sulfur, and nitrogen instead of carbon hydrogen in the functional group on the surface of the carbon nanotube are adamantyl, norbornyl, cyclo At least one selected from pentyl and cyclohexyl.

Examples of the aromatic hydrocarbon group substituted with at least one selected from fluorine, chlorine, bromine, iodine, oxygen, sulfur, and nitrogen instead of carbon hydrogen in the functional group on the surface of the carbon nanotube are benzyl, tolyl, mesityl, 2,6 -At least one selected from diisopropylphenyl and 2,4,6-trimethyl.

Examples of heterocyclic groups in which at least one member selected from fluorine, chlorine, bromine, iodine, oxygen, sulfur, and nitrogen are substituted for carbon hydrogen in the functional group on the surface of the carbon nanotube are selected from 2-pyridinyl and 2-pyrrolyl. At least one selected.

Carbon nanotubes including the functional groups include single-well carbon nanotubes (SWNTs), double-well carbon nanotubes (DWNTs), and multi-wall carbon nanotubes (multi-well carbon nanotubes). , MWNT).

* Surface treatment of carbon nanotubes containing functional groups

Surface treatment of any one or more selected from the carbon nanotubes containing the functional group by one or more methods of stirring, ultrasonic vibration or reflux using any one or more selected from an organoaluminum compound and an organic boron compound in the presence of an organic solvent. do.

Tetrahydrofuran (THF), 1,2-dichlorobenzene (o-DCB), toluene, n-hexane, n- Pentane, n-heptane, chlorobenzene, dichloromethane, chloroform, 1,2-dichloroethane, 1, 1,2,2-tetrachloroethane (1,1,2,2-tetrachloroethane), N, N-dimethyl formamide (N, N-dimethyl formamide (DMF), dimethyl solfoxided (DMSO) selected from 1 or more types can be used.

Examples of organoaluminum compounds include methyl aluminoxane (MAO), trimethyl aluminum (TMA), triethyl aluminum (TEA), triiso-butyl aluminum (TIBAL), dimethylchloro Any one or more selected from dimethyl chloro aluminum (DMCA), diethyl chloro aluminum (DECA), methyl dichloro aluminum (MDCA) and ethyl dichloro aluminum (EDCA) can be used. The organic boron compounds include triphenylboron, trispentafluoropheneyl (boron), tris (3,5-di (trifluoromethyl) phenyl) boron (tris (3,5-) di (trifluoromethyl) phenyl) boron), tetraphenylborate salt, or tetrakis (pentapluorophenyl) borate salt The can be used.

The surface-treated carbon nanotubes are washed five times using at least one selected from the above organic solvents to complete the surface treatment of the carbon nanotubes.

* Catalyst Support

The carbon nanotubes treated with the organoaluminum compound or the organic boron compound are supported by one or more methods of stirring, ultrasonic vibration or reflux using any one or more selected from organometallic compound catalysts in the presence of an organic solvent.

As an example of an organometallic catalyst in the present invention, any one or more selected from compounds of the following formulas (1) to (3) are shown.

Formula (1)

In the formula (1), R1 is a C1 to C4 alkylene group, C1 to C5 linear, pulverized or cyclic alkylidene group; Silicone compound containing C1-C5 linear or crushed alkyl group; Or a compound comprising a germanium atom containing a C1 to C5 straight or crushed alkyl group; Two CpR2n rings may or may not be linked.

In CpR2n, Cp can be a cyclopentadienyl group or a cyclopentadienyl group substituted with R2, and R2 is halogen including hydrogen, phosphorus, fluorine, chlorine, bromine and the like; Silicone compounds such as trimethylsilyl, triethylsilyl and triphenylsilyl; C1-C10 linear or pulverized alkyl group; C1-C10 linear alkyl group substituted by halogen, C1-C4 linear alkoxy group; And C1 to C4 linear or pulverized aryloxy group, wherein R2 may be the same or different, R3 is hydrogen, phosphorus, fluorine, chlorine or halogen selected from bromine, C1-20 linear or pulverized alkyl group It is a silicon compound containing; M is a transition metal compound of Groups 4, 5 and 6; In this case, when n is 0, it means that two cyclopentadienyl groups are not connected.In this case, R2 is substituted in Cp with 5, and when n is 1, two cyclopentadienyl groups are connected. In this case, four substituted forms of R2 in Cp. In the above R1, the alkylene group of C1 to C4 is selected from the group consisting of methylene group, ethylene group, propylene group and butylene group, and the linear, pulverized or cyclic alkylidene group of C1 to C5 is methylidene group, ethylidene group , Propylidene group, isopropylidene group, phenylmethylidene group and diphenylmethylidene group. In addition, the silicone compound containing a C1 to C5 linear or pulverized alkyl group is selected from the group consisting of dimethylsilylene group, diethylsilylene group, diisopropylsilylene group, diphenylsilylene group, methylethylsilylene group and methylphenylsilylene group The compound containing a zirconium atom containing a C1-C5 linear or crushed alkyl group is selected from the group consisting of an ethylene group, a dimethylsilylene group, and a methylphenylsilylene group. Preferably, C1-C4 alkylene group, C1-C5 linear, crushed or cyclic alkylidene group; Or a silicone compound containing a C1 to C5 straight or crushed alkyl group, more preferably an alkylene group of dimethylene; Alkylidene groups of ethylidene; It is to use a silicone compound of dimethylsilylene. Most preferably, dimethylene and dimethylsilylene are used.

In R2, C1 to C10 linear or pulverized alkyl group is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isobutyl, isopentyl and phenyl, and C1 to C10 substituted with halogen. Linear alkyl groups include chloromethyl, chloroethyl, chloropropyl, chlorobutyl, chloropentyl and the like, and C 1 to C 4 linear alkoxy groups include methoxy, ethoxy, propoxy and butoxy. In addition, C1-C4 linear or crushed aryloxy groups include phenoxy, methylphenoxy, pentamethylphenoxy and the like. Most preferably, they are hydrogen, a C1-C10 linear or pulverized alkyl group, More preferably, it selects and uses from the group which consists of methyl, indenyl, tetrahydroindenyl, and flurenyl. R3 is halogen including hydrogen, phosphorus, fluorine, chlorine, bromine and the like; Silicon-containing compounds such as trimethylsilyl, triethylsilyl and triphenylsilyl; And a C1-20 straight or branched alkyl group, wherein the alkyl group is methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, hexyl, heptyl, octyl nonyl, decyl and phenyl. Most preferably hydrogen, chlorine or methyl group.

M is a Group 4 element consisting of titanium, zirconium and hafnium; A Group 5 element consisting of vanadium, niobium and tantalum; And a group 6 element composed of chromium, molybdenum and tungsten. More preferably titanium, zirconium or hafnium is used.

When the metal (M) of the formula (1) is zirconium, preferred specific compounds are as follows. Examples thereof include methylcyclopentadienyl zirconium dichloride; Ethylcyclopentadienyl zirconium dichloride; Methylcyclopentadienyl zirconium dimethyl; Ethylcyclopentadienyl zirconium dimethyl; Dimethylcyclopentadienyl zirconium dichloride; Tetramethylcyclo zirconium dichloride; Indenyl zirconium dichloride; Dimethylcyclopentadienyl zirconium dimethyl; Trimethylsilyl cyclopentadienyl zirconium dimethyl; Trifluoromethylcyclopentadienyl zirconium dichloride; Isopropylidene indenyl zirconium dichloride; Methylcyclopentadienylcyclopentadienyl zirconium dichloride; Dimethylcyclopentadienylcyclopentadienyl zirconium dichloride; Indecylcyclopentadienyl zirconium dimethyl; Trimethylsilylcyclopentadienyl cyclopentadienyl zirconium dichloride can be used.

Formula (2)

Formula (3)

In the compounds of Formulas (2) and (3), X is independently one selected from oxygen, nitrogen, phosphorus, sulfur, and carbon. R1, R2, R3 are independently halogen, hydroxy, carboxylic acid, sulfonic acid, alkoxy, siloxy hydrocarbon, sulfoxy hydrocarbon, aliphatic hydrocarbon, cycloaliphatic hydrocarbon, aromatic hydrocarbon, alkyl substituted aromatic hydrocarbon, heterocyclic group and in the group At least one selected from derivatives substituted with a hetero element instead of carbon or hydrogen, and R1, R2, R3 may be connected to each other to form a ring, or may not be connected. R4, R5 are halogenated elements of fluorine, chlorine, bromine, iodine, alkoxy, siloxy hydrocarbons, aliphatic hydrocarbons, aromatic hydrocarbons, alkyl substituted aromatic hydrocarbons, heterocyclic groups and derivatives substituted with hetero elements in place of carbon, hydrogen in said groups It is any 1 type selected from any 1 or more types selected from among.

Examples of the alkoxy group in the compounds of the formulas (2) and (3) are any one or more selected from methoxy, ethoxy, propoxy, butoxy, isopropoxy and phenoxy.

Examples of aliphatic hydrocarbons in the compounds of the formulas (2) and (3) are any one or more selected from methyl, ethyl, propyl, butyl, iso-propyl and tert-butyl.

Examples of the alicyclic hydrocarbon group in the compounds of the formulas (2) and (3) are any one or more selected from adamantyl, norbornyl, cyclopentyl, and cyclohexyl.

Examples of the aromatic hydrocarbon group in the compounds of the formulas (2) and (3) are any one or more selected from phenyl, biphenyl, naphthyl, phenanthrenyl, and anthracenyl.

Examples of the alkyl-substituted aromatic hydrocarbon group in the compounds of formulas (2) and (3) include any one or more selected from benzyl, tolyl, mesityl, 2,6-diisopropylphenyl, 2,4,6-trimethyl to be.

Examples of the heterocyclic group in the compounds of the formulas (2) and (3) are any one or more selected from 2-pyridinyl and 2-pyrrolyl.

Suitable substituents for forming a heterosubstituted derivative in the compounds of formulas (2) and (3) are any one or more selected from chloro, bromo, fluorine, and iodo.

Examples of the anion X in the compounds of the formulas (2) and (3) are any one or more selected from chloro, bromo, fluorine, iodo, and methyl groups.

In the compounds of Formulas (2) and (3), M is a metal of Groups 8 to 10 of the periodic table, and is one selected from nickel, cobalt, palladium, and iron.

At least one selected from the organometallic compound catalysts represented by Formulas (1) to (3) is mixed with at least one selected from the above organic solvents, and then mixed with surface treated carbon nanotubes to support the catalyst.

The organometallic compound catalyst supported on the carbon nanotubes is washed five times using at least one selected from the above organic solvents to complete the catalyst support on the surface of the carbon nanotubes.

* Manufacture of Carbon Nanotubes and Polymer Composites

At least one selected from the organometallic compounds of the above-mentioned formulas (1) to (3) in the preparation of the carbon nanotubes and the polymer composite by the in-situ olefin polymerization method by the catalyst supported on the carbon nanotubes of the present invention In order for an organometallic compound to exhibit activity as a catalyst, use of any one or more promoters selected from organoaluminum compounds and organoborone compounds is required.

The monomer as a raw material for preparing the carbon nanotubes and the polymer composite using the in-situ olefin polymerization method using the catalyst supported on the carbon nanotubes may be used as long as the monomer can form a polymer. In the present invention, the olefin monomer is at least one selected from acrylate and its derivatives, α-olefin and its derivatives, styrene and its derivatives, butadiene and its derivatives, ε-carrolactam and its derivatives, and hexamethylenediamine and its derivatives. Can be used.

As one example of the acrylate among the monomers, methyl acrylate (methyl acrylate), methyl methacrylate (methyl methacrylate), tert-butyl acrylate (tert-butyl acrylate) can be used.

Among the monomers, α-olefin includes one or more double bonds in a linear chain hydrocarbon compound, and ethylene and propylene may be used as an example.

The compounds of the formulas (1) to (3) which can be used as catalysts in the preparation of carbon nanotubes and polymer composites using in-situ olefin polymerization by the catalysts supported on carbon nanotubes are mentioned in detail above. The contents will be omitted.

In the preparation of the carbon nanotubes and the polymer composite using the in-situ olefin polymerization method by the catalyst supported on the carbon nanotubes, the promoter may be any one or more selected from an organoaluminum compound and an organic boron compound. As an example of such a promoter, the organoaluminum compound may be methyl aluminoxane (MAO), trimethyl aluminum (TMA), triethyl aluminum (TEA), triiso-butyl aluminum (TIBAL). ), Dimethyl chloro aluminum (DMCA), diethyl chloro aluminum (DECA) can be used any one or more, the organic boron compound is triphenylboron (triphenylboron), trispentafluorophenyl Boron (tris (pentafluoropheneyl) boron), tris (3,5-di (trifluoromethyl) phenyl) boron (tris (3,5-di (trifluoromethyl) phenyl) boron), tetraphenylborate salt, Any one or more selected from tetrakis (pentafluorophenyl) borate salts may be used.

In the preparation of carbon nanotubes and polymer composites using the in-situ monomer polymerization method using a catalyst supported on the carbon nanotubes of the present invention, the monomers are in-situ polymerized in the presence of a catalyst, a promoter and an organic solvent to Polymers can be prepared. As an example of the solvent in the present invention, 1,2-dichlorobenzene, toluene, n-pentane, n-hexane, n-heptane, chlorobenzene, dichloromethane, chloroform, 1,2-dichloroethane or 1,1,2, Any one selected from 2-tetrachloroethane can be used.

Hereinafter, the content of the present invention will be described in detail through examples. However, these are intended to explain the present invention in more detail, and the scope of the present invention is not limited thereto. Meanwhile, in the examples, compounds sensitive to air or water were performed using Schlenk line technology or a glove box.

<Example 1>: Single-walled carbon nanotube surface treatment having a hydroxyl group on the surface

<Example 1a>: Treatment of single-walled carbon nanotubes having a hydroxyl group on the surface with triethyl aluminum

In a 100 mL round bottom flask, 20 mg of single-walled carbon nanotubes containing 3.96 wt% of hydroxy groups on the surface and 10 mL of toluene were added and subjected to ultrasonic vibration at 50 ° C for 1 hour. Again 10 mL of toluene was added and ultrasonic vibration was performed at 50 degrees for 1 hour. Again 10 mL of toluene was added and refluxed for 1 hour. After the temperature was lowered to room temperature, triethylaluminum (0.5 mmol) was added thereto, and the mixture was refluxed for 6 hours. After the temperature was lowered to room temperature, all liquid solutions were removed by filtration, and the reacted carbon nanotubes were washed five times using 50 mL of toluene.

<Example 1b>: Treatment of single-walled carbon nanotubes having a hydroxyl group on the surface with methyl aluminoxane

In a 100 mL round bottom flask, 20 mg of single-walled carbon nanotubes (containing 3.96% by weight of hydroxy group) with hydroxy groups on the surface and 10 mL of toluene were added and subjected to ultrasonic vibration at 50 degrees for 1 hour. Again 10 mL of toluene was added and ultrasonic vibration was performed at 50 degrees for 1 hour. Again 10 mL of toluene was added and refluxed for 1 hour. After lowering the temperature to room temperature, methyl aluminoxane (1 mmol) was added, and the mixture was refluxed for 6 hours. After the temperature was lowered to room temperature, all liquid solutions were removed by filtration, and the reacted carbon nanotubes were washed five times using 50 mL of toluene.

<Example 2>: Supporting organometallic compound catalyst on single-walled carbon nanotubes having a hydroxyl group on the surface

<Example 2a>: Supporting metallocene catalyst on single-walled carbon nanotubes having a hydroxyl group on the surface

30 mL of toluene was added to the surface treated carbon nanotubes obtained in Example 1a. 5 μmol of metallocene (Cp 2 ZrCl 2) dissolved in toluene was added using a syringe into a 100 mL round bottom flask containing carbon nanotubes and toluene. The carbon nanotube, metallocene, and toluene mixed solution was stirred at 50 ° C. for 1 hour. After the temperature was lowered to room temperature, all liquid solutions were removed by filtration, and the metallocene catalyst supported on the carbon nanotubes was washed five times using 50 mL of toluene.

<Example 2b>: Nickel (II) acetylacetonate catalyst supported on a single-walled carbon nanotube having a hydroxyl group on its surface

30 mL of toluene was added to the surface treated carbon nanotubes obtained in Example 1a. 40 μmol of nickel (II) acetylacetonate (Ni (acac) 2) dissolved in toluene was added using a syringe into a 100 mL round bottom flask containing carbon nanotubes and toluene. The carbon nanotube, nickel (II) acetylacetonate, and toluene mixed solution were stirred at 50 ° C. for 1 hour. After the temperature was lowered to room temperature, all liquid solutions were removed by filtration, and the nickel (II) acetylacetonate catalyst supported on carbon nanotubes was washed five times using 50 mL of toluene.

Example 3 Olefin Polymerization Using an Organometallic Compound Catalyst Supported on Carbon Nanotubes

Example 3a: Ethylene Polymerization Using Metallocene Catalyst Supported on Carbon Nanotubes

Addition polymerization of ethylene monomer in the presence of toluene solvent, carbon nanotube supported on carbon nanotube prepared in Example 2a and methyl aluminoxane (catalyst: metallocene catalyst supported on carbon nanotube, monomer pressure: 1.2 atm) , Ratio of methyl aluminoxane (mol) / catalyst (mg) (MAO-mol / catalyst-mg): 1000/1, polymerization time: 30 minutes)

The catalyst (20 mg) supported in Example 2a was added to 30 mL of toluene in a 100 mL round bottom flask, and the ethylene pressure was adjusted to 1.2 atm. The ratio of methyl aluminoxane (MAO) and the catalyst precursor (MAO-mol / catalyst-mg) was set to 1,000: 1, and the polymerization was allowed to proceed for 30 minutes by magnetic stirring at 28 ° C.

Methanol mixed solution to which 10 volume% hydrochloric acid was added was added to the flask in reaction, and the polymerization reaction was complete | finished. The gray solid polymer was collected by filtration through a glass funnel and then dried in a vacuum oven at 100 ° C. for 24 hours to obtain 1.20 g of the polymer. The results are shown in Table 1 below.

<Example 3b>: Methyl methacrylate polymerization using a nickel (II) acetylacetonate catalyst supported on carbon nanotubes

Addition polymerization of a methyl methacrylate monomer in the presence of a toluene solvent, a nickel (II) acetylacetonate catalyst supported on carbon nanotubes prepared in Example 2b and methyl aluminoxane (catalyst: nickel (II) supported on carbon nanotubes) Acetylacetonate catalyst, amount of monomer: 10 mL, ratio of methyl aluminoxane (mol) / catalyst (mg) (MAO-mol / catalyst-mg): 200/1, polymerization time: 24 hours)

30 mL of toluene was added to a 100 mL round bottom flask of the catalyst (20 mg) supported in Example 2b, 10 mL of methyl methacrylate as a monomer was added thereto, and the ratio of methyl aluminoxane (MAO) to the catalyst precursor (MAO). -mol / catalyst-mg) was set to 200: 1, and the polymerization was carried out for 24 hours by magnetic stirring at 28 ° C.

Methanol mixed solution to which 10 volume% hydrochloric acid was added was added to the flask in reaction, and the polymerization reaction was complete | finished. The gray solid polymer was collected by filtration through a glass funnel and then dried in a vacuum oven at 100 ° C. for 24 hours to obtain 2.06 g of the polymer. The results are shown in Tables 1-1 and 1-2 below.

Table 1-1. Polymerization Conditions and Results of Examples 3a and 3b

Example Catalyst Supported on Carbon Nanotubes Polymerization time MAO-mol / catalyst-mg Example 3a Cp2ZrCl2 30 minutes 1,000: 1 Example 3b Ni (acac) 2 24 hours 200: 1

Table 1-2. Polymerization Conditions and Results of Examples 3a and 3b

Example Monomer type Monomer injection Yield (g) Example 3a Ethylene 1.2 atm 1.20 Example 3b Methyl methacrylate 10 mL 2.06

Example 4 Analysis of Carbon Nanotubes and Polymer Composites

<Example 4a>: Analysis of the content of carbon nanotubes in carbon nanotubes and polymer composites by thermogravimetric analysis

The gray carbon nanotubes and polymer composites obtained in Examples 3a and 3b were subjected to thermogravimetric analysis under conditions of starting at room temperature and raising the temperature to 500 ° C. in a nitrogen atmosphere. The content is shown in Table 2 below.

Table 2. Content of carbon nanotubes in the carbon nanotubes and the polymer composite of Examples 3a and 3b

Example Type of polymer Content of Carbon Nanotubes (wt%) Example 3a Polyethylene 1.6 Example 3b Polymethyl methacrylate 1.0

<Example 4b>: Scanning electron microscope analysis

The gray carbon nanotubes and the polymer composites obtained in Examples 3a and 3b were coated with gold in powder form, and then observed by scanning electron microscopy, and are shown in FIGS. 1 and 2 below. FIG. 1 is a scanning electron micrograph of a carbon nanotube and a polyethylene composite magnified 50,000 times, and FIG. 2 is a scanning electron micrograph of a carbon nanotube and a polymethyl methacrylate complex magnified 50,000 times.

<Example 4c>: Measurement of hardness and modulus of elasticity of carbon nanotubes and polymer composites by nano-indentation

The carbon nanotubes and the polymer composites obtained in Examples 3a and 3b were pressed at high temperature, processed into a thin film sample, and hardness and elastic modulus were measured using nanoindentation. Apply Berkovich tip at 0 μN for the first 5 seconds, apply 500 μN of force to the sample, maintain 500 μN for the next 5 seconds, and start at 500 μN for the next 5 seconds It was measured while removing the force to 0 μN, carbon nanotubes and polyethylene samples obtained from pure polyethylene samples and Example 3a, pure polymethyl methacrylate samples, carbon nanotubes and polymethyl methacrylate samples obtained from Example 3b The hardness and modulus of elasticity of are shown in Table 3.

Table 3. Comparison of hardness and elastic modulus using nanoindentation

sample Hardness (GPa) Modulus of elasticity (GPa) Pure polyethylene 0.09 3.08 Example 3a 0.12 3.78 Pure Polymethyl Methacrylate 0.19 4.61 Example 3b 0.33 6.23

Surface treatment of the carbon nanotubes with the functional group of the present invention as shown in Table 1 and after carrying the organometallic compound catalyst was found that the carbon nanotubes and the polymer composite in the presence of a promoter. It can be seen that the composite of the carbon nanotubes and the polymer obtained through FIGS. 1 and 2 is a nanocomposite in which carbon nanotubes are dispersed in nano size. As shown in Table 3, the composite of carbon nanotubes and polyethylene obtained through Example 3a was compared to pure polyethylene, and the composite of carbon nanotubes and polymethyl methacrylate obtained through Example 3b was added to pure polymethyl methacrylate. In comparison, it can be seen that the hardness and the elastic modulus are excellent.

As described above, although described with reference to a preferred embodiment of the present invention, those skilled in the art will be variously modified and modified within the scope of the present invention without departing from the spirit and scope of the invention described in the claims below. It will be appreciated that it can be changed.

As shown in Table 1 above, the present invention may provide a composite of carbon nanotubes and a polymer through an in-situ polymerization of monomers using an organometallic catalyst supported on carbon nanotubes to which functional groups are attached. In addition, the present invention can provide a nanocomposite in which the carbon nanotubes are dispersed in the nano-scale between the polymer through the above Figure 1 and 2, the composite of the carbon nanotube and the polymer provided in the present invention through Table 3 Compared with the pure polymer, it is possible to provide a composite having improved hardness and modulus of elasticity.

Claims

In the production of carbon nanotubes and polymer composites,

A method for producing a polymer composite comprising carbon nanotubes by supporting carbon nanotubes having functional groups on their surfaces in an organometallic catalyst and an organic solvent using an in-situ olefin polymerization method.

The functional group of claim 1, wherein the functional group is a fluorine, chlorine, bromine, iodine, amine, hydroxy group, carboxylic acid, sulfonic acid, alkoxy, siloxy hydrocarbon, sulfoxy hydrocarbon, heterocyclic group, aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, alkyl Phosphorus by a catalyst supported on a carbon nanotube with a functional group substituted with at least one selected from fluorine, chlorine, bromine, iodine, oxygen, sulfur or nitrogen in place of at least one carbon or hydrogen contained in the substituted aromatic hydrocarbon; A method for producing a polymer composite comprising carbon nanotubes using a cet olefin polymerization method.

The catalyst supported on the carbon nanotubes according to claim 1, wherein the alkoxy group in the functional group on the surface of the carbon nanotubes is any one or more selected from methoxy, ethoxy, propoxy, butoxy, isopropoxy or phenoxy. Method for producing a polymer composite containing carbon nanotubes using the in-situ olefin polymerization method.

The aliphatic hydrocarbon according to claim 1, wherein at least one substituted aliphatic hydrocarbon selected from fluorine, chlorine, bromine, iodine, oxygen, sulfur or nitrogen in the functional group on the surface of the carbon nanotube is methyl, ethyl, propyl, butyl, A method for producing a polymer composite comprising carbon nanotubes using an in-situ olefin polymerization method using a catalyst supported on carbon nanotubes by any one or more selected from iso-propyl or tert-butyl.

The alicyclic hydrocarbon group according to claim 1, wherein at least one member selected from fluorine, chlorine, bromine, iodine, oxygen, sulfur or nitrogen is substituted for carbon hydrogen in the functional group on the surface of the carbon nanotubes, adamantyl, norbornyl A method for producing a polymer composite comprising carbon nanotubes using an in-situ olefin polymerization method using a catalyst supported on carbon nanotubes by any one or more selected from cyclopentyl and cyclohexyl.

The aromatic hydrocarbon group according to claim 1, wherein at least one substituted at least one selected from fluorine, chlorine, bromine, iodine, oxygen, sulfur or nitrogen in the functional group on the surface of the carbon nanotube is benzyl, tolyl, mesityl, 2 Method for producing a polymer composite comprising carbon nanotubes using an in-situ olefin polymerization method using a catalyst supported on carbon nanotubes by any one or more selected from 6-diisopropylphenyl or 2,4,6-trimethyl .

The heterocyclic group according to claim 1, wherein at least one member selected from fluorine, chlorine, bromine, iodine, oxygen, sulfur or nitrogen in the functional group on the surface of the carbon nanotube is substituted with 2-pyridinyl or 2-pyridine. A method for producing a polymer composite comprising carbon nanotubes using an in-situ olefin polymerization method by a catalyst supported on carbon nanotubes by any one or more selected from rollyl.

The method of claim 1, wherein the carbon nanotubes comprising the functional groups are single-well carbon nanotubes, double-well carbon nanotubes or multi-well carbon nanotubes. A method for producing a polymer composite comprising carbon nanotubes using an in-situ olefin polymerization method by a catalyst supported on carbon nanotubes by any one or more selected from the following).

The surface treatment of the carbon nanotubes having the functional group of claim 1 is to prepare a polymer composite comprising carbon nanotubes using an in-situ olefin polymerization method by a catalyst supported on carbon nanotubes using an organoaluminum compound or an organic boron compound. Way.

The method of claim 9, wherein the organoaluminum compound is methyl aluminoxane, trimethyl aluminum, triethyl aluminum, triiso-butyl aluminum, dimethyl chloro aluminum, diethyl chloro aluminum, methyl dichloro aluminum, or ethyl dichloro aluminum (ethyl dichloro aluminum) any one or more selected from the catalyst supported on the carbon nanotubes A method for producing a polymer composite comprising carbon nanotubes using an in-situ polymerization method.

The method of claim 9, wherein the organic boron compound is triphenylboron, trispentafluoropheneyl (boron), tris (3,5-di (trifluoromethyl) phenyl) boron (tris ( Carbon nanotubes comprising at least one selected from 3,5-di (trifluoromethyl) phenyl) boron), tetraphenylborate salt, or tetrakis (pentapluorophenyl) borate salt A method for producing a polymer composite comprising carbon nanotubes using an in-situ olefin polymerization method using a catalyst supported thereon.

Using the organoaluminum compound or organic boron compound of claim 9, the organic solvent is tetrahydrofuran, 1,2-dichlorobenzene, toluene, n-hexane (n-hexane). ), n-pentane, n-heptane, n-heptane, chlorobenzene, dichloromethane, chloroform, 1,2-dichloroethane ), 1,1,2,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, N, N-dimethyl formamide, or dimethyl solfoxided A method for producing a polymer composite comprising carbon nanotubes using an in-situ polymerization method using a catalyst supported on one or more carbon nanotubes.

In preparing a polymer composite including carbon nanotubes by carrying out an in-situ polymerization of a monomer by supporting an organometallic catalyst on carbon nanotubes, the organometallic compound catalyst used may be an organometallic compound having a structure represented by the following formula (1): A method for producing a polymer composite comprising carbon nanotubes using an in-situ olefin polymerization method using a catalyst supported on carbon nanotubes using a catalyst.

Formula (1)

In preparing a polymer composite including carbon nanotubes by carrying out an organometallic catalyst on carbon nanotubes and carrying out in-situ polymerization of monomers, the organometallic compound catalyst used is an organometallic compound having the structure of Formula (2) A method for producing a polymer composite comprising carbon nanotubes using an in-situ polymerization method using a catalyst supported on carbon nanotubes using a catalyst.

Formula (2)

In the preparation of a polymer composite including carbon nanotubes by carrying out an organometallic catalyst on carbon nanotubes and in-situ polymerization of monomers, the organometallic compound catalyst used may be an organometallic compound having the structure of Formula (3) A method for producing a polymer composite comprising carbon nanotubes using an in-situ polymerization method using a catalyst supported on carbon nanotubes using a catalyst.

Formula (3)

In the use of any one or more organometallic compounds selected from the organometallic compounds of any one of claims 13 to 15 as a catalyst supporting carbon nanotubes, carbon using an organoaluminum compound or an organic boron compound to be used together A method for producing a polymer composite comprising carbon nanotubes using an in-situ polymerization method using a catalyst supported on a nanotube.

The method of claim 16, wherein the organoaluminum compound is methyl aluminoxane, trimethyl aluminum, triethyl aluminum, triiso-butyl aluminum, dimethyl chloro aluminum. aluminum), diethyl chloro aluminum, methyl dichloro aluminum or methyl dichloro aluminum (ethyl dichloro aluminum) any one or more selected from phosphorus by the catalyst supported on the carbon nanotubes Method for producing a polymer composite containing carbon nanotubes using the CIT polymerization method.

The method of claim 16, wherein the organic boron compound is triphenylboron, trispentafluoropheneyl (boron), tris (3,5-di (trifluoromethyl) phenyl) boron (tris ( 3,5-di (trifluoromethyl) phenyl) boron), tetraphenylborate salt (tetraphenylborate salt) or tetrakis (pentapluorophenyl) borate salt (carbon) characterized in that at least one selected from A method for producing a polymer composite comprising carbon nanotubes using an in-situ polymerization method using a catalyst supported on a nanotube.

In the preparation of carbon nanotubes and polymer composites using an in-situ polymerization method using a catalyst supported on carbon nanotubes, monomers as raw materials include acrylates and derivatives thereof, α-olefins and derivatives thereof, styrene and derivatives thereof, butadiene and Carbon nanotubes using an in-situ polymerization method using a catalyst supported on carbon nanotubes, characterized in that any one or more of the derivatives, ε-carrolactam and derivatives thereof or hexamethylenediamine and derivatives thereof are used. Method for producing a polymer composite comprising.

The method of claim 1, wherein the monomer is any one selected from methyl acrylate, methyl methacrylate or tert-butyl acrylate.