JP4956978B2 - Carbon nanotube-polyolefin composite - Google Patents

Description

  The present invention relates to a carbon nanotube-polyolefin composite containing carbon nanotubes and polyolefin.

  Polyolefins are used as various molding materials in many fields, including home appliance parts, industrial parts, building materials, and household goods. Depending on the required performance of each molding material, polyolefins are compounded with various additives to form composites. It is used as For example, composites in which conductive additives are blended with polyolefins are used for molded products that require electrical conductivity, such as containers for packaging electronic components and radio wave shielding materials. Recently, carbon nanotubes have been used for polyolefins. A melt-kneaded carbon nanotube-polyolefin composite has been proposed (see, for example, Non-Patent Document 1).

Rodney Andrews, David Jacques, Mickael Minot, Terry Rantell, “Fabrication of Carbon Multiwall Nanotube / Polymer Composites by Shear Mixing ”, Macromolecular Materials and Engineering, (Germany), Wiley-VCH, 2002, 287, 6, p. .395-403

However, a carbon nanotube-polyolefin composite obtained by melting and kneading carbon nanotubes in the above-mentioned polyolefin has not been sufficiently satisfactory in terms of conductivity.
Under such circumstances, the problem to be solved by the present invention is to provide a carbon nanotube-polyolefin composite containing carbon nanotubes and polyolefin, which is excellent in conductivity. is there.

  The present invention polymerizes olefin in the presence of a contact-treated product obtained by contact-treating (C) an activation promoter with a contact-treated product obtained by contact-treating (A) a carbon nanotube and (B) an organometallic complex. The present invention relates to a carbon nanotube-polyolefin composite.

  According to the present invention, a carbon nanotube-polyolefin composite containing carbon nanotubes and polyolefin, which is excellent in conductivity, can be provided. In addition, the carbon nanotube-polyolefin composite of the present invention can be excellent in mechanical strength.

  (A) A carbon nanotube (CNT) is a fibrous carbon-based material having a graphene sheet as a constituent element, such as a single-walled carbon nanotube (SWCNT), a double-walled carbon nanotube (DWCNT), or a multi-walled carbon nanotube (MWCNT). One or more of these may be used. Further, as the carbon nanotube (A), a carbon-based material called carbon nanohorn, carbon nanocoil, or cup-stacked carbon nanotube can also be used. Furthermore, the carbon nanotube that can be used in the present invention may be one in which a metal or the like is included in the carbon nanotube, or one that has been subjected to surface modification or modification treatment.

  (A) When the carbon nanotube is a single-walled carbon nanotube, the diameter of the carbon nanotube is usually 10 nm or less, preferably 5 nm or less, more preferably 3 nm or less, and the length of the carbon nanotube is usually 0. .1 to 500 μm, preferably 1 to 100 μm. Further, (A) when the carbon nanotube is a double-walled or multi-walled carbon nanotube, the diameter of the carbon nanotube is usually 1000 nm or less, preferably 100 nm or less, and the length of the carbon nanotube is usually 0.1 to 500 μm. Preferably, it is 1-100 micrometers.

  (A) A carbon nanotube is manufactured by a well-known method, for example, an arc discharge method, a laser vapor deposition method, a vapor phase chemical vapor deposition method, etc. Moreover, as a commercial item, HiPco (trademark) SWCNT by Carbon Nanotechnologies company etc. are mention | raise | lifted.

Examples of (B) organometallic complexes include transition metal compounds represented by the following general formula [1].
L _a MX _b [1]
(In the formula, M represents a transition metal compound, a represents a number satisfying 0 <a ≦ n, b represents a number satisfying 0 <b ≦ n, and n satisfied a valence of the transition metal M. L represents a ligand coordinated to a transition metal, X represents a halogen atom, a hydrocarbon group, or a hydrocarbon oxy group (however, the L ligand is not included), and X is a plurality. In some cases, two or more may be linked, and L and X may be linked.)

  Examples of the ligand L of the general formula [1] include (B1) a ligand having a cyclopentadienyl skeleton and (B2) a ligand having a diimine skeleton.

  Examples of the ligand having a cyclopentadienyl skeleton include a (substituted) cyclopentadienyl group, a (substituted) indenyl group, and a (substituted) fluorenyl group. Specifically, the cyclopentadienyl group, methylcyclo Pentadienyl group, tert-butylcyclopentadienyl group, dimethylcyclopentadienyl group, tert-butyl-methylcyclopentadienyl group, methyl-isopropylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethyl Cyclopentadienyl group, pentamethylcyclopentadienyl group, indenyl group, 4,5,6,7-tetrahydroindenyl group, 2-methylindenyl group, 3-methylindenyl group, 4-methylindenyl group 5-methylindenyl group, 6-methylindenyl group, 7-methylindenyl group Group, 2-tert-butylindenyl group, 3-tert-butylindenyl group, 4-tert-butylindenyl group, 5-tert-butylindenyl group, 6-tert-butylindenyl group, 7-tert -Butylindenyl group, 2,3-dimethylindenyl group, 4,7-dimethylindenyl group, 2,4,7-trimethylindenyl group, 2-methyl-4-isopropylindenyl group, 4,5- Benzindenyl group, 2-methyl-4,5-benzindenyl group, 4-phenylindenyl group, 2-methyl-5-phenylindenyl group, 2-methyl-4-phenylindenyl group, 2-methyl-4-naphthyl Indenyl group, fluorenyl group, 2,7-dimethylfluorenyl group, 2,7-di-tert-butylfluorenyl group, substituted products thereof, And a group in which these are directly linked or linked via a residue containing at least one atom selected from a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. .

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴は水素原子、または炭化水素基を表し、任意に結合して環を形成してもよい。） Examples of the ligand having a diimine skeleton include a ligand represented by the following general formula [2].

(In the formula, R ¹ , R ² , R ³ , and R ⁴ represent a hydrogen atom or a hydrocarbon group, and may be arbitrarily bonded to form a ring.)

Examples of the hydrocarbon group represented by R ¹ and R ^{2 in} the general formula [2] include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. An aryl group such as a phenyl group, a 2-methylphenyl group, and a 2,6-dimethylphenyl group. R ¹ and R ² may be bonded to each other, and examples thereof include a group represented by the following formula.

Examples of the hydrocarbon group represented by R ³ and R ^{4 in} the general formula [2] include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. An aryl group such as phenyl group, 2-methylphenyl group, 2,6-dimethylphenyl group, 2,6-diisopropylphenyl group, 2-isopropylphenyl group, and the like. A 2,6-diisopropylphenyl group is preferred.

  Examples of the transition metal compound M of the general formula [1] include atoms of Group 3 to 11 of the Periodic Table of Elements (IUPAC 1989), and specific examples thereof include scandium atoms, yttrium atoms, titanium atoms, zirconium atoms. , Hafnium atom, vanadium atom, niobium atom, tantalum atom, chromium atom, iron atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom, palladium atom, samarium atom, ytterbium atom and the like. When L is a ligand having a cyclopentadienyl skeleton, M is preferably a Group 3-6 atom, more preferably titanium, zirconium, or hafnium. Further, when L is a ligand having a diimine skeleton, M is preferably a group 8-10 atom, and more preferably nickel, palladium, iron, or cobalt.

  In the general formula [1], a represents a number satisfying 0 <a ≦ n, b represents a number satisfying 0 <b ≦ n, and n represents a number satisfying the valence of the transition metal M. When L is a ligand having a cyclopentadienyl skeleton, it is preferable to satisfy a + b ≦ n. When M is a group 4 atom (titanium atom, zirconium atom, hafnium atom, etc.) or a group 10 atom (nickel atom, palladium atom, etc.) of the periodic table, b is 1 or 2. Preferably there is.

  Specific examples of the halogen atom of X in the general formula [1] include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an isobutyl group, and a tert-pentyl group; an aralkyl group such as a benzyl group; an aryl group such as a phenyl group; An alkenyl group etc. are mention | raise | lifted. The hydrocarbon oxy group includes an alkoxy group such as a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group, an isobutoxy group, a neopentyloxy group, and a tert-pentyloxy group; an aralkyloxy group such as a benzyloxy group. An aryloxy group such as a phenoxy group;

  L and X may be directly connected, and are connected via a residue containing at least one atom selected from a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. May be. Examples of such residues include alkylene groups such as methylene group, ethylene group, propylene group; substituted alkylene groups such as dimethylmethylene group (isopropylidene group) and diphenylmethylene group; silylene group; dimethylsilylene group, diethylsilylene group, Substituted silylene groups such as diphenylsilylene group, tetramethyldisilylene group, dimethoxysilylene group; heteroatoms such as nitrogen atom, oxygen atom, sulfur atom, phosphorus atom and the like, particularly preferably methylene group, ethylene group, dimethylmethylene Group (isopropylidene group), diphenylmethylene group, dimethylsilylene group, diethylsilylene group, diphenylsilylene group or dimethoxysilylene group.

  Examples of organometallic complexes in which L is a ligand having a cyclopentadienyl skeleton include cyclopentadienylzirconium dichloride, bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride, bis (1,3 -N-propylmethylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (1,3-diethylcyclopenta Dienyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (4-methyl-1-indenyl) zirconium dichloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, etc. And the like.

  Examples of the organometallic complex in which L is a ligand having a diimine skeleton include the following compounds.

  (C) The activation cocatalyst includes (c1) an organoaluminum oxy compound, (c2) an ionic compound capable of reacting with an organometallic complex to form an ionic complex, and (c3) a compound group consisting of an organoaluminum compound. The at least 1 sort (s) of compound chosen from these can be mention | raise | lifted.

  (C1) Examples of the organoaluminum oxy compound include tetramethyldialuminoxane, tetraethyldiaminooxane, tetrabutyldialuminoxane, tetrahexyldialuminoxane, methylaluminoxane, ethylaluminoxane, butylaluminoxane, isobutylaluminoxane, hexylaluminoxane, and the like. Mixtures may be used. Examples of commercially available products include PMAO, TMAO, MMAO, and PBAO manufactured by Tosoh Finechem Corporation.

  (C2) Ionic compounds that can react with organometallic complexes to form ionic complexes, tris (pentafluorophenyl) borane, triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis Examples thereof include boron compounds such as (pentafluorophenyl) borate and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

  (C3) Examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, diisobutylhexylaluminum, diisobutyloctylaluminum, isobutyldihexylaluminum, isobutyldioctylaluminum and the like.

  The carbon nanotube-polyolefin composite of the present invention comprises (C) activation in a contact treated product (hereinafter referred to as component (D)) obtained by subjecting (A) carbon nanotubes and (B) an organometallic complex to contact treatment. It is obtained by polymerizing an olefin in the presence of a contact-treated product (hereinafter referred to as contact-treated product (X)) obtained by contact-treating a cocatalyst.

  Examples of the contact treatment between component (A) and component (B) include a method of mixing component (A) and component (B) in the presence of a solvent inert to component (B). Examples of the solvent include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, and octane, aromatic hydrocarbon solvents such as benzene and toluene, and halogenated hydrocarbons such as methylene chloride, and aliphatic hydrocarbons. Or an aromatic hydrocarbon is preferable.

In the contact treatment between component (A) and component (B), the amount of component (B) used is usually 1 × 10 ^{−7 to} 0.1 mol in terms of transition metal atom per 1 g of component (A), Preferably it is 1 * 10 < ^-5 > -0.01 mol.

  The temperature of the contact treatment is usually −50 to 150 ° C. The temperature is preferably 0 ° C. or higher from the viewpoint of increasing conductivity, and preferably 80 ° C. or lower from the viewpoint of increasing polymerization activity. Moreover, the time of a contact process is 1 minute-5 days normally. The time is preferably 10 minutes or more from the viewpoint of increasing the conductivity, and is preferably 1 day or less from the viewpoint of increasing the polymerization activity.

  Examples of the contact treatment of component (D) and component (C) include a method of mixing component (D) and component (C) in the presence of a solvent inert to component (B). Examples of the solvent include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, and octane, aromatic hydrocarbon solvents such as benzene and toluene, and halogenated hydrocarbons such as methylene chloride, and aliphatic hydrocarbons. Or an aromatic hydrocarbon is preferable. When the contact treatment is performed in the presence of a solvent, the concentration of the component (D) in the solution is usually 0.01 to 500 g / L in terms of the component (A).

  In the contact treatment between the component (D) and the component (C), the amount of the component (C) used is the organoaluminum oxy of the component (C) per 1 mol of transition metal atoms derived from the component (B) in the component (D). In terms of the aluminum atom of the compound, the boron atom of the boron compound, or the aluminum atom of the organoaluminum compound, it is usually 0.01 to 10000 mol, preferably 0.1 to 5000 mol, more preferably 1 to 2000 mol.

  The temperature of the contact treatment is usually −50 to 150 ° C., and preferably 0 to 100 ° C. from the viewpoint of increasing the polymerization activity. The time for the contact treatment is usually within 10 hours, and preferably 1 to 60 minutes from the viewpoint of increasing the polymerization activity.

  When olefin polymerization is performed in the presence of the contact treated product (X), the contact treated product (X) obtained by performing contact treatment of each component in advance is supplied to the polymerization reactor to perform olefin polymerization. The components may be supplied to the polymerization reactor, and contact treatment may be performed in the polymerization reactor to polymerize the olefin. For example, (1) component (A) and component (B) are contact-treated, then component (D) obtained by the contact treatment is contact-treated with component (C), and contact-treated product (X) is obtained. A method of preparing in advance and then charging the contact treated product (X) into the polymerization reaction tank. (2) After charging the component (A) and the component (B) into the polymerization reaction tank, the component (C) is added. (3) The component (A) and the component (B) are contact-treated in advance, the component (D) obtained by the contact treatment is charged into the polymerization reaction vessel, and then the component ( C) Method of charging the polymerization reactor, (4) Component (A) and component (B) are contacted in advance, and component (D) obtained by the contact processing is already charged with component (C). And the like, and the like.

  Examples of the olefin to be polymerized in the presence of the contact treated product (X) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, -Dodecene, 4-methyl-1-pentene, 4-methyl-1-hexene and the like can be mentioned, and these may be used alone or in combination of two or more. As the olefin, an olefin having 2 to 12 carbon atoms is preferable.

  Examples of polyolefins produced by the polymerization of olefins in the presence of the contact treated product (X) include ethylene homopolymers, propylene homopolymers, 1-butene homopolymers, 1-hexene homopolymers, 4-methyl- 1-pentene homopolymer, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-octene Copolymer, ethylene-propylene-1-butene copolymer, ethylene-1-butene-1-hexene copolymer, ethylene-1-butene-1-octene copolymer, propylene-1-butene copolymer, Examples thereof include propylene-1-butene-1-hexene copolymer.

  Examples of olefin polymerization methods include known polymerization methods such as slurry polymerization, gas phase polymerization, and bulk polymerization. As the polymerization mode, either batch type or continuous type is possible. The polymerization temperature is usually −78 to 300 ° C., preferably −78 to 100 ° C. The polymerization pressure is usually 0.1 to 350 MPa, preferably 0.1 to 5 MPa. In general, the polymerization time is appropriately determined by a polymerization reactor or the like, but is usually 1 minute to 24 hours. In order to adjust the molecular weight of the polyolefin, a chain transfer agent such as hydrogen may be added.

  In the carbon nanotube-polyolefin composite of the present invention, the content of carbon nanotubes is defined as 100% by weight of the total amount of polyolefin and carbon nanotubes produced by polymerization of olefins in the presence of the contact treated product (X). -From a viewpoint of improving the electroconductivity of a polyolefin composite, Preferably it is 0.01 weight% or more, More preferably, it is 0.1 weight% or more. Further, from the viewpoint of increasing the mechanical strength of the carbon nanotube-polyolefin composite, it is preferably 20% by weight or less, and more preferably 10% by weight or less.

  The carbon nanotube-polyolefin composite of the present invention may contain various additives such as an antioxidant, an antiblocking agent, a lubricant, and a pigment as necessary.

  The carbon nanotube-polyolefin composite of the present invention can be produced by various moldings (for example, extrusion molding methods such as an inflation film molding method and a T-die film molding method, an injection molding method, a compression molding method). Film, sheet, etc.). The obtained molded body is used for various applications, but it is used for the packaging of electronic parts, etc. Antistatic film and molded body, static elimination sheet, personal computer and other household appliance housing materials, thermal conductive film, surface heating element, powder It is suitably used for body transport pipes, radio wave shielding materials and the like.

Hereinafter, the present invention will be described with reference to examples and comparative examples.
The measured value of each item in the examples and comparative examples was measured according to the following method.

(1) Molecular Weight and Molecular Weight Distribution Using a gel permeation chromatography (GPC) method, the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene were measured under the following conditions, and Mw was divided by Mn. The value was defined as molecular weight distribution (Mw / Mn). As a measurement solution, a filtrate obtained by dissolving 5 mg of a sample in 5 ml of orthodichlorobenzene at 140 ° C. and filtering with a fine filter (1000 #) was used.
Equipment: HOS-8121 GPC / HK made by TOSOH
Separation column: TOSOH TSK-gelGMHR-H (20) HD
Measurement temperature: 140 ° C
Carrier: Orthodichlorobenzene Flow rate: 1.0 mL / min Injection volume: 500 μL

(2) Volume resistivity (Ω · cm)
Using a sheet (diameter 6 cm, thickness 0.1 mm) press-molded at 150 ° C., measurement was performed under the following conditions. The smaller this value, the better the conductivity.
Apparatus: HIRESTAIP MCP-HT260 manufactured by Mitsubishi Yuka
Probe: HA
Applied voltage: 10V

<Example 1>
(1) Preparation of carbon nanotube / cyclopentadienylzirconium dichloride / methylaluminoxane contact-treated product Carbon nanotubes dried in a Schlenk tube at 300 ° C. for 2 hours (L-SWCNT manufactured by Shenzhen Nanotechport Co., Ltd .; outer diameter < 2 g, length 5-15 μm) and 20 ml of a cyclopentadienylzirconium dichloride toluene solution having a concentration of cyclopentadienylzirconium dichloride of 0.01 mmol / ml, and stirred at 60 ° C. for 4 hours. And allowed to stand at room temperature for 12 hours. Thereafter, the supernatant was removed, and the mixture was washed twice with 20 ml of toluene. Next, 20 ml of toluene and 5 ml of a toluene solution of methylaluminoxane having a methylaluminoxane concentration of 1 mmol were added and stirred at room temperature for 10 minutes.

(2) Polymerization of olefin The contact-treated product obtained in (1) above was put into a 100 ml autoclave, the autoclave was cooled with liquid nitrogen, and then 7 L of ethylene was introduced into the autoclave. Polymerization was performed for 2 hours to obtain 4.7 g of a carbon nanotube-polyolefin composite. Table 1 shows the evaluation results of the physical properties of the obtained carbon nanotube-polyolefin composite.

<Example 2>
3. Carbon nanotube-polyolefin composite as in Example 1 except that L-MWCNT-4060 (outer diameter 40-60 nm, length 5-15 μm) manufactured by Shenzhen Nanotechport Co., Ltd. was used as the carbon nanotube. 8 g was obtained. Table 1 shows the evaluation results of the physical properties of the obtained carbon nanotube-polyolefin composite.

<Comparative Example 1>
(1) Preparation of contact treated product of cyclopentadienyl zirconium dichloride / methylaluminoxane 20 ml of a toluene solution of cyclopentadienyl zirconium dichloride having a cyclopentadienyl zirconium dichloride concentration of 0.01 mmol / ml is placed in a Schlenk tube. Then, 5 ml of a toluene solution of methylaluminoxane having a methylaluminoxane concentration of 1 mmol was added and stirred at room temperature for 10 minutes.

(2) Polymerization of olefin The contact-treated product obtained in (1) above was put into a 100 ml autoclave, the autoclave was cooled with liquid nitrogen, and then 7 L of ethylene was introduced into the autoclave. Polymerization was performed for 2 hours to obtain 4.3 g of polyethylene. Table 1 shows the evaluation results of the molecular weight and molecular weight distribution of the obtained polyethylene.

(3) Preparation of carbon nanotube-polyolefin composite 0.96 g of polyethylene obtained in (2) above and 0.04 g of carbon nanotube (L-SWCNT manufactured by Shenzhen Nanotechport Co., Ltd.) were used using a biaxial roll kneader. And kneaded to obtain a carbon nanotube-polyolefin composite. Table 1 shows the evaluation results of the volume resistivity of the obtained carbon nanotube-polyolefin composite.

<Comparative example 2>
A carbon nanotube-polyolefin composite was obtained in the same manner as in Comparative Example 1 except that L-MWCNT-4060 (outer diameter 40-60 nm, length 5-15 μm) manufactured by Shenzhen Nanotechport Co., Ltd. was used as the carbon nanotube. It was. Table 1 shows the evaluation results of the volume resistivity of the obtained carbon nanotube-polyolefin composite.

Claims (3)

A carbon nanotube-polyolefin composite containing an olefin polymer and a carbon nanotube, wherein (A) a carbon nanotube and (B) an organometallic complex represented by the following general formula [1] are contact-treated. A carbon nanotube-polyolefin composite obtained by polymerizing an olefin in the presence of a contact-treated product obtained by contact-treating (C) an activation promoter with the contact-treated product,
In the contact treatment between the component (A) and the component (B), the amount of the component (B) used is 1 × 10 ^{−5 to} 0.01 mol in terms of transition metal atom per 1 g of the component (A). Yes,
In the contact treatment between the contact treated product and the component (C), the amount of the component (C) used is the organoaluminum of the component (C) per 1 mol of the transition metal atom derived from the component (B) in the contact treated product. The said carbon nanotube-polyolefin complex which is 0.1-5000 mol in conversion of the aluminum atom of an oxy compound, the boron atom of a boron compound, or the aluminum atom of an organoaluminum compound.

L _a MX _b [1]
(In the formula, M represents an atom belonging to Group 4 of the periodic table. A represents 2 and b represents 2. L represents a ligand having a cyclopentadienyl skeleton . X represents a halogen atom or a hydrocarbon. Group represents a hydrocarbon oxy group (however, the L ligand is not included) X may be linked to each other , and L and X may be linked to each other.
  2. The carbon nanotube-polyolefin composite according to claim 1, wherein the content of the carbon nanotube is 0.01 to 20% by weight, where the total amount of the polyolefin and the carbon nanotube is 100% by weight. A carbon nanotube-polyolefin composite containing an olefin polymer and a carbon nanotube, wherein (A) a carbon nanotube and (B) an organometallic complex represented by the following general formula [1] are contact-treated. A method for producing a carbon nanotube-polyolefin composite, comprising: polymerizing an olefin in the presence of a contact-treated product obtained by contact-treating (C) an activation promoter with the contact-treated product,
In the contact treatment between the component (A) and the component (B), the amount of the component (B) used is 1 × 10 ^{−5 to} 0.01 mol in terms of transition metal atom per 1 g of the component (A). Yes,
In the contact treatment between the contact treated product and the component (C), the amount of the component (C) used is the organoaluminum of the component (C) per 1 mol of the transition metal atom derived from the component (B) in the contact treated product. The said manufacturing method which is 0.1-5000 mol in conversion of the aluminum atom of an oxy compound, the boron atom of a boron compound, or the aluminum atom of an organoaluminum compound.

L _a MX _b [1]
(In the formula, M represents an atom belonging to Group 4 of the periodic table. A represents 2 and b represents 2. L represents a ligand having a cyclopentadienyl skeleton . X represents a halogen atom or a hydrocarbon. Group represents a hydrocarbon oxy group (however, the L ligand is not included) X may be linked to each other , and L and X may be linked to each other.