JP2009120748A - Ethylene based polymer and manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ethylene based polymer excellent in oxidation resistance and heat stability even without addition of a heat stabilizer. <P>SOLUTION: The ethylene based polymer comprises 50-99.9 mol% ethylene unit and 0.1-50 mol% 2-substitution-1-olefin unit and has a molecular weight of 5,000-5,000,000 and a content of an unsaturated bond present in the ethylene based polymer of 0.001 to 0.4 bonds/100C. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an ethylene polymer. More specifically, the present invention relates to an ethylene polymer that is superior in heat stability and oxidation resistance as compared with conventionally known ones.

Ethylene polymers are the most widely used resins in the world. It is said that an ethylene polymer is excellent in oxidation resistance as compared with a propylene resin. This is because tertiary carbon is present in the main chain of polypropylene due to methyl branching, and since the bond energy of the carbon-hydrogen bond existing in this tertiary carbon is low, this bond is cleaved and radicals are generated. Non-Patent Document 1 reports that the reaction that occurs is likely to occur.
On the other hand, an ethylene polymer is generally controlled by copolymerizing with an α-olefin to control the physical properties of the polymer. This copolymerization of ethylene and α-olefin is very effective in controlling physical properties, but tertiary carbon is generated in the main chain. For this reason, the oxidation resistance of the ethylene polymer is deteriorated.

It is also known that an unsaturated bond exists at the polymerization terminal of the ethylene polymer. It is known that this unsaturated bond also becomes an important factor that deteriorates the oxidation resistance.
Usually, a heat stabilizer is added to suppress oxidation of the ethylene-based polymer. However, in some food and functional membrane fields, there is a use in which a heat stabilizer cannot be used from the viewpoint of safety, and there has been a demand for improving the oxidation resistance of ethylene polymers.
By the way, 2-substituted-1-olefin has been conventionally known as a comonomer to be copolymerized with ethylene. However, since this 2-substituted-1-olefin is sterically crowded around the double bond, it is very difficult to copolymerize with ethylene by coordination polymerization. Non-Patent Document 2 describes that 1,1-disubstituted olefins are not polymerized alone and are not copolymerized with other olefins. On the other hand, in the cationic polymerization, the 2-substituted-1-olefin is relatively easily polymerized, but the copolymerization is difficult because ethylene is not easily polymerized.

Regarding the copolymerization of ethylene and isobutylene, Non-Patent Document 3 reported a coordination polymerization. However, since the polymerization temperature and polymerization activity in this reported polymerization are low, it was difficult to carry out industrially. Moreover, there was no report regarding the physical property of the obtained copolymer.
Patent Document 1 discloses a copolymerization technique of ethylene and isobutylene. However, since the temperature in the polymerization of this document is extremely low and the polymerization activity is low, it has been difficult to implement industrially. Moreover, there was no report regarding the physical property of the obtained copolymer.
Patent Document 2 discloses a copolymer of ethylene and a 2-substituted-1-olefin, which contains more than 3.0 mol% of 2-substituted-1-olefin, Since this polymer contains a large amount of terminal unsaturated groups such as terminal vinylidene, it is very effective for use as an additive in petroleum products by functionalization through this terminal unsaturated group. The oxidation resistance was extremely low.

Mechanism of degradation and discoloration of polymer materials and its stabilization technology, Technical Information Association, 2006, p. 21 Encycl. of Polym. Sci. and Eng. Wiley Interscience, 1988, Vol. 8, P., USA. 175 “Isotactic Polymerization of Olefins with Homogeneous Zirconium Catalysts”, W. Kaminsky, A .; Bark, R.A. Spiehl, N .; Moeller-Lindenhof, S.M. Niedoba, Transition Metals and Organometallics as catalysts for Olefin Polymerization, Germany, Springer-Verlag, 1988, p. 291 JP-A-7-2919 JP 2000-511226 A

  This invention is made | formed in view of the above prior arts, and makes it a subject to provide the ethylene-type polymer excellent in oxidation resistance and heat stability even if it does not add a heat stabilizer.

As a result of intensive studies to improve the drawbacks of the prior art, the present inventors have determined that an ethylene-based polymer having a specific amount of a specific comonomer and having a molecular weight, density, terminal vinyl group content, and oxidation induction time within a specific range. The present inventors have found that the coalescence is very excellent in oxidation resistance, and have achieved the present invention.
That is, the present invention
1) An ethylene polymer containing 50 mol% or more and 99.9 mol% or less of ethylene units and 0.1 mol% or more and 50 mol% or less of 2-substituted-1-olefin units, and having a molecular weight of 5,000 or more and 5 million. An unsaturated polymer content in the ethylene polymer is 0.001 / 100C or more and 0.4 / 100C or less, an ethylene polymer,
2) The ethylene-based polymer according to 1), wherein the 2-substituted-1-olefin unit contains 6 or less carbon atoms.
3) The ethylene-based polymer as described in 1) or 2), wherein the retention ratio of the weight average molecular weight measured by oxidation induction time at 210 ° C. is from 50% to 99.9%,

4) At least [A] a solid component having substantially no hydroxyl group, [B] a soluble transition metal compound represented by the following formula (1), [C] a catalytic activity by reacting with the transition metal compound [B] The ethylene-based polymer according to any one of 1) to 3), wherein the ethylene-based polymer is produced by an olefin polymerization solid catalyst formed from an activator compound that forms a metal complex having a hydrogen atom.
L _j W _k MX _p X ′ _q (1)
(In the formula, each L is independently a η bond selected from the group consisting of a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, a tetrahydrofluorenyl group, and an octahydrofluorenyl group. A cyclic anionic ligand, which optionally has 1 to 8 substituents, each of which is independently a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, carbon A halogen-substituted hydrocarbon group having 1 to 12 carbon atoms, an aminohydrocarbyl group having 1 to 12 carbon atoms, a hydrocarbyloxy group having 1 to 12 carbon atoms, a dihydrocarbylamino group having 1 to 12 carbon atoms, and a hydrocarbyl phosphor having 1 to 12 carbon atoms Up to 20 non-chosen selected from the group consisting of a fino group, a silyl group, an aminosilyl group, a hydrocarbyloxysilyl group having 1 to 12 carbon atoms and a halosilyl group Is a substituent having an atom,

M is a transition metal selected from the group of transition metals belonging to Group 4 of the periodic table having a formal oxidation number of +2, +3, or +4, and represents a transition metal bonded to at least one ligand L by η ^5. ,
W is a divalent substituent having up to 50 non-hydrogen atoms, and binds to L and M with a valence of 1 each, thereby synergizing with L and M to perform a metallocycle. Represents a divalent substituent to be formed;
X is each independently a monovalent anionic σ-bonded ligand, a divalent anionic σ-bonded ligand that binds to M bivalently, and L and M each monovalently Represents an anionic σ-bonded ligand having up to 60 non-hydrogen atoms selected from the group consisting of divalent anionic σ-bonded ligands bonded by valence;
X ′ each independently represents a neutral Lewis base coordination compound having up to 40 non-hydrogen atoms;

j is 1 or 2, provided that when j is 2, in some cases two ligands L are bonded to each other via a divalent group having up to 20 non-hydrogen atoms, The valent group is a hydrocarbadiyl group having 1 to 20 carbon atoms, a halohydrocarbadiyl group having 1 to 12 carbon atoms, a hydrocarbyleneoxy group having 1 to 12 carbon atoms, or a hydrocarbyleneamino group having 1 to 12 carbon atoms. A group selected from the group consisting of a silanediyl group, a halosilanediyl group, and a silyleneamino group,
k is 0 or 1,
p is 0, 1 or 2, provided that X is a monovalent anionic σ-bonded ligand or a divalent anionic σ-bonded ligand bonded to L and M , P is an integer 1 or more smaller than the formal oxidation number of M, and when X is a divalent anionic σ-bonded ligand bonded only to M, p is smaller than the formal oxidation number of M ( j + 1) an integer smaller than or equal to
q is 0, 1 or 2),
5) Hydrogen is added to the reactor so as to have a concentration of 10 mol ppm or more and 1 mol% or less during the production of the ethylene-based polymer, and the ethylene-based weight according to any one of 1) to 4) This is a manufacturing method of coalescence.

  According to the present invention, an ethylene polymer having excellent oxidation resistance and excellent thermal stability can be provided.

Hereinafter, the present invention will be described in detail.
First, the ethylene polymer in the present invention will be described. In the present invention, an ethylene polymer is a polymer containing 50 mol% or more of ethylene.
Next, the 2-substituted-1-olefin in the present invention will be described. In the present invention, a 2-substituted-1-olefin is a 1-olefin having a hydrocarbon group at the carbon at the 2-position, determined according to the IUPAC nomenclature. In the present invention, the 2-substituted-1-olefin is represented by the following general formula (2).

式中、Ｒ^１およびＲ^２は独立であり、少なくとも炭素原子１つを含む炭化水素基である。Ｒ^１およびＲ^２は線状、分岐鎖状または環状の、置換または無置換の、炭素原子を１個以上３０個以下、好ましくは１０個以下、さらに好ましくは６個以下を含む炭化水素基である。Ｒ１とＲ２とは結合し、環を形成しても良い。従って、２−置換−１−オレフィンは、２−メチルプロペン等のモノマー類と、上記のマクロマー類の両方を包含する。
Ｒ^１およびＲ^２は本質的には炭化水素基であるが、炭素および水素以外の原子（酸素、硫黄、窒素、リン、ケイ素、ハロゲン、等）の包含は、その触媒による配位重合を妨げないように、かつ炭化水素溶媒に溶解するという本質的に炭化水素基の特徴を保持するために、二重結合から十分に離れているのであれば、許容される。

In the formula, R ¹ and R ² are independent and are hydrocarbon groups containing at least one carbon atom. R ¹ and R ² are linear, branched or cyclic, substituted or unsubstituted hydrocarbon groups containing 1 to 30 carbon atoms, preferably 10 or less, more preferably 6 or less. is there. R1 and R2 may combine to form a ring. Accordingly, 2-substituted-1-olefins include both monomers such as 2-methylpropene and the above macromers.
R ¹ and R ² are essentially hydrocarbon groups, but the inclusion of atoms other than carbon and hydrogen (oxygen, sulfur, nitrogen, phosphorus, silicon, halogen, etc.) hinders their coordinated polymerization. As long as it is sufficiently distant from the double bond in order to retain the inherent hydrocarbon character of being soluble in hydrocarbon solvents.

Examples of the 2-substituted-1-olefin in the present invention include 2-methylpropene (common name isobutylene), 2-methyl-1-butene, 2-methyl-1-pentene, 2-ethyl-1-pentene, and 2-methyl. -1-hexene, 2-methyl-1-heptene, α-methylstyrene, 3-trimethylsilyl-2-methyl-1-propene, and 6- (N, N-dimethylamino) -2-methyl-1-hexene are preferred. .
In the present invention, the content of the 2-substituted-1-olefin unit contained in the ethylene polymer can be controlled by controlling the ratio of ethylene and 2-substituted-1-olefin present in the polymerization system. Specifically, by increasing the proportion of 2-substituted-1-olefin relative to ethylene, the proportion of 2-substituted-1-olefin incorporated into the ethylene polymer can be increased. By reducing the proportion of 2-substituted-1-olefin, it is possible to reduce the proportion of 2-substituted-1-olefin incorporated in the ethylene polymer.

In the present invention, by using a 2-substituted-1-olefin as a comonomer, it is possible to control the mechanical properties by controlling the density of the ethylene-based polymer without generating tertiary carbon in the main chain. Become.
Next, the density of the ethylene polymer in the present invention will be described. In the present invention, the density is a value measured by a density gradient tube method (23 ° C.) according to JIS K7112-1999. This density is a measure of the 2-substituted-1-olefin content of the ethylene-based polymer, and the higher the 2-substituted-1-olefin content, the lower the density of the ethylene-based polymer. In the present invention, the density of the ethylene-based polymer can be controlled by polymerization conditions, and can be controlled by, for example, the concentration of 2-substituted-1-olefin in the polymerization vessel. Specifically, it is possible to reduce the density by increasing the 2-substituted-1-olefin concentration in the polymerization vessel. In the present invention, the 2-substituted-1-olefin concentration in the polymerization vessel is a concentration in the gas phase represented by the following formula.
Gas phase concentration of 2-substituted-1-olefin (mol%) =
Gas phase concentration of 2-substituted-1-olefin (mol / liter) × 100
/ {2-substituted-1-olefin gas phase concentration (mol / liter) + ethylene gas phase concentration (mol / liter)}

The density of the ethylene polymer of the present invention is 940 kg / ^{m 3} or more and 980 kg / ^{m 3} or less, preferably 945 kg / ^{m 3} or more, 975 kg / ^{m 3} or less, more preferably 950 kg / ^{m 3} or more, 970 kg / M ³ or less. In the present invention, if the density of the ethylene-based polymer is 940 kg / m ³ or more, the amount of eluate from the solvent is small and the generation of odor is suppressed. In the present invention, it is technically difficult for the density of the ethylene-based polymer of the present invention to exceed 980 kg / m ³ .
Next, the molecular weight in the present invention will be described. In the present invention, the molecular weight basically indicates a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC). However, when the molecular weight is high and the measurement sample cannot be dissolved and cannot be measured by GPC, the viscosity average molecular weight (Mv) calculated by measuring the intrinsic viscosity of the sample may be referred to as the molecular weight. is there. In the present invention, the Mv of the ethylene polymer is η (dl / g obtained by dissolving ultrahigh molecular weight ethylene copolymer in decalin at different concentrations and extrapolating the solution viscosity obtained at 135 ° C. to a concentration of 0. ) From the following equation 1.
Mv = (5.34 × 10 ⁴ ) × η ^1.49 Expression 1
Next, the oxidation induction time (OIP) in the present invention will be described. In the present invention, OIP is a value measured using DSC. First, after putting a predetermined amount of sample in the DSC measurement aluminum pan, the temperature is set to a predetermined temperature in a nitrogen atmosphere, and then the amount of heat generated when the sample is oxidized in an oxygen atmosphere at the predetermined temperature is measured. At this time, the OIP is measured by calculating the time from when the oxygen atmosphere is reached to when heat starts to be generated. OIP is closely related to the thermal stability and oxidation resistance of the sample, and the longer the OIP, the better the thermal stability and oxidation resistance.

Next, the unsaturated bond content contained in the ethylene polymer in the present invention will be described. In the present invention, the unsaturated bond content is the sum of the terminal vinyl group content, vinylidene group content, and transvinyl group content determined by infrared absorption spectrum. Specifically, the terminal vinyl group content is a value calculated by measuring the absorbance of a peak at 910 cm ⁻¹ of a film prepared by pressing a polymer, according to the following formula. The vinylidene group content is a value calculated by measuring the absorbance at the peak of 888 cm ⁻¹ of a film prepared by pressing a polymer and calculating the following formula. The transvinyl group content is a value calculated by measuring the absorbance at the peak of 963 cm ⁻¹ of a film prepared by pressing a polymer and calculating the following formula.
Terminal vinyl group content (pieces / 100 C) = 0.114 × ΔA ₉₁₀ / (t × d / 1000)
Vinylidene group content (pieces / 100 C) = 0.109 × ΔA ₈₈₈ / (t × d / 1000)
Transvinyl group content (pieces / 100C) = 0.083 × ΔA ₉₆₃ / (t × d / 1000)
{However, the density of d the polymer (kg ^{/ m} 3), the absorbance of the peak of each _{ΔA 910 · ΔA 888 · ΔA 963} 910cm -1 · 888cm -1 · 963cm -1, t is the thickness of the film (mm) In any content, the unit is the number of substituents per 100 carbon atoms contained in the main chain. }

  In the present invention, the unsaturated bond content contained in the ethylene-based polymer is 0.001 / 100C or more and 0.4 / 100C or less, but the smaller the better, the better 0.20.2 / 100C or less. More preferably, it is more preferably 0.1 piece / 100C or less. In the present invention, since tertiary carbon is not present in the ethylene-based polymer, the oxidation resistance is very excellent if the amount of unsaturated bonds is 0.4 / 100C or less. In the case of an ethylene polymer containing tertiary carbon, the oxidation resistance is inferior even if the amount of unsaturated bonds is 0.4 / 100C or less. In the present invention, the non-total bond content contained in the ethylene polymer can be controlled by the type of catalyst used and the polymerization conditions. Regarding the type of catalyst, since a 2-substituted-1-olefin which is difficult to polymerize by coordination polymerization must be copolymerized with ethylene, it is preferable to perform polymerization using a so-called metallocene catalyst.

In the present invention, the oxidation of the ethylene polymer caused by the decomposition of the terminal vinyl group can also be suppressed.
In the present invention, it is preferable to reduce the content of terminal vinyl groups in the ethylene-based polymer by selecting and using a catalyst having a low occurrence frequency of terminal vinyl groups. The copolymerization of ethylene and 2-substituted-1-olefin is preferably carried out using a so-called metallocene catalyst. However, since ordinary metallocene catalysts have a high frequency of terminal vinyl groups, the concentration of terminal vinyl groups in the ethylene polymer is high. There is a risk that will become high. Therefore, among metallocene catalysts, it is preferable to use a catalyst having a low occurrence frequency of terminal vinyl groups.

In the present invention, at least [A] a solid component having substantially no hydroxyl group, [B] a soluble transition metal compound represented by the following formula (1), [C] A solid catalyst for olefin polymerization formed from an activator compound that reacts with the transition metal compound [B] to form a metal complex having catalytic activity is preferred.
L _j W _k MX _p X ′ _q (1)
(In the formula, each L is independently a η bond selected from the group consisting of a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, a tetrahydrofluorenyl group, and an octahydrofluorenyl group. A cyclic anionic ligand, which optionally has 1 to 8 substituents, each of which is independently a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, carbon A halogen-substituted hydrocarbon group having 1 to 12 carbon atoms, an aminohydrocarbyl group having 1 to 12 carbon atoms, a hydrocarbyloxy group having 1 to 12 carbon atoms, a dihydrocarbylamino group having 1 to 12 carbon atoms, and a hydrocarbyl phosphor having 1 to 12 carbon atoms Up to 20 non-chosen selected from the group consisting of a fino group, a silyl group, an aminosilyl group, a hydrocarbyloxysilyl group having 1 to 12 carbon atoms and a halosilyl group Is a substituent having an atom,

M is a transition metal selected from the group of transition metals belonging to Group 4 of the periodic table having a formal oxidation number of +2, +3, or +4, and represents a transition metal bonded to at least one ligand L by η ^5. ,
W is a divalent substituent having up to 50 non-hydrogen atoms, and binds to L and M with a valence of 1 each, thereby synergizing with L and M to perform a metallocycle. Represents a divalent substituent to be formed;
X is each independently a monovalent anionic σ-bonded ligand, a divalent anionic σ-bonded ligand that binds to M bivalently, and L and M each monovalently Represents an anionic σ-bonded ligand having up to 60 non-hydrogen atoms selected from the group consisting of divalent anionic σ-bonded ligands bonded by valence;
X ′ each independently represents a neutral Lewis base coordination compound having up to 40 non-hydrogen atoms;

j is 1 or 2, provided that when j is 2, in some cases two ligands L are bonded to each other via a divalent group having up to 20 non-hydrogen atoms, The valent group is a hydrocarbadiyl group having 1 to 20 carbon atoms, a halohydrocarbadiyl group having 1 to 12 carbon atoms, a hydrocarbyleneoxy group having 1 to 12 carbon atoms, or a hydrocarbyleneamino group having 1 to 12 carbon atoms. A group selected from the group consisting of a silanediyl group, a halosilanediyl group, and a silyleneamino group,
k is 0 or 1,
p is 0, 1 or 2, provided that X is a monovalent anionic σ-bonded ligand or a divalent anionic σ-bonded ligand bonded to L and M , P is an integer 1 or more smaller than the formal oxidation number of M, and when X is a divalent anionic σ-bonded ligand bonded only to M, p is smaller than the formal oxidation number of M ( j + 1) an integer smaller than or equal to
q is 0, 1 or 2.

The solid component [A] having substantially no hydroxyl group used in the present invention is obtained by removing the hydroxyl group from the surface of the solid material [hereinafter referred to as “precursor of component [A]”]. It can be obtained by subjecting to a process for
Examples of the precursor of the component [A] include porous polymer materials (provided that the matrix is, for example, polyethylene, polypropylene, polystyrene, ethylene-propylene copolymer, ethylene-vinyl ester copolymer, styrene-divinylbenzene copolymer) Thermosetting properties such as polymers, polyolefins such as ethylene-vinyl ester copolymer or completely saponified products and modified products thereof, polyamides, polycarbonates, polyesters, thermoplastic resins, phenol resins, epoxy resins, urea resins, melamine resins, etc. Inorganic solid oxides of elements belonging to Groups 2 to 4, 13 or 14 of the periodic table (for example, silica, alumina, magnesia, magnesium chloride, zirconia, titania, boron oxide, calcium oxide, zinc oxide, Barium oxide, vanadium pentoxide, oxidation Lom, thorium oxide, or mixtures or complex oxides thereof thereof), and the like. Examples of composite oxides containing silica include composite oxides of silica and oxides of elements selected from elements belonging to Group 2 or Group 13 of the periodic table, such as silica-magnesia and silica-alumina. It is done. In the present invention, the precursor of component [A] may be selected from silica, alumina, and a composite oxide of silica and an oxide of an element selected from elements belonging to Group 2 or Group 13 of the periodic table. preferable. Of these inorganic solid oxides, silica is particularly preferred.

There is no restriction | limiting in particular regarding the shape of the silica product used as a precursor of component [A], A silica may be arbitrary shapes, such as a granular form, spherical shape, aggregated form, and a fume shape. Preferred examples of commercially available silica products include SD3216.30, SP-9-10046, Syloid ™ 245, Devison 948 or Devison 952 [all above, WR Devison, Inc. (US branch)), Aerosil 812 [Degusa AG (Germany)], ES70X [Crossfield (USA)], P-6 and P-10 [Fuji Silysia (Japan)], etc. Is mentioned.
Of the component [A] used in the present invention, B.I. E. T.A. Specific surface area determined by the (Brunauer-Emmett-Teller) nitrogen adsorption method according is preferably 10~1,000m ² / g, more preferably 100~600m ² / g. One representative example of the component [A] having such a high specific surface area is a component including a porous material having many pores.

In the present invention, the pore volume of the component [A] determined by the nitrogen gas adsorption method is usually preferably 5 cm ³ / g or less, more preferably 0.1 to ³ cm ³ / g, and still more preferably 0.2. ˜2 cm ³ / g.
There is no restriction | limiting in particular regarding the average particle diameter of component [A] used in this invention. The average particle diameter of the component [A] is usually preferably 0.5 to 500 μm, more preferably 1 to 200 μm, and still more preferably 10 to 100 μm.
In the present invention, the component [A] having substantially no hydroxyl group can be obtained by chemically treating the precursor of the component [A] to remove the hydroxyl group from the surface of the precursor of the component [A].
In the present invention, “the solid component has substantially no hydroxyl group” means that no hydroxyl group is detected on the surface of the solid component (component [A]) in the measurement by the method (i) or method (ii) described below. Means.

In method (i), a predetermined excess amount of dialkylmagnesium is added to a slurry obtained by dispersing component [A] in a solvent, the surface hydroxyl group of component [A] is reacted with dialkylmagnesium, and then In order to determine the amount of dialkylmagnesium reacted with the surface hydroxyl group of component [A], the amount of dialkylmagnesium remaining unreacted in the solvent is measured by a known method, and then the reacted dialkylmagnesium Based on the amount, the initial amount of the surface hydroxyl group of component [A] is determined. This method is based on the reaction of a hydroxyl group with a dialkyl magnesium represented by the following reaction formula:
S—OH + MgR ₂ → S—OMgR + RH
(In the formula, S represents a solid material (component [A]), and R represents an alkyl group).
In method (ii), which is more preferred than method (i), ethoxydiethylaluminum is used instead of dialkylmagnesium. Specifically, in the method (ii), ethoxydiethylaluminum was reacted with the surface hydroxyl group of component [A] to generate ethane gas, and the amount of ethane gas generated was measured using a gas burette, and then generated. Based on the amount of ethane gas, the initial amount of the surface hydroxyl group of component [A] is determined.

Furthermore, in the present invention, it is preferable to remove water (crystal water, adsorbed water, etc.) by heat-treating the precursor of component [A]. The heat treatment of the precursor of the component [A] is, for example, in an inert atmosphere or a reducing atmosphere, preferably at a temperature of 150 ° C. to 1,000 ° C., more preferably 250 ° C. to 800 ° C. for 1 hour to 50 ° C. Can be done by processing time.
In the present invention, after dehydrating by heat treatment, the precursor of component [A] is further chemically treated to remove all hydroxyl groups from the surface of the precursor of component [A] to obtain component [A]. More preferred.
Regarding the chemical treatment for removing all of the hydroxyl groups from the precursor of component [A], it is recommended to perform a chemical treatment in which the precursor of component [A] is brought into contact with an organometallic compound. Examples of organometallic compounds used for this chemical treatment include compounds of elements belonging to Groups 2 to 13 of the periodic table. Particularly preferred among these compounds are organoaluminum or organomagnesium.

Examples of preferred organoaluminum compounds used for the chemical treatment of the precursor of component [A] include compounds represented by the following formula (3):
AlR ³ _n X _3-n (3)
(In the formula, each R ³ independently represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms,
Each X independently represents a halide, hydride or alkoxide group having 1 to 10 carbon atoms;
n is 1, 2 or 3.
The compounds represented by the above formula (3) may be used alone or in combination.
Examples of the group R ³ in the formula (3) include methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, phenyl group, tolyl group and the like.
Examples of the group X in the formula (3) include a methoxy group, an ethoxy group, a butoxy group, a hydrogen atom, and a chlorine atom.

Specific examples of organoaluminum compounds used for the chemical treatment of the precursor of component [A] include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, and the like. Reaction products of these trialkylaluminum compounds and alcohols (for example, methyl alcohol, ethyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, octyl alcohol, decyl alcohol) can be mentioned.
Examples of such reaction products include methoxydimethylaluminum, ethoxydiethylaluminum, butoxydibutylaluminum and the like. In the case of producing such a reaction product, the ratio of trialkylaluminum to alcohol is preferably in the range of 0.3 to 20 and in the range of 0.5 to 5 in terms of Al / OH molar ratio. It is more preferable that it is in the range of 0.8-3.

In addition, an organoaluminum oxy compound described later as an example of the component [C] can also be used for chemical treatment of the precursor of the component [A].
As an example of the preferable organomagnesium compound used for the chemical treatment of the precursor of the component [A], a compound represented by the following formula (4) can be given.
MgR ⁴ _n X _2-n (4)
(In the formula, each R independently represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms,
Each X independently represents a halide, hydride or alkoxide group having 1 to 10 carbon atoms;
n is 1 or 2.
The compounds represented by the above formula (4) may be used alone or in combination.
Examples of the group R ⁴ in the formula (4) include methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, phenyl group, tolyl group and the like.
Examples of the group X in the formula (4) include methoxy group, ethoxy group, butoxy group, hydrogen atom, chlorine atom and the like.

Specific examples of the organic magnesium compound used for the chemical treatment of the precursor of component [A] include diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium, butyl octyl magnesium and the like.
When the precursor of component [A] is chemically treated, the organoaluminum compound or organomagnesium compound described above may be used in a mixed state.
When the component [A] is chemically treated to obtain the component [A], the organometallic compound is present in an amount equal to or greater than the molar amount of the hydroxyl group present on the surface of the precursor of the component [A]. Used. The upper limit of the organometallic compound used for the chemical treatment is usually preferably 10 times the molar amount of the hydroxyl group present on the surface of the precursor of component [A], more preferably 5 times the amount, and even more preferably 2 times the amount. The amount is particularly preferably 1.5 times, and most preferably 1.3 times.

In the present invention, the component [A] is particularly preferably silica having substantially no hydroxyl group. The silica is preferably heated at a temperature of 150 ° C. or higher, more preferably 250 ° C. or higher, so that the amount of surface hydroxyl groups is preferably 0.05 to 10 mmol / g of silica. What is obtained by the method of processing with a metal compound is preferable. As the organometallic compound for the treatment of silica [precursor of component [A]], an organoaluminum compound is preferably used, and an organoaluminum compound of the formula (3) is particularly preferably used. The amount of the organoaluminum compound used is preferably 1 to 10 times the molar amount of the surface hydroxyl group of the pretreated silica.
The surface hydroxyl group of the pretreated silica is more preferably 0.1 to 5 mmol, and most preferably 0.5 to 2 mmol, per 1 g of the pretreated silica.

Next, the soluble transition metal compound [B] used in the present invention will be described. Component [B] used in the present invention is an ordinary metallocene catalyst, but is preferably a compound represented by the following formula (1).
L _j W _k MX _p X ′ _q (1)
(In the formula, each L is independently a η bond selected from the group consisting of a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, a tetrahydrofluorenyl group, and an octahydrofluorenyl group. A cyclic anionic ligand, which optionally has 1 to 8 substituents, each of which is independently a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, carbon A halogen-substituted hydrocarbon group having 1 to 12 carbon atoms, an aminohydrocarbyl group having 1 to 12 carbon atoms, a hydrocarbyloxy group having 1 to 12 carbon atoms, a dihydrocarbylamino group having 1 to 12 carbon atoms, and a hydrocarbyl phosphor having 1 to 12 carbon atoms Up to 20 non-chosen selected from the group consisting of a fino group, a silyl group, an aminosilyl group, a hydrocarbyloxysilyl group having 1 to 12 carbon atoms and a halosilyl group Is a substituent having an atom,

M is a transition metal selected from the group of transition metals belonging to Group 4 of the periodic table having a formal oxidation number of +2, +3, or +4, and represents a transition metal bonded to at least one ligand L by η ^5. ,
W is a divalent substituent having up to 50 non-hydrogen atoms, and binds to L and M with a valence of 1 each, thereby synergizing with L and M to perform a metallocycle. Represents a divalent substituent to be formed;
X is each independently a monovalent anionic σ-bonded ligand, a divalent anionic σ-bonded ligand that binds to M bivalently, and L and M each monovalently Represents an anionic σ-bonded ligand having up to 60 non-hydrogen atoms selected from the group consisting of divalent anionic σ-bonded ligands bonded by valence;
X ′ each independently represents a neutral Lewis base coordination compound having up to 40 non-hydrogen atoms;

j is 1 or 2, provided that when j is 2, in some cases two ligands L are bonded to each other via a divalent group having up to 20 non-hydrogen atoms, The valent group is a hydrocarbadiyl group having 1 to 20 carbon atoms, a halohydrocarbadiyl group having 1 to 12 carbon atoms,
A group selected from the group consisting of 12 hydrocarbyleneoxy groups, 1 to 12 hydrocarbyleneamino groups, silanediyl groups, halosilanediyl groups, and silyleneamino groups;
k is 0 or 1,
p is 0, 1 or 2, provided that X is a monovalent anionic σ-bonded ligand or a divalent anionic σ-bonded ligand bonded to L and M , P is an integer 1 or more smaller than the formal oxidation number of M, and when X is a divalent anionic σ-bonded ligand bonded only to M, p is smaller than the formal oxidation number of M ( j + 1) an integer smaller than or equal to
q is 0, 1 or 2. )

Examples of the ligand X in the compound of the above formula (1) include a halide, a hydrocarbon group having 1 to 60 carbon atoms, a hydrocarbyloxy group having 1 to 60 carbon atoms, a hydrocarbylamide group having 1 to 60 carbon atoms, Examples thereof include a hydrocarbyl phosphido group having 1 to 60 carbon atoms, a hydrocarbyl sulfide group having 1 to 60 carbon atoms, a silyl group, and a composite group thereof.
Examples of the neutral Lewis base coordination compound X ′ in the compound of the above formula (1) include phosphine, ether, amine, olefin having 2 to 40 carbon atoms, diene having 1 to 40 carbon atoms, and these compounds. Examples thereof include a derived divalent group.
Examples of the component [B] used in the present invention include compounds represented by the following formula (5).

（式中、Ｒ^５及びＲ^８は、それぞれ独立に炭素数１〜２０の脂肪族炭化水素基又は全炭素数７〜２０の環上に炭化水素基を有する芳香族基、Ｒ^６及びＲ^７は、それぞれ独立に水素原子又は炭素数１〜２０の炭化水素基を示し、Ｒ^６とＲ^７はたがいに結合して環を形成していてもよく、ＸおよびＹは、それぞれ独立にハロゲン原子又は炭素数１〜２０の炭化水素基、Ｍは、ニッケル又はパラジウムを示す。）で表される錯体化合物を挙げることができる。

(In the formula, R ⁵ and R ⁸ are each independently an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic group having a hydrocarbon group on a ring having 7 to 20 carbon atoms, R ⁶ and R ^7. Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ⁶ and R ⁷ may be bonded to each other to form a ring, and X and Y are each independently a halogen atom. Or a hydrocarbon group having 1 to 20 carbon atoms, and M represents nickel or palladium.)

In the general formula (5), the aliphatic hydrocarbon group having 1 to 20 carbon atoms of R ⁵ and R ^8,. 3 to linear or branched alkyl group or carbon number of 1 to 20 carbon atoms 20 cycloalkyl groups, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl Group, decyl group, tetradecyl group, hexadecyl group, octadecyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group and the like. An appropriate substitution difference such as a lower alkyl group may be introduced on the ring of the cycloalkyl group.
The aromatic group having a hydrocarbon group on the ring having 7 to 20 carbon atoms is, for example, a linear or branched chain having 1 to 10 carbon atoms on an aromatic ring such as a phenyl group or a naphthyl group. Examples include a group in which one or more cyclic alkyl groups are introduced. As R ⁵ and R ⁸ , an aromatic group having a hydrocarbon group on the ring is preferable, and a 2,6-diisopropylphenyl group is particularly preferable. R ⁵ and R ⁸ may be the same or different.

The hydrocarbon group having 1 to 20 carbon atoms of ^{R 6} and ^{R 7,} for example, straight-chain or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, carbon atoms A 6-20 aryl group, a C7-20 aralkyl group, etc. are mentioned. Here, as a linear or branched alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms, an aliphatic hydrocarbon group having 1 to 20 carbon atoms among the R ⁵ and R ^8. The same as those exemplified in the description of FIG. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, tolyl group, xylyl group, naphthyl group, and methylnaphthyl group. Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group and phenethyl group. Etc.

R ⁶ and R ⁷ may be the same or different. Further, they may be bonded to each other to form a ring. On the other hand, examples of the halogen atom in X and Y include a chlorine, bromine or iodine atom, and the hydrocarbon group having 1 to 20 carbon atoms is the one having 1 to 20 carbon atoms in R ⁶ and R ⁷ . The hydrocarbon group is as described above. X and Y are particularly preferably a bromine atom or a methyl group. X and Y may be the same or different.
In the present invention, the component [B] is preferably a transition metal compound represented by the formula (1) (where j = 1).
Preferable examples of the compound represented by the formula (1) (where j = 1) include a compound represented by the following formula (6).

（式中、Ｍは、チタン、ジルコニウム及びハフニウムからなる群より選ばれる遷移金属であって、形式酸化数が＋２、＋３または＋４である遷移金属を表し、
Ｒ^９は、各々独立して、水素原子、炭素数１〜８の炭化水素基、シリル基、ゲルミル基、シアノ基、ハロゲン原子及びこれらの複合基からなる群より選ばれる、２０個までの非水素原子を有する置換基を表し、但し、該置換基Ｒ^９が炭素数１〜８の炭化水素基、シリル基またはゲルミル基である時、場合によっては２つの隣接する置換基Ｒ^９が互いに結合して２価の基を形成し、これにより該２つの隣接する該置換基Ｒ^９にそれぞれ結合するシクロペンタジエニル環の２つの炭素原子間の結合と共働して環を形成し、

(Wherein, M represents a transition metal selected from the group consisting of titanium, zirconium and hafnium, and represents a transition metal having a formal oxidation number of +2, +3 or +4,
Each R ⁹ is independently selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a silyl group, a germyl group, a cyano group, a halogen atom, and a composite group thereof; Represents a substituent having a hydrogen atom, provided that when the substituent R ⁹ is a hydrocarbon group having 1 to 8 carbon atoms, a silyl group or a germyl group, in some cases, two adjacent substituents R ⁹ are bonded to each other. To form a ring by cooperating with a bond between two carbon atoms of the cyclopentadienyl ring bonded to each of the two adjacent substituents R ⁹ .

X ″ each independently represents a halide, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 18 carbon atoms, a hydrocarbylamino group having 1 to 18 carbon atoms, a silyl group, or a group having 1 to 18 carbon atoms. Represents a substituent having up to 20 non-hydrogen atoms selected from the group consisting of a hydrocarbyl amide group, a hydrocarbyl phosphide group having 1 to 18 carbon atoms, a hydrocarbyl sulfide group having 1 to 18 carbon atoms, and a composite group thereof; However, in some cases, two substituents X ″ may cooperate to form a neutral conjugated diene having 4 to 30 carbon atoms or a divalent group,
Y ′ represents —O—, —S—, —NR ^* — or —PR ^* —, wherein R ^* is a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a hydrocarbyl having 1 to 8 carbon atoms. Oxy group, silyl group,
A halogenated alkyl group having 1 to 8 carbon atoms, a halogenated aryl group having 6 to 20 carbon atoms, or a composite group thereof;
Z represents _{^{SiR * 2, CR * 2,}} SiR * 2 -SiR * 2, CR * 2 -CR * 2, CR * = CR *, CR * 2 -SiR * 2 or ^GeR _{* 2,} where, ^{R *} Is as defined above and n is 1, 2 or 3.

Specific examples of the component [B] used in the present invention include the following compounds.
Bis (cyclopentadienyl) methylzirconium hydride, bis (cyclopentadienyl) ethylzirconium hydride, bis (cyclopentadienyl) phenylzirconium hydride, bis (cyclopentadienyl) benzylzirconium hydride, bis (cyclopentadienyl) ) Neopentylzirconium hydride, bis (methylcyclopentadienyl) zirconium dimethyl, bis (n-butylcyclopentadienyl) zirconium dimethyl, bis (indenyl) zirconium dimethyl, (pentamethylcyclopentadienyl) (cyclopentadienyl) ) Zirconium dimethyl, bis (cyclopentadienyl) zirconium dimethyl, bis (pentamethylcyclopentadienyl) zirconium dimethyl, bis ( Clopentadienyl) zirconium diphenyl, bis (cyclopentadienyl) zirconium dibenzyl, bis (cyclopentadienyl) zirconium dihydride, bis (fluorenyl) zirconium dimethyl, ethylenebis (indenyl) zirconium dimethyl, ethylenebis (indenyl) Zirconium diethyl, ethylenebis (indenyl) zirconium dihydride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dimethyl, ethylenebis (4-methyl-1-indenyl) zirconium dimethyl, ethylenebis (5 -Methyl-1-indenyl) zirconium dimethyl, ethylenebis (6-methyl-1-indenyl) zirconium dimethyl, ethylenebis (7-methyl-1-indenyl) zyl Nitrodimethyl, ethylenebis (5-methoxy-1-indenyl) zirconium dimethyl, ethylenebis (2,3-dimethyl-1-indenyl) zirconium dimethyl, ethylenebis (4,7-dimethyl-1-indenyl) dimethylzirconium, ethylene Bis- (4,7-dimethoxy-1-indenyl) zirconium dimethyl, methylene bis (cyclopentadienyl) zirconium dihydride, methylene bis (cyclopentadienyl) zirconium dimethyl, isopropylidene (cyclopentadienyl) zirconium dihydride, isopropyl Liden (cyclopentadienyl) zirconium dimethyl, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dihydride, isopropylidene (cyclopentadienyl-fluorene) Nyl) zirconium dimethyl, silylene bis (cyclopentadienyl) zirconium dihydride, silylene bis (cyclopentadienyl) zirconium dimethyl, dimethylsilylene (cyclopentadienyl) zirconium dihydride, dimethylsilylene (cyclopentadienyl) zirconium dimethyl, (Nt-Butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl] titanium dimethyl, [(Nt-butyramide) (tetramethyl-η ⁵ -cyclopentadienyl) dimethyl Silane] titanium dimethyl, [(N-methylamido) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilane] titanium dimethyl, [(N-phenylamido) (tetramethyl-η ⁵ -cyclopentadie Nyl) dimethylsilane] titanium dimethyl, [(N-benzylamide) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilane] titanium dimethyl, [(Nt-butylamide) (η ⁵ -cyclopentadienyl) -1,2-ethanediyl] titanium dimethyl, [(Nt-butylamide) (η ⁵ -cyclopentadienyl) dimethylsilane] titanium dimethyl, [(N-methylamide) (η ⁵ -cyclopentadienyl) -1 , 2-ethanediyl] titanium dimethyl, [(N-methylamido) (η ⁵ -cyclopentadienyl) dimethylsilane] titanium dimethyl, [(Nt-butylamido) (η ⁵ -indenyl) dimethylsilane] titanium dimethyl, (N-benzylamide) (η ⁵ -indenyl) dimethylsilane ] Titanium dimethyl and the like.

Specific examples of the component [B] used in the present invention include the “dimethyl” part of the names of the zirconium and titanium compounds listed above as specific examples of the component [B] (this is the name of each compound). The last part, that is, the part appearing immediately after the part of “zirconium” or “titanium”, which is the name corresponding to the part of X ″ in the formula (6), is any of the following: Also included are compounds with names that can be substituted for.
“Dibenzyl”, “2- (N, N-dimethylamino) benzyl”, “2-butene-1,4-diyl”, “s-trans-η ⁴ -1,4-diphenyl-1,3-butadiene” , “S-trans-η ⁴ -3-methyl-1,3-pentadiene”, “s-trans-η ⁴ -1,4-dibenzyl-1,3-butadiene”, “s-trans-η ⁴ -2” , 4-hexadiene, "" s- trans eta ⁴ -1,3-pentadiene "," s- trans eta ^{4-1,4-ditolyl-1,3-butadiene,} "" s- trans eta ⁴ - 1,4-bis (trimethylsilyl) -1,3-butadiene ”,“ s-cis-η ⁴ -1,4-diphenyl-1,3-butadiene ”,“ s-cis-η ⁴ -3-methyl-1 ” , 3-pentadiene ”,“ s-cis-η ⁴ -1,4-dibenzyl ”. -1,3-butadiene "," s-cis-η ⁴ -2,4-hexadiene "," s-cis-η ⁴ -1,3-pentadiene "," s-cis-η ⁴ -1,4- “Ditolyl-1,3-butadiene”, “s-cis-η ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene” and the like.

The transition metal compound [B] used in the present invention can be synthesized by a generally known method. Examples of a preferable synthesis method of the transition metal compound used as component [B] in the present invention include the method disclosed in US Pat. No. 5,491,246.
In the present invention, these transition metal compound components [B] may be used alone or in combination.
Next, the activator compound [C] capable of reacting with the transition metal compound [B] to form a metal complex having catalytic activity in the present invention will be described.
Examples of the component [C] include an organoaluminum oxy compound. The preferred organoaluminum oxy compound used in the present invention can be produced, for example, by the following method and is usually obtained as a solution in a hydrocarbon solvent.

(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the above suspension of the hydrocarbon medium.
(2) A method of allowing water, ice or water vapor to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.
The organoaluminum oxy compound may contain a small amount of an organometallic component. Further, after removing the solvent or the unreacted organoaluminum compound by distillation from the recovered solution of the organoaluminum oxy compound, it may be redissolved in a solvent or suspended in a poor solvent of the organoaluminum oxy compound.

Specific examples of the organoaluminum compound used in preparing the organoaluminum oxy compound include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butylaluminum, Tri-tert-butylaluminum,
Trialkylaluminum such as tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diisobutylaluminum Dialkylaluminum halides such as chloride, dialkylaluminum hydride such as diethylaluminum hydride and diisobutylaluminum hydride, dialkylaluminum alkoxide such as dimethylaluminum methoxide and diethylaluminum ethoxide, and dialkylaluminum such as diethylaluminum phenoxide Aryloxide, and the like.

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.
In addition, examples of the component [C] include clay, clay minerals, and ion-exchangeable layered compounds. In this case, the organoaluminum compound represented by the above formula (3) is preferably used at the same time. At this time, trialkylaluminum is preferably used.
The clay used in the present invention is usually preferably composed mainly of a clay mineral, and the ion-exchangeable layered compound has a crystal structure in which the surfaces constituted by ionic bonds and the like are stacked in parallel with a weak binding force. A compound that can be exchanged is preferable. Examples of the clay, clay mineral, or ion-exchangeable layered compound include ionic crystalline compounds having a layered crystal structure such as a hexagonal close packing type, an antimony type, a CdCl ₂ type, and a CdI ₂ type. These clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used.

Specific examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, Naclite, dickite, halloysite and the like can be mentioned. Examples of the ion exchange layered compound include α-Zr (HAsO ₄ ) ₂ .H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ .3H. ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti Examples thereof include crystalline acidic salts of polyvalent metals such as (HPO ₄ ) ₂ and γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O.
Such clays, clay minerals, and ion-exchange layered compounds are preferably those having a pore volume of 0.1 cm ³ / g or more with a radius of 2 nm or more measured by a mercury intrusion method from the viewpoint of polymerization activity. Those of ˜5 cm ³ / g are particularly preferred. Here, the pore volume is measured by a mercury intrusion method using a mercury porosimeter in the range of 2 to 3 × 10 ³ nm as the pore radius.

The clay and clay mineral used in the present invention can be subjected to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of the clay can be used. Specifically, acid treatment, alkali treatment, salt treatment, organic matter treatment and the like can be mentioned. In addition to removing impurities on the surface, the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic matter treatment, an ion complex, a molecular complex, an organic derivative, and the like can be formed, and the surface area and interlayer distance can be changed.
The ion-exchangeable layered compound used in the present invention can also obtain a layered compound in a state where the layers are expanded by exchanging the exchangeable ions between the layers with other large and bulky ions, utilizing the ion-exchangeability. . Here, the bulky ions play a pillar-like role to support the layered structure and are called pillars. Introducing another substance (guest compound) between layers of a layered substance is called intercalation.

Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ ; Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , B (OR) ₃ , and R (carbonized) Metal alcoholates such as hydrogen groups; metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , and [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ Is mentioned. These compounds may be used alone or in combination of two or more.
In addition, when intercalating these compounds, obtained by hydrolyzing metal alcoholates such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group, etc.) Polymers, colloidal inorganic compounds such as SiO _2, and the like can also coexist. Other examples of pillars include oxides generated by heat dehydration after intercalation of the hydroxide ions between layers.
The clay, clay mineral, and ion-exchangeable layered compound used in the present invention may be used as they are, or after being subjected to treatment such as pulverization and sieving with a ball mill. Further, it may be used after water is newly added and adsorbed, or after heat dehydration treatment. Furthermore, you may use individually or in combination of 2 or more types. Among these, preferred is clay or clay mineral, and particularly preferred is montmorillonite.

Furthermore, examples of the component [C] include compounds defined by the following general formula (7).
[L−H] ^{d +} [M _m Q _p ] ^d− (7)
In the formula, [L—H] ^{d +} is a proton-providing Bronsted acid, and L is a neutral Lewis base.
[M _m Q _p ] ^d- is a compatible non-coordinating anion, M is a metal or metalloid selected from Groups 5 to 15 of the periodic table, and Q is independently A hydride, a dialkylamide group, a halide, an alkoxide group, an allyloxide group, a hydrocarbon group, a substituted hydrocarbon group having up to 20 carbon atoms, and Q as a halide is 1 or less. M is an integer from 1 to 7, p is an integer from 2 to 14, d is an integer from 1 to 7, and pm = d.

In the present invention, a preferred example of the component [C] is represented by the following general formula (8).
_{[M m Q n (G q} (T-H) r) z] d- (8)
M is a metal or metalloid selected from Groups 5 to 15 of the periodic table. Q is as defined in the general formula (7), G is a polyvalent hydrocarbon group having a valence of r + 1 bonded to boron and T, T is O, S, NR, or PR, Here, R is hydrocarbyl, trihydrocarbylsilyl group, trihydrocarbylgermanium group, or hydrogen. Moreover, m is an integer of 1-7, n is an integer of 0-7, q is an integer of 0 or 1, r is an integer of 0-3, z is an integer of 1-8. Yes, d is an integer of 1 to 7, and n + z−m = d. A more preferred example of the component [C] of the present invention is represented by the following general formula (9).
[L-H] ⁺ [BQ ₃ Q] ⁻ (9)
In the formula, [L—H] ⁺ is a proton-providing Bronsted acid, and L is a neutral Lewis base. In the formula, [BQ ₃ Q ′] ⁻ is a compatible non-coordinating anion, Q is a pentafluorophenyl group, and the remaining one Q ′ has 6 carbon atoms having one OH group as a substituent. To 20 substituted aryl groups.

Specific examples of the compatible non-coordinating anion of the present invention include, for example, tetrakisphenyl borate, tri (p-tolyl) (phenyl) borate, tris (pentafluorophenyl) (phenyl) borate, tris (2,4 -Dimethylphenyl) (hydrphenyl) borate, tris (3,5-dimethylphenyl) (phenyl) borate, tris (3,5-di-trifluoromethylphenyl) (phenyl) borate, tris (pentafluorophenyl) (cyclohexyl) Borate, tris (pentafluorophenyl) (naphthyl) borate, tetrakis (pentafluorophenyl) borate, triphenyl (hydroxyphenyl) borate, diphenyl-di (hydroxyphenyl) borate, triphenyl (2,4-dihydroxyphenyl) volley , Tri (p-tolyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) (hydroxyphenyl) borate, tris (2,4-dimethylphenyl) (hydroxyphenyl) borate, tris (3,5-dimethylphenyl) ( Hydroxyphenyl) borate, tris (3,5-di-trifluoromethylphenyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) (2-hydroxyethyl) borate, tris (pentafluorophenyl) (4-hydroxybutyl) Borate, tris (pentafluorophenyl) (4-hydroxy-cyclohexyl) borate, tris (pentafluorophenyl) (4- (4′-hydroxyphenyl) phenyl) borate, tris (pentafluorophenyl) (6-hydride) Carboxymethyl-2-naphthyl) borate, and the like, most preferably tris (pentafluorophenyl) (4-hydroxyphenyl) include borate.

Examples of other preferred compatible non-coordinating anions include borates in which the hydroxy group of the borate exemplified above is replaced with an NHR group. Here, R is preferably a methyl group, an ethyl group or a t-butyl group. Specific examples of the proton-providing Bronsted acid of the present invention include, for example, triethylammonium, tripropylammonium, tri (n-butyl) ammonium, trimethylammonium, tributylammonium, and tri (n-octyl) ammonium. And trialkyl group-substituted ammonium cations such as N, N-dimethylanilinium, N, N-diethylanilinium, N, N-2,4,6-pentamethylanilinium, N, N- Also suitable are N, N-dialkylanilinium cations such as dimethylbenzylanilinium and the like.
Furthermore, dialkylammonium cations such as di- (i-propyl) ammonium and dicyclohexylammonium are also suitable, such as triphenylphosphonium, tri (methylphenyl) phosphonium, tri (dimethylphenyl) phosphonium and the like. Such triarylphosphonium cations or dimethylsulfonium, diethylfuronium, diphenylsulfonium and the like are also suitable.

In the present invention, these activator compound components [C] may be used alone or in combination.
In the present invention, the amount of each component used and the ratio of the amounts used are not particularly limited, but it is preferable to use a sufficient amount of component [C] for the reaction of component [B].
In the present invention, component [B] is preferably used in an amount of 5 × 10 ⁻⁶ to 10 ⁻² mol, more preferably 10 ⁻⁵ to 10 ⁻³ mol, relative to 1 g of component [A].
When the components [A], [B] and [C] are brought into contact with each other, depending on the conditions, a partially unreacted component [B] may be present in the reaction solvent, and the component [B] is a soluble solvent. Removal of the unreacted component [B] is performed by a method of washing using a method, a method of heating and / or decompressing, or the like.

Further, the unsaturated bond content of the ethylene polymer can be controlled by the polymerization conditions. For example, it is possible to reduce the unsaturated bond content of the ethylene polymer by lowering the polymerization temperature and / or increasing the hydrogen concentration in the polymerization vessel. Specifically, the lower the polymerization temperature, the higher the molecular weight and the lower the unsaturated bond content. Further, the higher the hydrogen concentration in the polymerization vessel, the lower the molecular weight and the lower the unsaturated bond content. Therefore, when producing an ethylene polymer having the same molecular weight, the polymerization temperature is lowered and the hydrogen concentration is raised to lower the unsaturated bond content, the polymerization temperature is raised, and the hydrogen concentration is lowered. Thus, the unsaturated bond content can be increased.
In the present invention, the ethylene polymer is preferably produced at a hydrogen concentration in the polymerization vessel of 10 mol ppm to 1 mol%. If the hydrogen concentration is 10 mol ppm or more, industrially stable operation is possible, and if it is 1 mol% or less, an ethylene polymer having an appropriate molecular weight region can be produced.

In the present invention, the polymerization temperature is not particularly limited, but is preferably 0 ° C. or higher and 200 ° C. or lower, more preferably 20 ° C. or higher and 130 ° C. or lower, and 40 ° C. or higher and 90 ° C. or lower. Further preferred. When the temperature is 0 ° C. or higher, industrially sufficient polymerization activity can be expressed, and the heat removal of the polymerization vessel can be stably performed. When the temperature is 200 ° C. or lower, the unsaturated bond content Can be controlled. By lowering the polymerization temperature, it is possible to increase the molecular weight of the ethylene polymer to be produced, and to increase the hydrogen concentration here to adjust the molecular weight to an appropriate range.
Next, a specific embodiment in which the polymerization of ethylene is performed in the presence of the catalyst of the present invention will be described.
The density and physical properties of the ethylene polymer can be controlled by copolymerization of ethylene and 2-substituted-1-olefin. The polymerization of olefins according to the present invention can be carried out either by suspension polymerization or gas phase polymerization. In the suspension polymerization method, an inert hydrocarbon medium can be used as a suspension polymerization medium, and the olefin itself can also be used as a solvent.
Specific examples of the inert hydrocarbon medium include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic rings such as cyclopentane, cyclohexane, and methylcyclopentane. Aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethyl chloride, chlorobenzene and dichloromethane, or mixtures thereof.

The amount of the catalyst feed in the polymerization of ethylene using the olefin polymerization catalyst of the present invention is, for example, 1 wt% to 0.001 wt% of the catalyst with respect to the weight of the polymer obtained per hour. It is desirable to adjust the catalyst concentration in the polymerization system. The polymerization temperature is usually preferably 0 ° C. or higher, more preferably 50 ° C. or higher, further preferably 60 ° C. or higher, and 150 ° C. or lower, more preferably 110 ° C. or lower, more preferably 100 ° C. or lower. It is a range. The polymerization pressure is usually preferably from normal pressure to 10 MPa, more preferably from 0.2 to 5 MPa, and even more preferably from 0.5 to 3 MPa. The polymerization reaction can be carried out batchwise, semi-continuously, or continuously. Any method can be used. It is also possible to carry out the polymerization in two or more stages having different reaction conditions.
Furthermore, the molecular weight of the resulting olefin polymer can also be adjusted, for example, by the presence of hydrogen in the polymerization system or by changing the polymerization temperature, as described in DE 31 17 133.2. In the present invention, the olefin polymerization catalyst may contain other components useful for olefin polymerization in addition to the above components.
Next, the present invention will be described more specifically based on examples and reference examples, but the present invention is not limited to these examples.

[Measurement of melt flow rate]
The melt flow rate (MFR) was measured according to JIS K7210-1999, code D.
[Density measurement]
The density of the polymer was measured by a density gradient tube method (23 ° C.) in accordance with JIS K7112-1999.
[Measurement of 2-substituted-1-olefin content]
Measurement of olefin content {x (mol%)} J. et al. This was performed according to the method disclosed in Ray et al., Macromolecules, 10, 773 (1977), and x was calculated from the area intensity using a signal of methylene carbon observed by a ¹³ C-NMR spectrum. The equipment used was Lambda-400 manufactured by JEOL. The solvent used was o-orthodichlorobenzene-d ₄ , the measurement temperature was 140 ° C., and the observation frequency was 100 MHz ( ^1
3 C), pulse width 45 ° (7.5μsec), accumulation number was 10,000 times. The measurement standard was PE (-eeee-) signal, which was 29.9 ppm.

[Measurement of weight average molecular weight (Mw)]
The apparatus used for the measurement was GPC-2000 manufactured by Waters. The columns used were one Showex D-Shadex AT-807S and two Tosoh TSK-GELGMH-H (S), first through one Shodex AT-807S, then two Used in series connected through TSK-GELGMH-H (S). 1,2,4-Trichlorobenzene containing 10 mass ppm of pentaerythrityl tetrakis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] was used as the mobile phase solvent. The measurement temperature was 140 ° C. The mobile phase solvent flow rate was 1.0 milliliters / minute. The measurement sample was prepared by adding 20 ml of 1,2,4-trichlorobenzene to 20 mg of polymer, dissolving at 145 ° C. for 2 hours, and passing through a 0.5 μm sintered filter. The number average molecular weight (Mn) is 0.43 (polyethylene Q factor / polystyrene Q factor) using a calibration curve prepared using a monodisperse polystyrene manufactured by Tosoh Corporation as a standard substance. = 17.7 / 41.3). The weight average molecular weight (Mw) is 0.43 (polyethylene Q factor / polystyrene Q factor) using a calibration curve prepared using monodispersed polystyrene manufactured by Tosoh Corporation as a standard substance. = 17.7 / 41.3).

[Measurement of unsaturated bond content]
The unsaturated bond content contained in the polymer was measured by the following method.
1 g of the polymer was placed in a mold of length × width × thickness 5 cm × 5 cm × 0.5 mm placed on a 0.2 mm aluminum plate, and the aluminum plate was placed and pressed at 180 ° C. to form a film. The infrared absorption spectrum of this film was measured using FT-IR5300A manufactured by JASCO Corporation. The terminal vinyl group content was calculated according to the following formula by measuring the absorbance at the peak of 910 cm ⁻¹ of the film prepared by pressing the polymer. The vinylidene group content was calculated according to the following formula by measuring the absorbance at the peak of 888 cm ⁻¹ of the film prepared by pressing the polymer. The transvinyl group content was calculated according to the following equation by measuring the absorbance at the 963 cm ⁻¹ peak of the film prepared by pressing the polymer. The total content of these three functional groups was taken as the unsaturated bond content.
Terminal vinyl group content (pieces / 100 C) = 0.114 × ΔA ₉₁₀ / (t × d / 1000)
Vinylidene group content (pieces / 100 C) = 0.109 × ΔA ₈₈₈ / (t × d / 1000)
Transvinyl group content (pieces / 100C) = 0.083 × ΔA ₉₆₃ / (t × d / 1000)
{However, the density of d the polymer (kg ^{/ m} 3), the absorbance of the peak of each _{ΔA 910 · ΔA 888 · ΔA 963} 910cm -1 · 888cm -1 · 963cm -1, t is the thickness of the film (mm) In any content, the unit is the number of substituents per 100 carbon atoms contained in the main chain. }

[Measurement of Mw and Mw retention after measurement of oxidation induction time (OIP) at 210 ° C.]
First, OIP was measured at 210 ° C. DSC-50 (manufactured by Shimadzu Corporation) was used for the measurement. 10 mg of the sample was put in an aluminum pan for DSC measurement (aluminum sample pan kit manufactured by PerkinElmer). This was set on the right side of the furnace of DSC-50, and an aluminum pan containing 10 mg of aluminum oxide was set on the left side of the furnace. The inner lid was closed, the protective cover was lowered, and the furnace was left in a nitrogen atmosphere for 5 minutes. Thereafter, the measurement temperature was set to 210 ° C. and measurement was started. The heating rate was 99.9 ° C./min. The sampling interval during measurement was set to 0.8 seconds. After 7 minutes, the nitrogen was switched to oxygen to oxidize the sample. It passes through a point on the chart when nitrogen is switched to oxygen, a straight line with the slope of the chart at that point, the chart rises, passes through the inflection point before passing the first peak, and at that inflection point OIP was measured by calculating the time of intersection with a straight line having the slope of the chart.
A sample after the OIP measurement was taken out, and Mw after the OIP measurement was measured by the same operation as the GPC measurement. The Mw retention was calculated by dividing Mw after OIP measurement by Mw before OIP measurement. A higher Mw retention is considered to be superior in oxidation resistance and thermal stability.

[Reference Example 1]
Silica P-10 [manufactured by Fuji Silysia Ltd. (Japan)] was calcined at 400 ° C. for 5 hours in a nitrogen atmosphere and dehydrated. The amount of surface hydroxyl groups of dehydrated silica was 1.29 mmol / g-SiO ₂ . 5 kg of this dehydrated silica was dispersed in 100 liters of hexane in a stainless steel autoclave having an internal volume of 200 liters to obtain a slurry. While maintaining the resulting slurry at 50 ° C. with stirring, 7.5 liters of a hexane solution of triethylaluminum (concentration 1M) was added, and then stirred for 2 hours to react triethylaluminum with the surface hydroxyl group of silica to be treated with triethylaluminum. The carrier (A-1) containing all the surface hydroxyl groups of the silica treated with triethylaluminum was obtained. Thereafter, the supernatant liquid in the obtained reaction mixture was removed by decantation to remove unreacted triethylaluminum in the supernatant liquid. Thereafter, an appropriate amount of hexane was added to obtain 100 liters of a silica hexane slurry treated with triethylaluminum.

  457 g of bis (hydrogenated tallow alkyl) methylammonium-tris (pentafluorophenyl) (4-hydroxyphenyl) borate (hereinafter abbreviated as “borate”) was added to 5 liters of toluene to dissolve, and a borate 100 mM toluene solution Got. 400 ml of a 1M hexane solution of ethoxydiethylaluminum was added to this toluene solution of borate at 25 ° C., and further hexane was added so that the borate concentration in the toluene solution was 70 mM. Then, it stirred at room temperature for 1 hour and obtained the reaction mixture (C-1) containing a borate.

400 mmol of [(Nt-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilane] titanium-1,3-pentadiene (hereinafter referred to as “titanium complex”) was added to Isopar E [Exxon Chemical Company (USA) 1) hexane of general formula AlMg ₆ (C ₂ H ₅ ) ₉ (n-C ₄ H ₉ ) ₆ dissolved in 4 liters and previously synthesized from triethylaluminum and butylethylmagnesium 20 ml of the solution was added, and further hexane was added to adjust the titanium complex concentration to 0.1 M, to obtain a transition metal compound (B-1).
The total amount of this reaction mixture (C-1) containing borate was added to the carrier (A-1) slurry obtained above with stirring at 15 ° C., and the borate was supported on silica by physical adsorption.
Thus, a slurry of silica carrying borate was obtained. Further, the entire amount of the transition metal compound (B-1) obtained above was added, and the mixture was stirred at 15 ° C. for 3 hours to react (C-1) and (B-1). Thus, a solid catalyst component (1) containing silica and a supernatant liquid and having catalytically active species formed on the silica was obtained.

[Reference Example 2]
(1) Synthesis of carrier 1460 milliliters of a 2 mol / liter hydroxytrichlorosilane hexane solution was charged into a fully nitrogen-substituted 8 liter stainless steel autoclave and stirred at 80 ° C. with a composition formula of AlMg ₅ (C ₄ H ₉ ) ₁₁ A hexane solution of 3730 ml (corresponding to 2.68 mol of magnesium) of an organomagnesium compound represented by (OC ₃ H ₇ ) ₂ was added dropwise over 4 hours, and the reaction was continued with stirring at 80 ° C. for 1 hour. After completion of the reaction, the supernatant was removed and washed 4 times with 2600 ml of hexane. As a result of analyzing this solid, the magnesium contained in 1 g of the solid was 8.43 mmol.

(2) Preparation of solid catalyst component While stirring at 20 ° C. in 2880 ml of hexane slurry containing 160 g of the above support, 160 ml of 1 mol / liter titanium tetrachloride hexane solution and 1 mol / liter composition formula AlMg ₅ (C ₄ 160 ml of a hexane solution of an organomagnesium compound represented by H ₉ ) ₁₁ (OC ₃ H ₇ ) ₂ was simultaneously added over 1 hour. After the addition, the reaction was continued at 20 ° C. for 1 hour. After completion of the reaction, 1600 ml of the supernatant was removed, and the solid catalyst component (2) was prepared by washing twice with 1600 ml of hexane. The amount of titanium contained in 1 g of this solid catalyst component was 0.98 mmol, and the amount of chlorine was 14.9 mmol.

[Reference Example 3]
Adjustment 200ml flask cocatalyst component, 37.8 mmol added 40 ml of hexane and _{AlMg 6 (C 2 H 5)} 3 (n-C 4 H 9) organomagnesium compound represented by the ₁₂ as Mg + Al, 25 ° C. By adding 40 ml of hexane containing 2.27 g (37.8 mmol) of methylhydropolysiloxane (viscosity 20 centistokes @ 25 ° C.), then raising the temperature to 80 ° C. and reacting with stirring for 3 hours. A promoter component was obtained.

[Example 1]
(polymerization)
0.8 liters of dehydrated and deoxygenated hexane was placed in an autoclave having an internal volume of 1.5 liters that had been vacuum degassed and purged with nitrogen, and the interior of the autoclave was heated to 70 ° C. Next, 50 ml of 2-methylpropene was added, and 0.20 mmol of the above promoter component and 50 mg of the solid catalyst component (1) were added. Thereafter, the polymerization was started by adding ethylene to bring the total pressure to 0.8 MPa. Polymerization was performed at 70 ° C. for 60 minutes while maintaining the total pressure at 0.8 MPa by continuously replenishing ethylene and hydrogen necessary to control the melt flow rate (MFR) to 2 to 3 g / 10 min. The polymerization slurry was extracted, deactivated with methanol, filtered and dried at 90 ° C. for 1 hour. Thus, the polymer yield of the ethylene polymer was 130 g, and the polymerization activity per 1 g of the catalyst was 2600 g / g-catalyst. The melt flow rate (MFR) was 2.6 g / 10 min, the density was 943 kg / m ³ , and the 2-methylpropene content as measured by NMR was 0.8 mol%. Mw of the ethylene polymer thus obtained before and after the OIP measurement at 210 ° C. was 59200 and 33400, respectively, and the Mw retention was 0.56. The unsaturated bond content of this ethylene polymer was 0.143 / 100C.

[Comparative Example 1]
(polymerization)
Polymerization was conducted in the same manner as in Example 1 except that 3.5 ml of 1-butene was used instead of 50 ml of 2-methylpropene. The polymer yield was 130 g, and the polymerization activity per 1 g of the catalyst was 4000 g / g-catalyst. The melt flow rate (MFR) was 2.6 g / 10 min, the density was 943 kg / m ³ , and the 2-methylpropene content as measured by NMR was 0.6 mol%. Mw of the ethylene polymer thus obtained before and after the OIP measurement at 210 ° C. was 59000 and 28400, respectively, and the Mw retention was 0.48. The ethylenic polymer had an unsaturated bond content of 0.051 / 100C.

[Comparative Example 2]
(polymerization)
0.8 liters of dehydrated and deoxygenated hexane was placed in an autoclave with an internal volume of 1.5 liters that had been vacuum degassed and purged with nitrogen, and the interior of the autoclave was heated to 80 ° C. Next, 50 ml of 2-methylpropene was added, and 0.40 mmol of triisobutylaluminum and 20 mg of the solid catalyst component (2) were added as a promoter component. Thereafter, hydrogen was added at a gas phase concentration of 40 mol% with respect to ethylene, and ethylene was added to bring the total pressure to 0.5 MPa to initiate polymerization. Polymerization was carried out at 80 ° C. for 60 minutes while maintaining the total pressure at 0.5 MPa by continuously supplying ethylene. The polymerization slurry was extracted, deactivated with methanol, filtered and dried at 90 ° C. for 1 hour. Thus, the polymer yield of the ethylene polymer was 230 g, and the polymerization activity per 1 g of the catalyst was 12000 g / g-catalyst. The melt flow rate (MFR) was 2.5 g / 10 min and the density was 967 kg / m ³ , which was equivalent to the density of the ethylene homopolymer. No 2-methylpropene was detected by NMR measurement. Therefore, it is considered that ethylene and 2-methylpropene do not copolymerize with this catalyst.
From the above results, it is clear that the ethylene polymer of the present invention shown in Example 1 is superior in oxidation resistance and thermal stability to the ethylene polymer of Comparative Example 1. Moreover, the effectiveness of the catalyst used in Example 1 is also clear compared with Comparative Example 2.

  The present invention can provide an ethylene polymer excellent in oxidation resistance and thermal stability even without the addition of a thermal stabilizer. The provided ethylene polymer is suitable for applications requiring no addition of a heat stabilizer, such as containers and members for high-purity chemicals. In addition, the present invention can be particularly suitably used for electronic parts, precision parts, optical member wrapping materials, and slip sheets that do not want to contain impurities. Further, in the semiconductor field, the IT field, the medical and medical field, and the sanitary field, it is also suitably used for applications requiring cleanliness, and can be particularly suitably used as a part and member packaging material in the above fields.

Claims (5)

  An ethylene polymer containing 50 mol% or more and 99.9 mol% or less of ethylene units and 0.1 mol% or more and 50 mol% or less of 2-substituted-1-olefin units, and having a molecular weight of 5,000 or more and 5 million or less. An ethylene polymer, wherein the ethylene polymer has an unsaturated bond content of 0.001 / 100C or more and 0.4 / 100C or less.   The ethylene-based polymer according to claim 1, wherein the number of carbon atoms contained in the 2-substituted-1-olefin unit is 6 or less.   The ethylene-based polymer according to claim 1 or 2, wherein the retention of the weight average molecular weight measured by oxidation induction time at 210 ° C is 50% or more and 99.9% or less. At least [A] a solid component having substantially no hydroxyl group, [B] a soluble transition metal compound represented by the following formula (1), [C] reacting with the transition metal compound [B] and having catalytic activity The ethylene-based polymer according to any one of claims 1 to 3, wherein the ethylene-based polymer is produced by an olefin polymerization solid catalyst formed from an activator compound that forms a metal complex.
L _j W _k MX _p X ′ _q (1)
(In the formula, each L is independently a η bond selected from the group consisting of a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, a tetrahydrofluorenyl group, and an octahydrofluorenyl group. A cyclic anionic ligand, which optionally has 1 to 8 substituents, each of which is independently a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, carbon A halogen-substituted hydrocarbon group having 1 to 12 carbon atoms, an aminohydrocarbyl group having 1 to 12 carbon atoms, a hydrocarbyloxy group having 1 to 12 carbon atoms, a dihydrocarbylamino group having 1 to 12 carbon atoms, and a hydrocarbyl phosphor having 1 to 12 carbon atoms Up to 20 non-chosen selected from the group consisting of a fino group, a silyl group, an aminosilyl group, a hydrocarbyloxysilyl group having 1 to 12 carbon atoms and a halosilyl group Is a substituent having an atom,
M is a transition metal selected from the group of transition metals belonging to Group 4 of the periodic table having a formal oxidation number of +2, +3, or +4, and represents a transition metal bonded to at least one ligand L by η ^5. ,
W is a divalent substituent having up to 50 non-hydrogen atoms, and binds to L and M with a valence of 1 each, thereby synergizing with L and M to perform a metallocycle. Represents a divalent substituent to be formed;
X is each independently a monovalent anionic σ-bonded ligand, a divalent anionic σ-bonded ligand that binds to M bivalently, and L and M each monovalently Represents an anionic σ-bonded ligand having up to 60 non-hydrogen atoms selected from the group consisting of divalent anionic σ-bonded ligands bonded by valence;
X ′ each independently represents a neutral Lewis base coordination compound having up to 40 non-hydrogen atoms;
j is 1 or 2, provided that when j is 2, in some cases two ligands L are bonded to each other via a divalent group having up to 20 non-hydrogen atoms, The valent group is a hydrocarbadiyl group having 1 to 20 carbon atoms, a halohydrocarbadiyl group having 1 to 12 carbon atoms, a hydrocarbyleneoxy group having 1 to 12 carbon atoms, or a hydrocarbyleneamino group having 1 to 12 carbon atoms. A group selected from the group consisting of a silanediyl group, a halosilanediyl group, and a silyleneamino group,
k is 0 or 1,
p is 0, 1 or 2, provided that X is a monovalent anionic σ-bonded ligand or a divalent anionic σ-bonded ligand bonded to L and M , P is an integer 1 or more smaller than the formal oxidation number of M, and when X is a divalent anionic σ-bonded ligand bonded only to M, p is smaller than the formal oxidation number of M ( j + 1) an integer smaller than or equal to
q is 0, 1 or 2.   5. The ethylene polymer according to claim 1, wherein hydrogen is added to the reactor at a concentration of 10 mol ppm to 1 mol% during production of the ethylene polymer. Production method