JP2018178101A - Catalyst for olefin polymerization, and, method of producing the same, and method of producing olefin polymer using the catalyst for olefin polymerization - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst for olefin polymerization allowing for production of an olefin polymer less in fish eye and excellent in appearance after molding processing.SOLUTION: The catalyst for olefin polymerization is provided which contains component (A), component (B) and component (C), and in which the component (A) is a metallocene compound having a structure represented by general formula (1), the component (B) is an aluminoxane compound, the component (C) is an inorganic oxide carrier having a Tv value (mass%) calculated by following formula of 0.4 to 2.0. Formula: Tv={m1/(m1-m2)}×100, wherein m1:mass after heating from room temperature to 200°C under nitrogen, m2:mass after heating from 200°C to 1100°C under nitrogen. The content of the component (B) per 1 mol of transition metal M in the component (A) is in a specific range, and the content of the component (B) per 1 g of the component (C) is in a specific range.SELECTED DRAWING: None

Description

  The present invention relates to an olefin polymerization catalyst capable of producing an olefin polymer excellent in appearance after molding, a method for producing the same, and a method for producing an olefin polymer using the olefin polymerization catalyst.

In recent years, plastic films, sheets, injection molded articles, pipes, extrusion molded articles, hollow molded articles and the like have been actively used in various industrial fields. In particular, polyethylene resins (ethylene polymers) are widely used because they are inexpensive and lightweight, and are excellent in moldability, rigidity, impact strength, transparency, chemical resistance, and recyclability.
Methods of using a catalyst comprising a metallocene compound and an aluminoxane compound in producing an ethylene-based polymer are already known. It is known that the polymerization method using these catalysts has high polymerization activity per transition metal and a polymer having a narrow molecular weight distribution and composition distribution as compared with the conventional method using a so-called Ziegler-Natta catalyst. It is done.

  However, metallocene-type polyethylene is inferior in molding processability as compared with Ziegler-Natta-type polyethylene. As a method of improving molding processability, a method of blending high-pressure low-density polyethylene (HPLD) excellent in melt properties with metallocene-based polyolefin and modifying it (for example, see Patent Document 1), molecular weight separately manufactured A method of blending metallocene-type polyolefins of different distributions and broadening the molecular weight distribution to improve melting characteristics (see, for example, Patent Document 2), blending high-pressure low-density polyethylene (HPLD) excellent in melt properties with metallocene-based polyolefin There is known a method of reforming (see, for example, Patent Document 2), a method of producing a metallocene-based polyolefin having a wide molecular weight distribution by multistage polymerization using a metallocene catalyst (see, for example, Patent Document 3), and the like. However, sufficient flowability and moldability can not be obtained yet, and the impact strength of the molded body Decrease or, or is easily tackiness product surface, such as a film increases low temperature elution component, problems such transparency and gel is deteriorated has occurred.

  Under such circumstances, the long chain branch structure useful for the development of an ethylene-based polymer excellent in both molding processing characteristics and product strength by solving the problems of the conventional ethylene-based polymer and polyethylene-based resin composition The research on metallocene polymerization catalysts capable of controlling H and ethylene polymers obtained therefrom is continued (Patent Documents 4 to 7).

Japanese Patent Publication No. 06-65443 JP 06-136196 A Unexamined-Japanese-Patent No. 03-234717 gazette JP, 2009-143901, A JP 2011-137146 A Unexamined-Japanese-Patent No. 2013-227271 JP, 2016-17039, A

However, in the molded article of the olefin polymer obtained also by the technique described in the above-mentioned patent documents, a fish eye (another name, FE, gel) may be generated to deteriorate the appearance, and an improvement is necessary.
An object of the present invention is to provide a catalyst for olefin polymerization capable of producing an olefin polymer having a small number of fish eyes after molding and having an excellent appearance.

The inventors of the present invention conducted intensive studies to achieve the above object, and as a result, metallocene compounds having specific structures, aluminoxane compounds, and inorganic oxide carriers having weight loss (Tv value) heated under nitrogen having specific values. It has been found that by using an olefin polymerization catalyst containing an olefin polymer, it is possible to produce an olefin polymer having an excellent appearance after molding, and the present invention has been completed based on such findings.
That is, according to the present invention, an olefin polymerization catalyst, a method for producing the same, and a method for producing an olefin polymer using the olefin polymerization catalyst are provided as follows.

  According to a first aspect of the present invention, there is provided an olefin polymerization catalyst comprising the component (A), the component (B) and the component (C), wherein the component (A) has the following general formula (1) The component (B) is an aluminoxane compound, and the component (C) is a nitrogen compound relative to a mass (m1) after heating from room temperature to 200 ° C. under nitrogen. The ratio (Tv) of the value (m1-m2) obtained by subtracting the mass (m2) after heating from 200 ° C. to 1100 ° C. under nitrogen from the mass (m1) after heating to 200 ° C. is 0.4 to 2. It is an inorganic oxide support having 0% by mass, and the content of the component (B) per 1 mol of the transition metal M in the component (A) is in the range of 330 to 12500 mol, and 1 g of the component (C) Containing the component (B) A catalyst for olefin polymerization is provided, characterized in that the amount is in the range of 5.0 to 12.0 mmol.

[In Formula (1), M shows the transition metal selected from the group which consists of Ti, Zr, and Hf. X1 and X2 each independently represent a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing oxygen or nitrogen, or a hydrocarbon group having 1 to 20 carbon atoms 1 shows a substituent selected from the group consisting of an amino group and an alkoxy group having 1 to 20 carbon atoms.
Q represents an atom selected from the group consisting of a carbon atom, a silicon atom, and a germanium atom. R1 and R2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, m is 1 or 2, and when m is 2, plural Qs may be the same. The plurality of R 1 may be the same or different, and the plurality of R 2 may be the same or different. R1 and R2 may form a ring together with one or more Q.
R3, R4, R5, R6, R10, R11, R12 and R13 each independently represent a hydrogen atom, a halogen, a hydrocarbon group having 1 to 50 carbon atoms, a silicon number of 1 to 6, and the carbon number is A silicon-containing hydrocarbon group having 1 to 50 carbon atoms, a halogen-containing hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms containing an element selected from the group consisting of nitrogen, phosphorus, oxygen and sulfur, And a substituent selected from the group consisting of a hydrocarbon group-substituted silyl group having 1 to 50 carbon atoms.
Among R3 to R6, adjacent substituents may form a ring together with a carbon atom of a conjugated 5-membered ring to which the substituent is bonded. Among R10 to R13, adjacent substituents may form a ring together with a carbon atom of a conjugated 5-membered ring to which the substituent is bonded. ]

According to the second invention of the present invention, the component (C) is an inorganic oxide support having a pore volume of 1.20 to 2.50 mL / g and a BET surface area of 280 to 800 m ² / g. The above olefin polymerization catalyst is provided.
According to the third invention of the present invention, in the general formula (1), only one of adjacent substituents among R3, R4, R5, R6, R10, R11, R12 and R13 is only one group. There is provided the above-mentioned catalyst for olefin polymerization, which is a metallocene compound forming a ring together with a conjugated 5-membered ring carbon atom to which these substituents are bonded.

According to a fourth aspect of the present invention, the component (A) according to the first aspect, the component (B) according to the first aspect, the component (C) according to the first aspect, The component (B) per mol of transition metal M in the component (A) is in a range of 330 to 12500 mol, and the component (B) per gram of the component (C) is 5.0 to 12.0 mmol There is provided a process for the preparation of an olefin polymerization catalyst contacted in a range.
According to a fifth aspect of the present invention, the component (C) is an inorganic oxide support having a pore volume of 1.20 to 2.50 mL / g and a BET surface area of 280 to 800 m ² / g. There is provided a process for producing the catalyst for olefin polymerization, characterized in that
According to the sixth invention of the present invention, in the general formula (1), only one of adjacent substituents among R3, R4, R5, R6, R10, R11, R12 and R13 is only one set It is a metallocene compound in which a ring is formed together with a conjugated 5-membered ring carbon atom to which these substituents are bonded, and the method for producing a catalyst for olefin polymerization is provided.
According to a seventh aspect of the present invention, there is provided a method for producing a catalyst for olefin polymerization, which comprises bringing the component (A) into contact with the component (B) and then bringing the component (C) into contact. Provided.
According to an eighth aspect of the present invention, there is provided an olefin polymerization catalyst according to any one of the first to third inventions or a catalyst for olefin polymerization produced by the method according to any of the fourth to seventh inventions. A method is provided for producing olefin polymers that polymerize olefins.

  ADVANTAGE OF THE INVENTION According to this invention, the catalyst for olefin polymerization which can manufacture an olefin polymer which has few fish eyes and excellent appearance after shaping | molding process can be provided.

  Hereinafter, the catalyst for olefin polymerization of the present invention, the method for producing the same, the method for producing an olefin polymer using the catalyst for olefin polymerization of the present invention, and the olefin polymer obtained by the method for producing explain.

1. Olefin polymerization catalyst The olefin polymerization catalyst of the present invention is a catalyst for olefin polymerization comprising component (A), component (B), and component (C), wherein said component (A) has the following general formula ( The component (B) is an aluminoxane compound, and the component (C) is a nitrogen compound relative to a mass (m1) after heating from room temperature to 200 ° C. under nitrogen. The ratio (Tv) of the value (m1-m2) obtained by subtracting the mass (m2) after heating from 200 ° C. to 1100 ° C. under nitrogen from the mass (m1) after heating from room temperature to 200 ° C. It is an inorganic oxide support which is 2.0 mass%, content of the said component (B) per mol of transition metals M in the said component (A) is the range of 330-12500 mol, and the said component (C ) Per 1g The content of the serial component (B) is characterized in that it is a range of 5.0～12.0Mmol.

[In Formula (1), M shows the transition metal selected from the group which consists of Ti, Zr, and Hf. X1 and X2 each independently represent a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing oxygen or nitrogen, or a hydrocarbon group having 1 to 20 carbon atoms 1 shows a substituent selected from the group consisting of an amino group and an alkoxy group having 1 to 20 carbon atoms.
Q represents an atom selected from the group consisting of a carbon atom, a silicon atom, and a germanium atom. R1 and R2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, m is 1 or 2, and when m is 2, plural Qs may be the same. The plurality of R 1 may be the same or different, and the plurality of R 2 may be the same or different. R1 and R2 may form a ring together with one or more Q.
R3, R4, R5, R6, R10, R11, R12 and R13 each independently represent a hydrogen atom, a halogen, a hydrocarbon group having 1 to 50 carbon atoms, a silicon number of 1 to 6, and the carbon number is A silicon-containing hydrocarbon group having 1 to 50 carbon atoms, a halogen-containing hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms containing an element selected from the group consisting of nitrogen, phosphorus, oxygen and sulfur, And a substituent selected from the group consisting of a hydrocarbon group-substituted silyl group having 1 to 50 carbon atoms.
Among R3 to R6, adjacent substituents may form a ring together with a carbon atom of a conjugated 5-membered ring to which the substituent is bonded. Among R10 to R13, adjacent substituents may form a ring together with a carbon atom of a conjugated 5-membered ring to which the substituent is bonded. ]

In the olefin polymerization catalyst of the present invention, as the inorganic oxide carrier which is the component (C), one having a specific Tv value is used, and the component (A), the component (B) and the component (C) contained in the catalyst By setting the ratio of the content of) to a specific range, it is possible to produce an olefin polymer having few fish eyes and excellent in appearance after molding processing. The reason is presumed as follows.
Generally, adsorbed water evaporates by heating the inorganic oxide support at 200 ° C., but dehydration condensation of surface hydroxyl groups hardly progresses. On the other hand, when the inorganic oxide is heated at 1100 ° C., most of the surface hydroxyl groups are dehydrated and condensed.
Therefore, after heating from room temperature to 200 ° C. under nitrogen, the mass (m1) after heating from room temperature to 200 ° C. under nitrogen, after heating from 200 ° C. to 1100 ° C. under nitrogen There is a correlation between the ratio (Tv) of the value (m1-m2) obtained by subtracting the mass (m2) and the amount of surface hydroxyl groups.

First, the factor which a fisheye produces | generates when the Tv value of an oxide support is large is examined.
It is considered that in the case of an inorganic oxide carrier having a large amount of surface hydroxyl groups and a large Tv value remaining, dense points of the surface hydroxyl groups are present. The reaction product of the component (A) and the component (B) reacts with the surface hydroxyl group to form Zr ⁺ which is an active species from the Zr atom in the catalyst. It is thought that. At this active species concentration point, the heat generation at the time of polymerization becomes larger than at other portions. Where the exotherm is large, the complex structure is affected and the nature of the active species changes. When the active species is thus modified, the formation of a high molecular weight polymer and the development of long chain branching may result in the formation of a locally high viscosity polymer. The formation of a high viscosity polymer by this modified active species is considered to be one of the factors that produce fisheye.
In addition, when many hydroxyl groups exist on the surface of the inorganic oxide support, the contact probability with the component (A) is increased, so the influence of the surface hydroxyl groups on the complex structure becomes large, and there is a possibility of modifying the complex structure of the component (A) It is thought that it will increase. The modified component (A) may produce a polymer having a viscosity difference more than other portions. The formation of a polymer having a viscosity difference due to the modified component (A) is also considered to be one of the factors causing the fisheye.

Next, the factor which a fish eye produces when the Tv value of an oxide support is small is examined.
Since the amount of dehydration condensation of the surface hydroxyl groups depends on the heating temperature, the amount of dehydration condensation hardly increases even if the heating (baking) time at a certain temperature is increased (that is, the surface hydroxyl groups are not decreased). In order to reduce it, it is necessary to raise the firing temperature. However, if the calcination temperature is too high to reduce the Tv value of the inorganic oxide support, the pore structure of the inorganic oxide support is broken, and the loading ability of the component (A) and the component (B) decreases. Therefore, fouling is caused to cause polymerization to become unstable, and it is considered that fish eyes are generated. Here, in order to make the Tv value of the inorganic oxide support used as the component (C) in the present invention less than 0.4, it is necessary to heat at 700 ° C. or higher, but when heated at 700 ° C. or higher, the pore structure May break.
Therefore, it is extremely difficult to prepare an inorganic oxide support having a Tv value of less than 0.4 and a pore structure that is not collapsed.

  As mentioned above, in order to reduce a fish eye, control of Tv value is important and it is thought that a fish eye will be improved by using an inorganic oxide support | carrier whose Tv is 0.4-2.0 mass%.

  Further, as described above, when the surface hydroxyl groups in the component (A) and the component (C) react with each other, the component (A) is considered to be denatured to form a polymer causing fish eyes. In order to prevent this, the amount of component (B) is increased and the ratio of component (B) to the amount of surface hydroxyl groups is increased to suppress the modification reaction of component (A). I think it is important for On the other hand, when the amount of the component (B) is too large, it is considered that fouling is caused to cause the polymerization to be unstable and the risk of the fish eye increases. As mentioned above, in order to reduce a fish eye, control of the content ratio of a component (A), a component (B), and a component (C) is also considered to be important.

  Hereinafter, the content ratio of the component (A), the component (B), the component (C) and the component contained in the olefin polymerization catalyst of the present invention will be described in order.

1-1. Component A (metallocene compound)
Component (A) is a metallocene compound represented by the following general formula (1). By using the metallocene compound represented by the general formula (1), a long chain branched polyolefin can be produced with high activity.

  In the general formula (1), M represents a transition metal selected from the group consisting of Ti, Zr and Hf, preferably Zr or Hf, more preferably Zr.

X1 and X2 each independently represent a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing oxygen or nitrogen, or a hydrocarbon group having 1 to 20 carbon atoms And a substituent selected from the group consisting of an amino group and an alkoxy group having 1 to 20 carbon atoms, and examples of the halogen represented by X1 and X2 include a chlorine atom, a bromine atom and an iodine atom, and X1 and X2 The hydrocarbon group having 1 to 20 carbon atoms represented by X 2 preferably has 1 to 7 carbon atoms, and, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i -Butyl, t-butyl, n-pentyl, neopentyl, cyclopentyl, n-hexyl, cyclohexyl, phenyl, benzyl and the like.
The oxygen-containing hydrocarbon group having 1 to 20 carbon atoms which is represented by X1 and X2 preferably has 1 to 12 carbon atoms, and examples thereof include a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, and an i- Propoxymethyl group, n-butoxymethyl group, i-butoxymethyl group, t-butoxymethyl group, methoxyethyl group, methoxyethyl group, ethoxyethyl group, acetyl group, 1-oxopropyl group, 1-oxo-n-butyl group, 2- Methyl-1-oxopropyl group, 2,2-dimethyl-1-oxo-propyl group, phenylacetyl group, diphenylacetyl group, benzoyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, Examples thereof include 2-furyl group and 2-tetrahydrofuryl group.
The hydrocarbon group having 1 to 20 carbon atoms containing nitrogen preferably has 1 to 10 carbon atoms, and, for example, dimethylaminomethyl group, diethylaminomethyl group, di-propylaminomethyl group, bis (dimethylamino) Methyl group, bis (di-propylamino) methyl group, (dimethylamino) (phenyl) methyl group, methyl imino group, ethyl imino group, 1- (methyl imino) ethyl group, 1-(phenyl imino) ethyl group, 1-[ And (phenylmethyl) imino] ethyl group and the like.
The hydrocarbon substituted amino group having 1 to 20 carbon atoms and represented by X1 and X2 preferably has 1 to 12 carbon atoms. For example, dimethylamino, diethylamino, di n-propylamino, di And -propylamino group, di-n-butylamino group, di-butylamino group, di-t-butylamino group and diphenylamino group.
The C1-C20 alkoxy group represented by X1 and X2 preferably has 1 to 6 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and an n-butoxy group , I-butoxy group, t-butoxy group, phenoxy group and the like.

  Preferred examples of X1 and X2 include chlorine, bromine, methyl, n-butyl, i-butyl, methoxy, ethoxy, i-propoxy, n-butoxy, phenoxy, dimethylamino and di- An i-propylamino group is mentioned, Among these, a chlorine atom, a methyl group and a dimethylamino group are particularly preferable.

In the general formula (1), Q represents a carbon atom, a silicon atom or a germanium atom, preferably a carbon atom or a silicon atom, more preferably a silicon atom.
m is 1 or 2, preferably 1. When m is 2, plural Qs may be the same or different.

  In the general formula (1), R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and when m is 2, plural R 1 s are identical or different. The plurality of R2 may be the same or different. Also, R 1 and R 2 may form a ring together with one or more Q.

The hydrocarbon group having 1 to 10 carbon atoms represented by R1 and R2 preferably has 1 to 6 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, i-propyl and n-butyl groups. And i-butyl, t-butyl, n-pentyl, neopentyl, cyclopentyl, n-hexyl, cyclohexyl and phenyl groups.
In addition, R 1 and R 2 may form a ring together with Q to which they are attached, as a cyclobutylidene group, cyclopentylidene group, cyclohexylidene group, silacyclobutyl group, silacyclopentyl group, silacyclohexyl Groups and the like.

  Preferred examples of R1 and R2 include a hydrogen atom, a methyl group, an ethyl group, a phenyl group, an ethylene group and a cyclobutylidene group when Q is a carbon atom, and a methyl group and an ethyl when Q is a silicon atom. Groups, phenyl groups and silacyclobutyl groups.

R3, R4, R5, R6, R10, R11, R12 and R13 each independently represent a hydrogen atom, a halogen, a hydrocarbon group having 1 to 50 carbon atoms, a silicon number of 1 to 6, and the carbon number is A silicon-containing hydrocarbon group having 1 to 50 carbon atoms, a halogen-containing hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms containing an element selected from the group consisting of nitrogen, phosphorus, oxygen and sulfur, And a substituent selected from the group consisting of a hydrocarbon group-substituted silyl group having 1 to 50 carbon atoms.
Examples of the halogen represented by R3 to R6 and R10 to R13 include a chlorine atom, a bromine atom and an iodine atom.
The hydrocarbon group having 1 to 50 carbon atoms represented by R3 to R6 and R10 to R13 preferably has 1 to 20 carbon atoms, and more preferably 1 to 9 carbon atoms, and examples thereof include a methyl group, an ethyl group, and n- Propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, neopentyl, cyclopentyl, n-hexyl, cyclohexyl, phenyl, benzyl, 2- A methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3,5-dimethylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group etc. are mentioned.
The silicon-containing hydrocarbon group having 1 to 6 silicon atoms and 1 to 50 carbon atoms represented by R 3 to R 6 and R 10 to R 13 preferably has 1 to 2 silicon atoms, It is preferable that it is 1-18, especially 1-13. For example, bis (trimethylsilyl) methyl group, bis (t-butyldimethylsilyl) methyl group and the like can be mentioned.
The halogen-containing hydrocarbon group having 1 to 50 carbon atoms represented by R3 to R6 and R10 to R13 preferably has 1 to 20 carbon atoms, and examples thereof include a bromomethyl group, a chloromethyl group and a 2-chloroethyl group. Group, 2-bromoethyl group, 2-bromopropyl group, 3-bromopropyl group, 2-bromocyclopentyl group, 2,3-dibromocyclopentyl group, 2-bromo-3-iodocyclopentyl group, 2,3-dibromocyclohexyl group And 2-chloro-3-iodocyclohexyl group, 2-chlorophenyl group, 4-chlorophenyl group, 2,3,4,5,6-pentafluorophenyl group, 4-trifluoromethylphenyl group and the like.
The hydrocarbon group having 1 to 50 carbon atoms containing nitrogen and represented by R3 to R6 and R10 to R13 preferably has 1 to 40 carbon atoms, and more preferably 1 to 6 carbon atoms. For example, pyrrolyl group, tetrahydropylori And 2-methylpyrrolyl group.
The hydrocarbon group having 1 to 50 carbon atoms and containing phosphorus represented by R3 to R6 and R10 to R13 preferably has 1 to 40 carbon atoms, and more preferably 1 to 6 carbon atoms. For example, a phosphoryl group, tetrahydrophos Foryl group, 2-methyl phosphoryl group and the like can be mentioned.
The hydrocarbon group having 1 to 50 carbon atoms containing oxygen and represented by R3 to R6 and R10 to R13 preferably has 1 to 40 carbon atoms, and more preferably 1 to 6 carbon atoms. For example, furyl group, tetrahydrofuryl Group, 2-methyl furyl group and the like.
The C1-C50 hydrocarbon group containing sulfur represented by R3 to R6 and R10 to R13 preferably has 1 to 40 carbon atoms, and more preferably 1 to 6 carbon atoms. For example, a thienyl group or tetrahydrothienyl group And 2-methylthienyl group.
The hydrocarbon group-substituted silyl group having 1 to 50 carbon atoms represented by R 3 to R 6 and R 10 to R 13 preferably has 1 to 40 carbon atoms, and more preferably 1 to 18 carbon atoms. -Butylsilyl group, di-t-butylmethylsilyl group, t-butyldimethylsilyl group, triphenylsilyl group, diphenylmethylsilyl group, phenyldimethylsilyl group and the like.

Among R3 to R6, adjacent substituents may form a ring together with a carbon atom of a conjugated 5-membered ring to which the substituent is bonded. Among R10 to R13, adjacent substituents may form a ring together with a carbon atom of a conjugated 5-membered ring to which the substituent is bonded.
Specific examples of the methaceron compounds in which R3 to R6 and R10 to R13 do not form a ring are shown in Tables 1-1 to 1-5, but are not limited thereto.

Of R 3, R 4, R 5, R 6, R 10, R 11, R 12 and R 13, only any one adjacent substituent is combined with the carbon atom of the conjugated 5-membered ring to which these substituents are bonded Preferably form a ring on the
Of R 3, R 4, R 5, R 6, R 10, R 11, R 12, and R 13, only one adjacent pair has a ring together with the carbon atom of the conjugated 5-membered ring to which these substituents are bound Among the compounds formed, a crosslinked cyclopentadienylindenyl compound represented by the following general formula (2) is particularly preferable.
In the bridged cyclopentadienylindenyl compound represented by the following general formula (2), R 11 is preferably not a hydrogen atom, R 11 is not a hydrogen atom, and any one of R 3 to R 6 is a hydrogen atom. It is further preferred that none be present.

In General Formula (2), R14 to R17 each independently represent a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silicon containing 1 to 18 silicon atoms and 1 to 18 carbon atoms. It is selected from the group consisting of a hydrocarbon group, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms containing oxygen or sulfur, and a hydrocarbon group-substituted silyl group having 1 to 40 carbon atoms The substituent to be However, the total number of carbons contained in R14 to R17 does not exceed 96.
Examples of the substituent represented by R14 to R17 are the same as the examples represented by R3, R4, R5, R6, R10, R11, R12 and R13. Among R14 to R17, adjacent substituents may form a ring together with a carbon atom of a conjugated 6-membered ring to which the substituent is bonded.
R14 may be a substituted aryl group represented by the following general formula (3). When R 14 is a substituted aryl group represented by the following general formula (3), R 14 and R 15 may form a ring together with a carbon atom of a conjugated 6-membered ring to which the substituent is attached: There is not.

In the general formula (3), Y1 represents a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, an oxygen atom, or a sulfur atom.
R18, R19, R20, R21 and R22 each independently represent a hydrogen atom, a chlorine atom, a bromine atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing oxygen or nitrogen, Hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, silicon-containing hydrocarbon group having 1 to 18 silicon atoms and 1 to 18 carbon atoms, 1 to 20 carbon atoms The substituent selected from the group consisting of a halogen-containing hydrocarbon group and a hydrocarbon group substituted silyl group having 1 to 20 carbon atoms is shown.
Among R18 to R22, adjacent substituents may form a ring together with the atom of the ring to which the substituent is attached. n is 0 or 1, and when n is 0, a substituent R18 does not exist in Y1. p is 0 or 1, and when p is 0, there is no carbon atom to which R21 and R21 are bonded, and a conjugated 5-membered member in which the carbon atom to which R20 is bonded and the carbon atom to which R22 is directly bonded Indicates a ring structure.
As a cyclic skeleton of the substituted aryl group shown by General formula (3), a phenyl ring, a furyl ring, etc. are mentioned, for example.

  Specific examples of the bridged cyclopentadienylindenyl compound represented by the general formula (2), which is a general formula (1) methacerone compound in which R12 and R13 form a ring, are shown in Tables 2-1 and 2-3. Not limited to these.

  The metallocene compound used in the present invention can be synthesized by any method depending on the manner of substitution or bonding. An example of the synthesis route is shown below.

  In the above synthesis route, 1 is obtained by performing coupling reaction of 1 and phenylboronic acid in the presence of a palladium catalyst. After reacting 2 with methylmagnesium bromide, 3 is obtained by dehydration using p-toluenesulfonic acid. Anionization of 3 with 1 equivalent of n-butyllithium or the like is followed by reaction with an excess amount of dimethyldichlorosilane to distill off unreacted dimethyldichlorosilane, whereby 4 is obtained. The resulting 4 is reacted with sodium cyclopentadienide to give 5. After dianionization of 5 with 2 equivalents of n-butyllithium or the like, a metallocene compound 6 is obtained by reaction with zirconium tetrachloride.

The synthesis of substituted metallocene compounds can be carried out by using the corresponding substituted raw materials, and instead of phenylboronic acid, corresponding boronic acids such as 4-methylphenylboronic acid, 4-i- By using propylphenylboronic acid, 4-t-butylphenylboronic acid, 4-chlorophenylboronic acid, 4-methoxyphenylboronic acid or the like, substituents corresponding to the 4-position of the indenyl ring can be introduced.
Also, instead of methyl magnesium bromide which reacts with 2, the corresponding reagents may be introduced at the 3-position of the indenyl ring by using corresponding reagents such as ethyl magnesium bromide, n-propyl magnesium chloride and the like. it can.
Furthermore, instead of the cyclopentadienyl group (Cp), the anion of the corresponding substituted cyclopentadiene, such as t-butylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1-methyl-3-t-butylcyclopentadiene etc. By using, the complex which introduce | transduced the substituent respectively corresponded to cyclopentadiene can be synthesize | combined.

1-2. Component B (aluminoxane compound)
In the olefin polymerization catalyst of the present invention, an aluminoxane compound (also referred to as an alumoxane compound) is used as component (B) which is a compound which reacts with the metallocene compound of the component (A) to form a cationic metallocene compound during olefin polymerization reaction. Containing).
The aluminoxane compound is a compound obtained by reacting alkylaluminum and water among organic aluminum oxy compounds having an Al-O-Al bond in the molecule, and is combined with the component (A) and the component (C). By using it, it is possible to obtain an olefin polymer having few fish eyes and excellent in appearance after molding processing. The number of Al-O-Al bonds in the molecule of the aluminoxane compound is usually in the range of 1 to 100, preferably 1 to 50.

The reaction of alkyl aluminum with water is usually carried out in an inert hydrocarbon (solvent).
As the inert hydrocarbon, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene and the like, alicyclic hydrocarbons and aromatic hydrocarbons can be used, but aliphatic hydrocarbons or It is preferred to use aromatic hydrocarbons.
As the alkylaluminum used for the preparation of the aluminoxane compound, any of compounds represented by the following general formula (4) can be used, but preferably trialkylaluminum is used.
R23 _t AlX3 _{3- t} .. Formula (4)
(In the formula (4), R23 represents an alkyl group having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, X 3 represents a hydrogen atom or a halogen atom, and t represents an integer of 1 ≦ t ≦ 3. .)
Examples of the alkyl group of alkylaluminum include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group and dodecyl group. Among these, a methyl group (methylaluminoxane) is particularly preferable.
The said alkyl aluminum can also be used 1 type or in mixture of 2 or more types.
The reaction ratio of water to alkylaluminum (water / Al molar ratio) is preferably 0.25 / 1 to 1.2 / 1, especially 0.5 / 1 to 1/1, and the reaction temperature is It is usually in the range of -70 to 100 ° C, preferably -20 to 20 ° C. The reaction time is usually in the range of 5 minutes to 24 hours, preferably 10 minutes to 5 hours. As water required for the reaction, not only simple water but also crystal water contained in copper sulfate hydrate, aluminum sulfate hydrate and the like, and components capable of producing water in the reaction system can be used.

1-3. Component C (inorganic oxide carrier)
The catalyst for olefin polymerization of the present invention is a particulate carrier as component (C), which is a mass after heating from room temperature to 200 ° C. under nitrogen with respect to a mass (m 1) after heating from room temperature to 200 ° C. under nitrogen. Inorganic oxide in which the ratio (Tv) of the value (m1-m2) obtained by subtracting the mass (m2) after heating from 200 ° C. to 1100 ° C. from (m1) is 0.4 to 2.0 mass% Contains a carrier.
The inorganic oxide support includes metal oxides. Examples of the metal oxide include single oxides or composite oxides of elements of Groups 1 to 14 of the periodic table, such as SiO ₂ , Al ₂ O ₃ , MgO, CaO, B ₂ O ₃ , TiO ₂ , and ZrO _2. , Fe ₂ O ₃ , Al ₂ O ₃ · MgO, Al ₂ O ₃ · CaO, Al ₂ O ₃ · SiO ₂ , Al ₂ O ₃ · MgO · CaO, Al ₂ O ₃ · MgO · SiO ₂ , Al ₂ O Various natural or synthetic single oxides or complex oxides such as ₃ · CuO, Al ₂ O ₃ · Fe ₂ O ₃ , Al ₂ O ₃ · NiO, SiO ₂ · MgO can be exemplified. Here, the above formula is not a molecular formula but represents only the composition, and the structure and component ratio of the composite oxide used in the present invention are not particularly limited. Further, the metal oxide used in the present invention may absorb a small amount of water, and may contain an impurity of 1% by mass or less as long as the effect of the present invention is not affected. Among metal oxides, SiO ₂ , Al ₂ O ₃ , a single oxide or composite oxide of MgO is preferable, and SiO ₂ is particularly preferable.
The Tv value of the inorganic oxide support is a value determined by the following formula.
Tv value = {(m1-m2) / m1} × 100
The meanings of m1 and m2 in the above formula are as follows.
m1: Mass after heating from room temperature to 200 ° C. under nitrogen m2: Mass after heating from 200 ° C. to 1100 ° C. under nitrogen As described above, when the Tv value of the inorganic oxide support is large, inorganic Since a large amount of surface hydroxyl groups remain in the oxide, it is considered that fish eye is easily generated. In addition, when the Tv value of the inorganic oxide support is small, as described above, the pore structure of the inorganic oxide support is broken and the supporting ability of the component (A) and the component (B) is reduced. It is thought that it becomes easy to generate an eye.
Control of the Tv value of the particulate carrier, which is the component (C), is important in order to reduce the fish eye, and by using an inorganic oxide carrier having a Tv value of 0.4 to 2.0% by mass Eye improves. The Tv value of the inorganic oxide support is preferably in the range of 0.5 to 1.9% by mass, and more preferably in the range of 0.7 to 1.9% by mass.
When the Tv value of the inorganic oxide support exceeds 2.0% by mass, usually, the calcination temperature is 350 ° C. to 650 ° C., preferably 400 ° C. to 550 ° C., the calcination time 0 under an inert gas or dry air atmosphere. The above-mentioned predetermined range can be adjusted by firing under the conditions of 5 hours to 10 hours. It is possible to lower the Tv value by firing in a temperature range of 350 ° C. to 650 ° C., and since the firing temperature is 700 ° C. or less, the Tv value does not fall below 0.4. As a firing method, for example, firing with an electric furnace, a kiln, a fluidized bed furnace, reduced pressure firing and the like can be mentioned. Although an example of the baking conditions for obtaining the inorganic oxide support | carrier of the Tv value of the said predetermined range below is shown, it is not limited to this.
The crucible containing 100 g of the inorganic oxide support is placed in an electric furnace, and while raising the flow rate of nitrogen at 4 L / min, the temperature is raised from room temperature to 200 ° C. at a temperature rising rate of 3 ° C./min, and predried at 200 ° C. for 1 hour. Subsequently, the temperature is raised from 200 ° C. to 500 ° C. at a temperature rising rate of 7 ° C./min, and baking is performed at 500 ° C. for 2 hours. By cooling the furnace temperature to room temperature while flowing nitrogen at 4 L / min, it is possible to adjust the Tv value of the inorganic oxide support to the above-mentioned predetermined range.

The inorganic oxide support preferably has a pore volume of 1.20 to 2.50 mL / g, preferably in the range of 1.30 to 2.20 mL / g, and 1.40 to 2.00 mL. More preferably, it is in the range of / g.
In the present invention, the pore volume is a value measured by a nitrogen adsorption method.
The inorganic oxide support preferably has a BET surface area of 280 to 800 m ² / g, preferably 290 to 700 m ² / g, and more preferably 290 to 600 m ² / g. preferable.
In the present invention, the specific surface area is a value measured by a nitrogen adsorption method.
The properties of the other inorganic oxide carriers are not particularly limited, but the average particle size is usually 5 to 200 μm, preferably 10 to 150 μm, the average pore size is usually 20 to 1000 Å, preferably 50 to 500 Å, and the apparent specific gravity is usually It is preferred to use an inorganic oxide support having from 0.10 to 0.50 g / mL, preferably from 0.15 to 0.45 g / mL.

1-4. Content Ratio of Component (A), Component (B), and Component (C) As described above, when the content of component (B) relative to components (A) and (C) is too low, component (A) The reaction of a certain metallocene compound with the surface hydroxyl group in the component (C) is considered to result in the formation of fisheye because the component (A) is modified. In addition, when the content of the component (B) with respect to the components (A) and (C) is too large, fouling is caused to cause the polymerization to be unstable, and thus it is considered that the fish eye is easily generated.
Therefore, it is important to control the content ratio of the component (A), the component (B) and the component (C) as well as the Tv value of the inorganic oxide support which is the component (C) in order to reduce the fisheye. It is.
In the catalyst for olefin polymerization of the present invention, the content of the component (B) per 1 mol of the transition metal M in the component (A) is in the range of 330 to 12500 mol. The content of the component (B) per 1 mol of the transition metal M in the component (A) is preferably in the range of 330 to 2000 mol, and more preferably in the range of 330 to 1700 mol.
In the catalyst for olefin polymerization of the present invention, the content of the component (B) per 1 g of the component (C) is in the range of 5.0 to 12.0 mmol. Component (C) The content of the component (B) per 1 g is preferably in the range of 6.0 to 12.0 mmol, and more preferably in the range of 7.5 to 10.5 mmol.
In the olefin polymerization catalyst of the present invention, the content ratio of the component (A) to the component (C) is the content ratio of the component (A) to the component (B), and the component (B) to the component (C) There is no particular limitation as long as it satisfies the content ratio of

2. Process for Producing Olefin Polymerization Catalyst of the Present Invention In the process for producing an olefin polymerization catalyst of the present invention, the component (A), the component (B) and the component (C) are the transition in the component (A) The component (B) per mole of the metal M is in the range of 330 to 12500 mol, and the component (B) per gram of the component (C) is in the range of 5.0 to 12.0 mmol.
In the method for producing a catalyst for olefin polymerization of the present invention, the method for contacting the component (A) which is a metallocene compound, the component (B) which is an aluminoxane compound, and the component (C) which is an inorganic oxide carrier It will not be specifically limited if the quantitative ratio of (A), component (B), and component (C) is satisfy | filled, For example, the following method is employable arbitrarily.

After the component (A) and the component (B) are brought into contact with each other, the component (C) is brought into contact.
After bringing the component (A) into contact with the component (C), the component (B) is brought into contact.
After bringing the component (B) into contact with the component (C), the component (A) is brought into contact.
Of these contacting methods, (I) and (III) are preferred, and (I) is most preferred. In any contacting method, generally, in an inert atmosphere such as nitrogen or argon, generally aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene (usually having 6 to 12 carbon atoms), heptane, hexane, decane, dodecane A method is employed in which the components are brought into contact with or without stirring in the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon (usually having 5 to 12 carbon atoms) such as cyclohexane. This contact is usually performed at a temperature of -100 ° C to 200 ° C, preferably -50 ° C to 100 ° C, more preferably 0 ° C to 50 ° C, for 5 minutes to 50 hours, preferably 30 minutes to 24 hours, more preferably It is desirable to carry out for 30 minutes to 12 hours.
In addition, as the solvent used when contacting the component (A), the component (B) and the component (C), as described above, an aromatic hydrocarbon solvent in which certain components are soluble or poorly soluble, and certain solvents may be used. Any of aliphatic or alicyclic hydrocarbon solvents in which the components are insoluble or poorly soluble can be used.
When the contact reaction of each component is carried out stepwise, this may be used as it is as the solvent for the subsequent contact reaction without removing the solvent and the like used in the former step. In addition, liquid inactive hydrocarbons in which certain components are insoluble or sparingly soluble after the preceding catalytic reaction using a soluble solvent (for example, aliphatics such as pentane, hexane, decane, dodecane, cyclohexane, benzene, toluene, xylene, etc. Hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon) to recover the desired product as a solid, or once or partially removing the soluble solvent by drying or the like After removal of the product as a solid, the subsequent catalytic reaction of the desired product can also be carried out using any of the above-mentioned inert hydrocarbon solvents. In the present invention, multiple contact reactions of each component are not hindered.
Component (A), component (B), and component (C) are brought into contact with each other by any of the above-mentioned contact methods (I) to (III), and then the solvent is removed to obtain olefin polymerization. The catalyst can be obtained as a solid catalyst. The removal of the solvent is desirably carried out under normal pressure or reduced pressure, at 0 to 200 ° C., preferably at 20 to 150 ° C., for 1 minute to 50 hours, preferably 10 minutes to 10 hours.

3. Process for Producing Olefin Polymer Using Catalyst for Olefin Polymerization of the Present Invention The catalyst for olefin polymerization of the present invention can be used for olefin polymerization, in particular, homopolymerization of ethylene or copolymerization of ethylene and an α-olefin. After the molding process, a polymer with less FE can be produced.
The α-olefins which are comonomers include those having 3 to 30, preferably 3 to 8 carbon atoms, and specifically, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl- 1-Penten etc. are illustrated. The alpha-olefins can also be copolymerized with ethylene with two or more alpha-olefins. The copolymerization may be any of alternating copolymerization, random copolymerization and block copolymerization. When ethylene and another α-olefin are copolymerized, the amount of the other α-olefin can be optionally selected within the range of 90 mol% or less of the total monomers, but generally 40 mol%. It is selected in the range of preferably 30 mol% or less, more preferably 10 mol% or less. Of course, it is also possible to use a small amount of comonomers other than ethylene and α-olefin, in which case styrene, styrenes such as 4-methylstyrene, 4-dimethylaminostyrene, etc., 1,4-butadiene, 1,5- It has a polymerizable double bond such as dienes such as hexadiene, 1,4-hexadiene, 1,7-octadiene, cyclic compounds such as norbornene and cyclopentene, and oxygen-containing compounds such as hexenol, hexenoic acid and methyl octenoate Compounds can be mentioned.
In the present invention, the polymerization reaction can be carried out in the presence of the catalyst for olefin polymerization of the present invention, preferably by slurry polymerization or gas phase polymerization. In the case of slurry polymerization, aliphatic hydrocarbons such as isobutane, hexane, heptane and the like, aromatic hydrocarbons such as benzene, toluene, xylene and the like, alicyclic resins such as cyclohexane, methylcyclohexane and the like in a state where oxygen, water etc. are substantially cut off Ethylene and the like are polymerized in the presence or absence of an inert hydrocarbon solvent selected from group hydrocarbons and the like. Needless to say, liquid monomers such as liquid ethylene and liquid propylene can also be used as the solvent. In the case of gas phase polymerization, ethylene or the like is polymerized in a reactor in which a gas stream of ethylene or comonomer is introduced, circulated or circulated. In the present invention, a further preferred polymerization is gas phase polymerization. The polymerization conditions are such that the temperature is 0 to 250 ° C., preferably 20 to 110 ° C., more preferably 60 to 100 ° C., and a temperature of 60 to 90 ° C. tends to introduce more long chain branches. is there. The pressure is in the range of normal pressure to 10 MPa, preferably normal pressure to 4 MPa, more preferably 0.5 to 2 MPa, and polymerization time is 5 minutes to 10 hours, preferably 5 minutes to 5 hours That's normal.
Although the molecular weight of the formed polymer can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, the molecular weight can be controlled more effectively by adding hydrogen to the polymerization reaction system. Can.
Moreover, even if it adds the component for the purpose of water removal in the polymerization system, a so-called scavenger, it can be implemented without any problem. Such scavengers include organic aluminum compounds such as trimethylaluminum, triethylaluminum and triisobutylaluminum, the aforementioned organic aluminum oxy compounds, modified organic aluminum compounds containing branched alkyl, organic zinc compounds such as diethyl zinc and dibutyl zinc, diethyl Organic magnesium compounds such as magnesium, dibutyl magnesium and ethylbutyl magnesium, and Grignard compounds such as ethyl magnesium chloride and butyl magnesium chloride are used. Among these, triethylaluminum, triisobutylaluminum and ethylbutylmagnesium are preferable, and triethylaluminum is particularly preferable. The present invention can be applied to a multistage polymerization system of two or more stages having different polymerization conditions such as hydrogen concentration, amount of monomers, polymerization pressure, polymerization temperature and the like without any problem.

4. Olefin polymers produced using the olefin polymerization catalyst of the present invention The olefin polymers produced using the olefin polymerization catalyst of the present invention, in particular ethylene polymers, are compared to conventional metallocene polyethylene, It is characterized by having few fish eyes (FE) after fabrication processing, and being excellent in appearance.
In the olefin polymer obtained by the production method of the present invention, when a film obtained by press-molding 0.1 g of a kneaded sample of an olefin polymer is observed by a polarization microscope, the number of FEs per 0.1 g of a molded product is , Preferably 1.0 or less, more preferably 0.5 or less, still more preferably 0.4 or less, particularly preferably 0 or less.

  The olefin polymer obtained by the production method of the present invention preferably further has the following characteristics from the viewpoint of excellent moldability and mechanical properties.

(1) MFR
The MFR (melt flow rate, 190 ° C., 2.16 kg load) of the olefin polymer is preferably 0.001 to 1000 g / 10 min, more preferably 0.01 to 100 g / 10 min, still more preferably 0. It is preferably from 05 to 50 g / 10 min, particularly preferably from 0.1 to 50 g / 10 min.
In addition, MFR of an olefin polymer is a value when it measures based on JISK6760 (190 degreeC, 2.16 kg load).

(2) Density The density of the olefin polymer is preferably 0.85 to 0.97 g / mL, more preferably 0.88 to 0.95 g / mL, still more preferably 0.90 to 0.94 g / mL. It is.
The density of the olefin polymer is a value measured in accordance with JIS K7112.

  EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. The evaluation methods used in the examples are as follows, and the following catalyst synthesis step and polymerization step were all performed under a purified nitrogen atmosphere, and the solvent used was dehydrated and purified with molecular sieve 4A. Was used.

[Various evaluation (measurement) methods]
(1) MFR:
It measured at 190 degreeC and 2.16 kg load based on JISK6760. FR (flow rate ratio) was calculated from the ratio of MFR (10 kg) to MFR (= MFR 10 kg / MFR), which is MFR similarly measured under the conditions of 190 ° C. and 10 kg load.

(2) Copolymer density:
The olefin polymer was formed into a press sheet and measured in accordance with JIS K7112.

(3) Number of FEs per 0.1 g of molded body:
Using a DSM small twin screw kneader (Xplore MC15), 12.0 g of a sample prepared by adding 0.1 g of BHT to an olefin polymer is kneaded at 190 ° C., 50 rpm for 2 minutes, and 0.1 g of the kneaded product is obtained at 180 ° C. for 5 minutes. After hot-pressing with the above, the film was formed to a thickness of 50 μm by cold-pressing for 10 minutes. Then, this press film is observed in a 3 cm × 7 cm range with a polarization microscope (ECLIPSE LV100N POL, manufactured by NIKON), catalyst residues and fibers etc. observed as opaque particles from the number of fish eyes of 10 μm or more in the range The number of contaminants minus the number of contaminants was counted.

(4) Activity (g-PE / g-Cat / hr):
The polymer yield was divided by the amount of catalyst charged and the polymerization time to calculate the activity value.

(5) Tv value After putting 10 g of components (C) in the crucible which measured the empty weight under nitrogen, the weight of the crucible containing a component (C) is measured. Put the crucible containing the component (C) after weight measurement into an electric furnace (F150U-15C8S, manufactured by Hoshikazu Riko Co., Ltd.) and raise from room temperature to 200 ° C at a heating rate of 6 ° C / min while flowing nitrogen at 4 L / min Warm and heat at 200 ° C. for 1 hour. After heating, the crucible was removed, weighed immediately, and placed again in the electric furnace. Subsequently, while flowing nitrogen at 4 L / min, the temperature was raised from 200 ° C. to 1100 ° C. at a temperature rising rate of 8 ° C./min, and heated at 1100 ° C. for 2 hours. After heating, the reactor was cooled to room temperature while flowing nitrogen at 4 L / min, the crucible was taken out, and the weight was measured immediately. The mass (m1) after heating from room temperature to 200 ° C. under nitrogen and the mass (m 2) after heating from 200 ° C. to 1100 ° C. under nitrogen are calculated based on the respective weight measurement results, and , Tv values were calculated.
Tv value = {(m1-m2) / m1} × 100

[Component (A): Synthesis of Metallocene Compound]
(1) A metallocene compound A represented by the following formula (5):
Synthesis of dimethylsilylene (3-methyl-4- (2- (5-methyl) -furyl) -indenyl) (2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride

(1-1) Synthesis of 1-methyl-7- (2- (5-methyl) -furyl) -indene Synthesis of (1--1-a) 2-bromophenyl-2-chloroethyl ketone In a 100 mL flask, 2 -Bromobenzoic acid (5.30 g, 26.4 mmol) and 25 mL thionyl chloride were added and refluxed for 2 hours. After the reaction, excess thionyl chloride was distilled off under reduced pressure, and 5.50 g of the acid chloride product obtained was used for the next reaction without purification.
Acid chloride (5.00 g, 22.7 mmol) and 50 mL of dichloromethane were added to a 100 mL flask to make a solution, then aluminum chloride (3.02 g, 22.7 mmol) was further added, and ethylene was blown at 20 ° C. for 4 hours . The reaction is quenched with 4N hydrochloric acid, and after separating the organic phase and the aqueous phase, the aqueous phase is washed three times with 50 mL of methyl-t-butyl ether, the organic phases are collected, and three times with 50 mL of water, saturated sodium bicarbonate water The mixture was washed with 100 mL followed by 100 mL of saturated brine. After drying over sodium sulfate, the solvent was distilled off under reduced pressure to obtain 4.80 g (yield 85%) of 2-bromophenyl-2-chloroethyl ketone. It was used for the next reaction without further purification.

Synthesis of (1--1-b) 7-bromo-1-indanone In a 100 mL flask, aluminum chloride (7.40 g, 55.6 mmol) and sodium chloride (2.15 g, 37.1 mmol) are added and heated to 130 ° C. After, 2-bromophenyl-2-chloroethyl ketone (4.60 g, 18.5 mmol) was added slowly and the mixture was stirred at 160 ° C. for 1 hour. After the reaction, it was cooled to 30 ° C. and quenched with ice water.
After adjusting to pH = 5 with concentrated hydrochloric acid, the organic phase and the aqueous phase are separated, the aqueous phase is washed 3 times with 100 mL of dichloromethane, the organic phase is collected, washed with 100 mL of water, 100 mL of saturated brine, and with sodium sulfate After drying, the solvent was distilled off under reduced pressure to obtain a crude product. Furthermore, it refine | purified in the silica gel column (petroleum ether / ethyl acetate = 30/1), and obtained 1.60 g (yield 33%) of 7-bromo- 1-indanone.

Synthesis of (1--1-c) 7- (2- (5-methyl) -furyl) -1-indanone In a 100 mL flask, 2-methylfuran (0.933 g, 11.4 mmol) and 10 mL of THF were added to make a solution After that, n-butyllithium / hexane solution (2.5 M, 4.70 mL, 11.4 mmol) was added at -30.degree. C., and stirred at room temperature for 2 hours. Zinc chloride (1.55 g, 11.4 mmol) and 10 mL of THF were added to a separately prepared 100 mL flask, followed by addition of the above reaction solution at 0 ° C. and stirring at room temperature for 1 hour. Even further the prepared 100mL flask iodide _{(I) (90mg, 0.473mmol)} , Pd (dppf) Cl 2 (177mg, 0.236mmol), 7- bromo-1-indanone (2.00 g, 9.45 mmol The above reaction product was added to a suspension obtained by adding 10 mL of DMA and 10 mL of DMA, and refluxing was performed for 15 hours. The mixture was cooled to room temperature, 50 mL of water was added, and extraction was performed twice with 50 mL of ethyl acetate. The organic phase was collected, washed twice with 50 mL of water, and 50 mL of saturated brine, and dried over sodium sulfate, and then the solvent was evaporated under reduced pressure to obtain a crude product. Further, the residue was purified by silica gel column (petroleum ether / ethyl acetate = 20/1) to obtain 0.70 g (yield 35%) of 7- (2- (5-methyl) -furyl) -1-indanone.

Synthesis of (1--1-d) 1-methyl-7- (2- (5-methyl) -furyl) -indene 7- (2- (5-methyl) -furyl) -1-indanone (1) in a 100 mL flask After adding .40 g, 6.59 mmol) and 20 mL of THF to obtain a solution, methyllithium / diethyl ether solution (1.6 M, 7.5 mL, 11.9 mmol) was added at -78.degree. C., and the mixture was stirred at room temperature for 10 hours. The reaction was quenched with 20 mL of saturated aqueous ammonium chloride solution and volatiles were removed in vacuo. The remaining solution was extracted twice with 50 mL of ethyl acetate, and the organic phase was collected, washed with 50 mL of saturated brine, dried over sodium sulfate, and the solvent was evaporated under reduced pressure to obtain a crude product. It was used for the next reaction without further purification.
The above crude product and 30 mL of toluene were added to a 100 mL flask to make a solution, then p-toluenesulfonic acid (62.0 mg, 0.330 mmol) was added, and the mixture was stirred at 130 ° C. for 2 hours. While stirring, generated water was removed using a Dean-Stark trap. It cooled to room temperature, 30 mL of saturated sodium hydrogencarbonate aqueous solution was added, and the organic phase was isolate | separated. The aqueous phase was extracted three times with 50 mL of ethyl acetate, then the organic phase was collected, washed with 50 mL of saturated brine, and dried over sodium sulfate, and then the solvent was evaporated under reduced pressure to obtain a crude product. Furthermore, it refine | purified in the silica gel column (petroleum ether), and obtained 0.850 g (yield 61%) of 1-methyl 7- (2- (5-methyl) furyl) -indene.

Synthesis of (1-2) (2,3,4,5-tetramethylcyclopentadienyl) dimethylchlorosilane In a 200 mL flask, 2.40 g (19.6 mmol) of tetramethylcyclopentadiene and 40 mL of THF were added to make a solution After cooling to −78 ° C., 12.0 mL (30.0 mmol) of n-butyllithium / hexane solution (2.5 M) was added, and the mixture was returned to room temperature and stirred for 3 hours. In a separately prepared 200 mL flask, 5.00 g (38.7 mmol) of dimethyldichlorosilane and 20 mL of THF were added, cooled to −78 ° C., and the above reaction solution was added. It returned to room temperature and stirred for 12 hours. The volatiles were distilled off under reduced pressure to obtain 4.00 g of a yellow liquid. The resulting yellow liquid was used for the next reaction without further purification.

Synthesis of (1-3) (3-Methyl-4- (2- (5-methyl) -furyl) -indenyl) (2,3,4,5-tetramethylcyclopentadienyl) dimethylsilane In a 100 mL flask, After adding 2.60 g (12.4 mmol) of 1-methyl-7- (2- (5-methyl) -furyl) -indene and 40 mL of THF to form a solution, the solution is cooled to -78 ° C to obtain n-butyllithium / hexane The solution (2.5 M) 5.2 mL (13.0 mmol) was added, and it returned to room temperature and stirred for 3 hours. The crude yellow liquid 3.40g (15.8 mmol) obtained by (1-2) and THF10mL were added to the 200 mL flask prepared separately, and it cooled to -78 degreeC, and added the said reaction solution. It returned to room temperature and stirred for 12 hours. The reaction product was slowly added to 40 mL of ice water and extracted twice with 200 mL of ethyl acetate. The obtained organic phase was washed with 50 mL of saturated brine and dried over anhydrous sodium sulfate. The sodium sulfate is filtered and the solution is evaporated under reduced pressure and purified on a silica gel column (petroleum ether) to give (3-methyl-4- (2- (5-methyl) -furyl) -indenyl) (2,3, 3 1.40 g (25% yield) of a yellow oil of 4,5-tetramethylcyclopentadienyl) dimethylsilane was obtained.

Synthesis of (1-4) dimethylsilylene (3-methyl-4- (2- (5-methyl) -furyl) -indenyl) (2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride 200 mL flask In addition, 2.20 g (5.70 mmol) of (3-methyl-4- (2- (5-methyl) -furyl) -indenyl) (2,3,4,5-tetramethylcyclopentadienyl) dimethylsilane, 30 mL of diethyl ether was added and cooled to -78 ° C. The n-butyllithium / n-hexane solution (2.5M) 4.8mL (11.9 mmol) was dripped here, and it returned to room temperature, and stirred for 3 hours. The solvent of the reaction mixture was evaporated under reduced pressure, 60 mL of dichloromethane was added, and the mixture was cooled to -78 ° C. Thereto, 1.40 g (6.01 mmol) of zirconium tetrachloride was added, and the mixture was stirred overnight while gradually returning to room temperature. The solvent was distilled off under reduced pressure from the filtrate obtained by filtering the reaction solution, whereby 3.0 g of a yellow powder was obtained. The powder is washed with 25 mL of toluene and dimethylsilylene (3-methyl-4- (2- (5-methyl) -furyl) -indenyl) (2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride Of the yellow powder was obtained (yield 26%).
¹ H-NMR value (CDCl ₃ ): δ 0.94 (s, 3 H), δ 1.19 (s, 3 H), δ 1.90 (s, 3 H), δ 1.95 (s, 3 H), δ 1.98 ( s, 3 H), δ 2.0 4 (s, 3 H), δ 2. 28 (s, 3 H), δ 2. 38 (s, 3 H), δ 5.5 2 (s, 1 H), δ 6.07 (d, 1 H), δ 6.38 (d, 1 H), δ 7.04 (dd, 1 H), δ 7.37 (d, 1 H), δ 7.45 (d, 1 H).

(2) A metallocene compound B represented by the following formula (6):
Synthesis of dimethylsilylene (3-methyl-4-phenyl-indenyl) (2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride

(2-1) Synthesis of 7-bromo-1-indanone The synthesis is carried out in the same procedure as metallocene compounds A (1-1-a) to (1-1-b), and 10.60 g of 7-bromo-1-indanone (Yield 33%) was obtained.

(2-2) Synthesis of 3-methyl-4-bromoindene 10.00 g (47.38 mmol) of 7-bromo-1-indanone and 100 mL of toluene are added to a 200 mL flask to make a solution, and then methylmagnesium bromide is formed at 0 ° C. /23.69 mL (3 M, 71.07 mmol) of diethyl ether solution was added and stirred at 15 ° C. for 12 hours. The reaction solution was poured into 200 mL of ice water, and the precipitated solid was filtered and washed with 60 mL of ethyl acetate three times. The organic phase was separated from the filtrate and then washed twice with 100 mL of water and dried over anhydrous sodium sulfate. The sodium sulfate was filtered and the solvent was distilled off under reduced pressure to obtain 10.70 g of a crude product of 7-bromo-1-methylindanol.
After adding 10.70 g (47.12 mmol) of the crude product of 7-bromo-1-methylindanol and 300 mL of toluene to a 500 mL flask to obtain a solution, 179.25 mg of p-toluenesulfonic acid monohydrate is obtained at 15 ° C. (942.4 μmol) was added and stirred at 110 ° C. for 2 hours. While stirring, generated water was removed using a Dean-Stark trap. It cooled to room temperature, 100 mL of saturated sodium hydrogencarbonate aqueous solution was added, and the organic phase was isolate | separated. The aqueous phase was extracted three times with 50 mL of ethyl acetate, and then the organic phase was collected, washed three times with 50 mL of saturated brine, and dried over sodium sulfate. The sodium sulfate was filtered off and the solvent was distilled off under reduced pressure to obtain a crude product. Further, the residue was purified by silica gel column (petroleum ether) to obtain 5.80 g (yield 58.87%) of 3-methyl-4-bromoindene.

(2-3) Synthesis of 3-methyl-4-phenylindene In a 300 mL flask, 4.06 g (33.29 mmol) of phenylboronic acid, 5.80 g (27.74 mmol) of 3-methyl-4-bromoindene and dimethoxyethane were added. After 70 mL was added to make a solution, 8.83 g (41.61 mmol) of potassium phosphate, 30 mL of water, 1.32 g (2.77 mmol) of dicyclohexyl- [2- (2,4,6-triisopropylphenyl) phenyl] phosphane ), 0.798 g (1.39 mmol) of Pd (dba) 2 were sequentially added, and the mixture was stirred at 85 ° C. for 12 hours. The reaction solution was cooled to room temperature and extracted three times with 150 mL of ethyl acetate, and then the organic phase was collected, washed three times with 100 mL of saturated brine, and dried over sodium sulfate. After filtration of sodium sulfate, the filtrate was concentrated and purified by silica gel column to obtain 5.7 g (yield 99.6%) of 3-methyl-4-phenylindene.

(2-4) Synthesis of (2,3,4,5-tetramethylcyclopentadienyl) dimethylchlorosilane The synthesis is carried out in the same procedure as the metallocene compound A (1-2) to give 2,3,4,5-tetra A yellow suspension of methylcyclopentadienyl) dimethylchlorosilane was obtained. The resulting yellow suspension was used for the next reaction without further purification.

Synthesis of (2-5) (3-Methyl-4-phenylindenyl) (2,3,4,5-tetramethylcyclopentadienyl) dimethylsilane In a 200 mL flask, 3-methyl-4-phenylindene5. After 70 g (27.63 mmol) and 60 mL of THF were added to make a solution, the solution was cooled to -78 ° C, 11.6 mL (29.0 mmol) of n-butyllithium / hexane solution (2.5 M) was added, and returned to room temperature Stir for 3 hours. In a separately prepared 200 mL flask, 7.9 g (36.78 mmol) of the crude yellow suspension obtained in (2-4) and 60 mL of THF were added, cooled to −78 ° C., and the above reaction solution was added. . It returned to room temperature and stirred for 1 hour. The reaction product was slowly added to 100 mL of ice water and extracted three times with 100 mL of ethyl acetate. The resulting organic phase was dried over anhydrous sodium sulfate. The sodium sulfate is filtered, the solution is evaporated under reduced pressure, and the residue is purified by silica gel column (petroleum ether), (3-methyl-4-phenylindenyl) (2,3,4,5-tetramethylcyclopentadienyl) 6.68 g (yield 64%) of a yellow oil of dimethylsilane was obtained.

(2-6) Synthesis of dimethylsilylene (3-methyl-4-bromoindenyl) (2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride (3-methyl-4- (2- (5) (Methyl) -furyl) -indenyl) (2,3,4,5-tetramethylcyclopentadienyl) dimethylsilane 2.3-g (5.70 mmol) instead of (3-methyl-4-phenylindenyl) ( Using 6.80 g (17.68 mmol) of 2,3,4,5-tetramethylcyclopentadienyl) dimethylsilane, the synthesis is carried out in the same manner as for the metallocene compound A (1-4), and dimethylsilylene (3- 6.60 g (yield 69) of a yellow powder of methyl-4-bromoindenyl) (2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride Obtained as%).
1 H-NMR value (CDCl 3): δ 0.94 (s, 3 H), δ 1.22 (s, 3 H), δ 1.89 (s, 3 H), δ 1.93 (s, 3 H), δ 1.99 (s, 3) 3H), δ 2.02 (s, 3 H), δ 2.06 (s, 3 H), δ 5.47 (s, 1 H), δ 7.05 to 7.09 (m, 1 H), δ 7.14 (d, 1 H) ), Δ 7.40 (m, 4 H), δ 7. 50 (d, 2 H).

Example 1
(1) Preparation of catalyst for olefin polymerization Silica A (pore volume: 1.58 mL / g, BET surface area: 310 m ² / g) calcined under nitrogen atmosphere to have a Tv value of 1.9 under nitrogen atmosphere, 300 mL three-necked The flask was charged with 3.76 g, and 24.0 mL of dehydrated toluene was added and stirred to form a slurry. 20.6 mg of the above metallocene compound A was placed in a separately prepared 100 mL recovery flask under a nitrogen atmosphere, and dissolved in 21.0 mL of dehydrated toluene. 11.0 mL of 20% methylaluminoxane (MAO) / toluene solution (manufactured by Albemarle) was added to a toluene solution of metallocene compound A at room temperature, and stirred for 30 minutes. While heating and stirring a 300 mL three-necked flask containing a toluene slurry of silica A in a 40 ° C. oil bath, the entire toluene solution of the reactant of metallocene compound A and methylaluminoxane was added.
After stirring at 40 ° C. for 1 hour, the mixture was allowed to stand for 10 minutes, and the supernatant was removed by decantation. After removing the supernatant, the toluene solvent was distilled off under reduced pressure at 40 ° C., and the catalyst for olefin polymerization of Example 1 was obtained by drying under reduced pressure for 30 minutes.

(2) Production of ethylene / 1-hexene copolymer An ethylene / 1-hexene copolymer was produced using the catalyst for olefin polymerization of Example 1 obtained by the preparation of the above (1) catalyst.
That is, 30 mL of 1-hexene, 0.30 mmol of triethylaluminum, 800 mL of diluted hydrogen of H ₂ / N ₂ = 5% by mass, and 800 mL of isobutane are added to a 1.6 L autoclave with induction stirring device, and the temperature is raised to 85 ° C. The ethylene partial pressure was maintained at 0.7 MPa by introduction. Subsequently, 0.0247 g of the catalyst for olefin polymerization of Example 1 obtained in the above (1) was injected with nitrogen, and polymerization was continued for 60 minutes while maintaining an ethylene partial pressure of 0.7 MPa and a temperature of 85 ° C.
During the polymerization reaction, additional supply of hydrogen was carried out at a supply rate proportional to the ethylene consumption rate. Thus, the ethylene / 1-hexene copolymer obtained in Example 1 was 140.1 g.

Example 2
(1) Preparation of catalyst for olefin polymerization Silica A (pore volume: 1.58 mL / g, BET surface area: 310 m ² / g) calcined under nitrogen atmosphere to have a Tv value of 1.9 under nitrogen atmosphere, 300 mL three-necked The flask was charged with 3.19 g, and 22.0 mL of dehydrated toluene was added and stirred to form a slurry. Under nitrogen atmosphere, 9.0 mg of the above metallocene compound A was added to a separately prepared 100 mL recovery flask, and dissolved with 9.0 mL of dehydrated toluene. 9.0 mL of a 20% methylaluminoxane (MAO) / toluene solution (manufactured by Albemarle) was added to a toluene solution of metallocene compound A at room temperature, and the mixture was stirred for 30 minutes. While heating and stirring a 300 mL three-necked flask containing a toluene slurry of silica A in a 40 ° C. oil bath, the entire toluene solution of the reactant of metallocene compound A and methylaluminoxane was added.
After stirring at 40 ° C. for 1 hour, the mixture was allowed to stand for 10 minutes, and the supernatant was removed by decantation. After removing the supernatant, the toluene solvent was distilled off under reduced pressure at 40 ° C., and the catalyst for olefin polymerization of Example 2 was obtained by drying under reduced pressure for 30 minutes.

(2) Production of ethylene / 1-hexene copolymer An ethylene / 1-hexene copolymer was produced using the catalyst for olefin polymerization of Example 2 obtained by the preparation of the above (1) catalyst.
That is, 47 mL of 1-hexene, 0.30 mmol of triethylaluminum, 1500 mL of diluted hydrogen of H ₂ / N ₂ = 5% by mass, and 800 mL of isobutane are added to a 1.6 L autoclave with induction stirring device, and the temperature is raised to 85 ° C. The ethylene partial pressure was maintained at 1.4 MPa by introduction. Subsequently, 0.0235 g of the catalyst for olefin polymerization of Example 2 obtained in the above (1) was injected with nitrogen, and polymerization was continued for 60 minutes while maintaining an ethylene partial pressure of 1.4 MPa and a temperature of 85 ° C.
During the polymerization reaction, additional supply of hydrogen was carried out at a supply rate proportional to the ethylene consumption rate. The amount of the ethylene / 1-hexene copolymer thus obtained in Example 2 was 114.4 g.

[Example 3]
(1) Preparation of catalyst for olefin polymerization Silica A (pore volume: 1.58 mL / g, BET surface area: 310 m ² / g) calcined under nitrogen atmosphere to a Tv value of 1.7 under nitrogen atmosphere, 300 mL three-necked The flask was charged with 5.02 g, and 32.5 mL of dehydrated toluene was added and stirred to form a slurry. 13.8 mg of the above metallocene compound A was placed in a separately prepared 100 mL recovery flask under a nitrogen atmosphere, and was dissolved with 13.3 mL of dehydrated toluene. 13.8 mL of a 20% methylaluminoxane (MAO) / toluene solution (manufactured by Albemarle) was added to a toluene solution of metallocene compound A at room temperature, and the mixture was stirred for 30 minutes. While heating and stirring a 300 mL three-necked flask containing a toluene slurry of silica A in a 40 ° C. oil bath, the entire toluene solution of the reactant of metallocene compound A and methylaluminoxane was added.
After stirring at 40 ° C. for 1 hour, the mixture was allowed to stand for 10 minutes, and the supernatant was removed by decantation. After removing the supernatant, the toluene solvent was evaporated under reduced pressure at 40 ° C., and the catalyst for olefin polymerization of Example 3 was obtained by drying under reduced pressure for 30 minutes.

(2) Production of ethylene / 1-hexene copolymer An ethylene / 1-hexene copolymer was produced using the catalyst for olefin polymerization of Example 3 obtained by the preparation of the above (1) catalyst.
That is, 30 mL of 1-hexene, 0.30 mmol of triethylaluminum, 1800 mL of diluted hydrogen of H ₂ / N ₂ = 5% by mass, and 800 mL of isobutane are added to a 1.6 L autoclave equipped with an induction stirrer, and ethylene is heated to 85 ° C. The ethylene partial pressure was maintained at 0.7 MPa by introduction. Subsequently, 0.0298 g of the catalyst for olefin polymerization of Example 3 obtained in the above (1) was pressurized with nitrogen, and polymerization was continued for 60 minutes while maintaining an ethylene partial pressure of 0.7 MPa and a temperature of 85 ° C.
During the polymerization reaction, additional supply of hydrogen was carried out at a supply rate proportional to the ethylene consumption rate. Thus, the amount of the ethylene / 1-hexene copolymer obtained in Example 3 was 80.7 g.

Example 4
(1) Preparation of catalyst for olefin polymerization Silica A (pore volume: 1.58 mL / g, BET surface area: 310 m ² / g) calcined under nitrogen atmosphere to a Tv value of 1.7 under nitrogen atmosphere, 300 mL three-necked The flask was charged with 5.43 g, 35.0 mL of dehydrated toluene was added, and the mixture was stirred and slurried. 31.0 mg of the above metallocene compound A was placed in a 100 mL eggplant flask prepared separately under a nitrogen atmosphere, and dissolved in 30.0 mL of dehydrated toluene. 15.0 mL of 20% methylaluminoxane (MAO) / toluene solution (manufactured by Albemarle) was added to a toluene solution of metallocene compound A at room temperature and stirred for 30 minutes. While heating and stirring a 300 mL three-necked flask containing a toluene slurry of silica A in a 40 ° C. oil bath, the entire toluene solution of the reactant of metallocene compound A and methylaluminoxane was added.
After stirring at 40 ° C. for 1 hour, the mixture was allowed to stand for 10 minutes, and the supernatant was removed by decantation. After removing the supernatant, the toluene solvent was distilled off under reduced pressure at 40 ° C., and the catalyst for olefin polymerization of Example 4 was obtained by drying under reduced pressure for 30 minutes.

(2) Production of ethylene / 1-hexene copolymer An ethylene / 1-hexene copolymer was produced using the catalyst for olefin polymerization of Example 4 obtained by the preparation of the above (1) catalyst.
That is, 47 mL of 1-hexene, 0.30 mmol of triethylaluminum, 1800 mL of diluted hydrogen of H ₂ / N ₂ = 5 mass%, and 800 mL of isobutane are added to a 1.6 L autoclave equipped with an induction stirrer, and the temperature is raised to 85 ° C. The ethylene partial pressure was maintained at 0.7 MPa by introduction. Subsequently, 0.0345 g of the catalyst for olefin polymerization of Example 4 obtained in the above (1) was pressured in with nitrogen, and polymerization was continued for 60 minutes while maintaining an ethylene partial pressure of 0.7 MPa and a temperature of 85 ° C.
During the polymerization reaction, additional supply of hydrogen was carried out at a supply rate proportional to the ethylene consumption rate. The amount of the ethylene / 1-hexene copolymer thus obtained in Example 4 was 112.6 g.

[Example 5]
(1) Preparation of catalyst for olefin polymerization Silica A (pore volume: 1.58 mL / g, BET surface area: 310 m ² / g) calcined under nitrogen atmosphere to a Tv value of 1.4 under nitrogen atmosphere, 300 mL three-necked The flask was charged with 5.18 g, and 32.5 mL of dehydrated toluene was added and stirred to form a slurry. 13.8 mg of the above metallocene compound A was placed in a separately prepared 100 mL recovery flask under a nitrogen atmosphere, and was dissolved with 13.3 mL of dehydrated toluene. 13.8 mL of a 20% methylaluminoxane (MAO) / toluene solution (manufactured by Albemarle) was added to a toluene solution of metallocene compound A at room temperature, and the mixture was stirred for 30 minutes. While heating and stirring a 300 mL three-necked flask containing a toluene slurry of silica A in a 40 ° C. oil bath, the entire toluene solution of the reactant of metallocene compound A and methylaluminoxane was added.
After stirring at 40 ° C. for 1 hour, the mixture was allowed to stand for 10 minutes, and the supernatant was removed by decantation. After removing the supernatant, the toluene solvent was distilled off under reduced pressure at 40 ° C., and the catalyst for olefin polymerization of Example 5 was obtained by drying under reduced pressure for 30 minutes.

(2) Production of ethylene / 1-hexene copolymer An ethylene / 1-hexene copolymer was produced using the catalyst for olefin polymerization of Example 5 obtained by the preparation of the above (1) catalyst.
That is, 30 mL of 1-hexene, 0.30 mmol of triethylaluminum, 1800 mL of diluted hydrogen of H ₂ / N ₂ = 5% by mass, and 800 mL of isobutane are added to a 1.6 L autoclave equipped with an induction stirrer, and ethylene is heated to 85 ° C. The ethylene partial pressure was maintained at 0.7 MPa by introduction. Subsequently, 0.0337 g of the catalyst for olefin polymerization of Example 5 obtained in the above (1) was injected with nitrogen, and polymerization was continued for 60 minutes while maintaining an ethylene partial pressure of 0.7 MPa and a temperature of 85 ° C.
During the polymerization reaction, additional supply of hydrogen was carried out at a supply rate proportional to the ethylene consumption rate. Thus, the ethylene / 1-hexene copolymer obtained in Example 5 was 88.3 g.

[Example 6]
(1) Preparation of catalyst for olefin polymerization: Silica A (pore volume: 1.58 mL / g, BET surface area: 310 m ² / g) calcined under nitrogen atmosphere to a Tv value of 1.1 under nitrogen atmosphere, 500 mL three ports The flask was charged with 11.12 g, and 73.0 mL of dehydrated toluene was added and stirred to form a slurry. 31.0 mg of the above metallocene compound A was placed in a 200 mL eggplant flask prepared separately under a nitrogen atmosphere, and dissolved in 32.0 mL of dehydrated toluene. 31.0 mL of 20% methylaluminoxane (MAO) / toluene solution (manufactured by Albemarle) was added to a toluene solution of metallocene compound A at room temperature, and the mixture was stirred for 30 minutes. While heating and stirring a 500 mL three-necked flask containing a toluene slurry of silica A in a 40 ° C. oil bath, the entire toluene solution of the reactant of metallocene compound A and methylaluminoxane was added.
After stirring at 40 ° C. for 1 hour, the mixture was allowed to stand for 10 minutes, and the supernatant was removed by decantation. After removing the supernatant, the toluene solvent was distilled off under reduced pressure at 40 ° C., and the catalyst for olefin polymerization of Example 6 was obtained by drying under reduced pressure for 30 minutes.

(2) Production of ethylene / 1-hexene copolymer An ethylene / 1-hexene copolymer was produced using the catalyst for olefin polymerization of Example 6 obtained by the preparation of the above (1) catalyst.
That is, 30 mL of 1-hexene, 0.30 mmol of triethylaluminum, 1800 mL of diluted hydrogen of H ₂ / N ₂ = 5% by mass, and 800 mL of isobutane are added to a 1.6 L autoclave equipped with an induction stirrer, and ethylene is heated to 85 ° C. The ethylene partial pressure was maintained at 0.7 MPa by introduction. Subsequently, 0.0326 g of the catalyst for olefin polymerization of Example 6 obtained in the above (1) was injected with nitrogen, and polymerization was continued for 60 minutes while maintaining an ethylene partial pressure of 0.7 MPa and a temperature of 85 ° C.
During the polymerization reaction, additional supply of hydrogen was carried out at a supply rate proportional to the ethylene consumption rate. The amount of the ethylene / 1-hexene copolymer thus obtained in Example 6 was 95.9 g.

[Example 7]
(1) Preparation of catalyst for olefin polymerization: Silica A (pore volume: 1.58 mL / g, BET surface area: 310 m ² / g) calcined under nitrogen atmosphere to a Tv value of 1.1 under nitrogen atmosphere, 500 mL three ports The flask was charged with 10.56 g, and 70.0 mL of dehydrated toluene was added and stirred to form a slurry. 58.0 mg of the above metallocene compound A was placed in a 200 mL eggplant flask prepared separately under a nitrogen atmosphere, and dissolved in 29.0 mL of dehydrated toluene. 29.0 mL of 20% methylaluminoxane (MAO) / toluene solution (manufactured by Albemarle) was added to a toluene solution of metallocene compound A at room temperature and stirred for 30 minutes. While heating and stirring a 500 mL three-necked flask containing a toluene slurry of silica A in a 40 ° C. oil bath, the entire toluene solution of the reactant of metallocene compound A and methylaluminoxane was added.
After stirring at 40 ° C. for 1 hour, the mixture was allowed to stand for 10 minutes, and the supernatant was removed by decantation. After removing the supernatant, the toluene solvent was distilled off under reduced pressure at 40 ° C., and the catalyst for olefin polymerization of Example 7 was obtained by drying under reduced pressure for 30 minutes.

(2) Production of ethylene / 1-hexene copolymer An ethylene / 1-hexene copolymer was produced using the catalyst for olefin polymerization of Example 7 obtained by the preparation of the above (1) catalyst.
That is, 30 mL of 1-hexene, 0.30 mmol of triethylaluminum, 1800 mL of diluted hydrogen of H ₂ / N ₂ = 5% by mass, and 800 mL of isobutane are added to a 1.6 L autoclave equipped with an induction stirrer, and ethylene is heated to 85 ° C. The ethylene partial pressure was maintained at 0.7 MPa by introduction. Subsequently, 0.0311 g of the catalyst for olefin polymerization of Example 7 obtained in the above (1) was injected with nitrogen, and polymerization was continued for 60 minutes while maintaining the ethylene partial pressure 0.7 MPa and the temperature 85 ° C.
During the polymerization reaction, additional supply of hydrogen was carried out at a supply rate proportional to the ethylene consumption rate. Thus, the amount of the ethylene / 1-hexene copolymer obtained in Example 7 was 130.8 g.

[Example 8]
(1) Preparation of catalyst for olefin polymerization: Silica A (pore volume: 1.58 mL / g, BET surface area: 310 m ² / g) calcined under nitrogen atmosphere to a Tv value of 1.1 under nitrogen atmosphere, 500 mL three ports The flask was charged with 11.21 g, and 73.0 mL of dehydrated toluene was added and stirred to form a slurry. 63.0 mg of the above metallocene compound A was placed in a 200 mL eggplant flask prepared separately under a nitrogen atmosphere, and dissolved in 31.0 mL of dehydrated toluene. 31.0 mL of 20% methylaluminoxane (MAO) / toluene solution (manufactured by Albemarle) was added to a toluene solution of metallocene compound A at room temperature, and the mixture was stirred for 30 minutes. While heating and stirring a 500 mL three-necked flask containing a toluene slurry of silica A in a 40 ° C. oil bath, the entire toluene solution of the reactant of metallocene compound A and methylaluminoxane was added.
After stirring at 40 ° C. for 1 hour, the mixture was allowed to stand for 10 minutes, and the supernatant was removed by decantation. After removing the supernatant, the toluene solvent was evaporated under reduced pressure at 40 ° C., and the catalyst for olefin polymerization of Example 8 was obtained by drying under reduced pressure for 30 minutes.

(2) Production of ethylene / 1-hexene copolymer An ethylene / 1-hexene copolymer was produced using the catalyst for olefin polymerization of Example 8 obtained by the preparation of the above (1) catalyst.
That is, 47 mL of 1-hexene, 0.30 mmol of triethylaluminum, 1500 mL of diluted hydrogen of H ₂ / N ₂ = 5% by mass, and 800 mL of isobutane are added to a 1.6 L autoclave with induction stirring device, and the temperature is raised to 85 ° C. The ethylene partial pressure was maintained at 0.7 MPa by introduction. Subsequently, 0.0235 g of the catalyst for olefin polymerization of Example 8 obtained in the above (1) was pressurized with nitrogen, and polymerization was continued for 60 minutes while maintaining an ethylene partial pressure of 0.7 MPa and a temperature of 85 ° C.
During the polymerization reaction, additional supply of hydrogen was carried out at a supply rate proportional to the ethylene consumption rate. Thus, the amount of the ethylene / 1-hexene copolymer obtained in Example 8 was 130.8 g.

[Example 9]
(1) Preparation of catalyst for olefin polymerization: Silica A (pore volume: 1.58 mL / g, BET surface area: 310 m ² / g) calcined under nitrogen atmosphere to have a Tv value of 0.9 under nitrogen atmosphere: 300 mL three ports The flask was charged with 5.52 g, and 36.0 mL of dehydrated toluene was added and stirred to form a slurry. 15.1 mg of the above metallocene compound A was placed in a 100 mL eggplant flask separately prepared under a nitrogen atmosphere, and dissolved in 15.0 mL of dehydrated toluene. 15.5 mL of 20% methylaluminoxane (MAO) / toluene solution (manufactured by Albemarle) was added to a toluene solution of metallocene compound A at room temperature, and stirred for 30 minutes. While heating and stirring a 300 mL three-necked flask containing a toluene slurry of silica A in a 40 ° C. oil bath, the entire toluene solution of the reactant of metallocene compound A and methylaluminoxane was added.
After stirring at 40 ° C. for 1 hour, the mixture was allowed to stand for 10 minutes, and the supernatant was removed by decantation. After removing the supernatant, the toluene solvent was distilled off under reduced pressure at 40 ° C., and the catalyst for olefin polymerization of Example 9 was obtained by drying under reduced pressure for 30 minutes.

(2) Production of ethylene / 1-hexene copolymer An ethylene / 1-hexene copolymer was produced by using the catalyst for olefin polymerization of Example 9 obtained by the preparation of the above (1) catalyst.
That is, 30 mL of 1-hexene, 0.30 mmol of triethylaluminum, 1800 mL of diluted hydrogen of H ₂ / N ₂ = 5% by mass, and 800 mL of isobutane are added to a 1.6 L autoclave equipped with an induction stirrer, and ethylene is heated to 85 ° C. The ethylene partial pressure was maintained at 0.7 MPa by introduction. Subsequently, 0.0300 g of the catalyst for olefin polymerization of Example 9 obtained in the above (1) was pressurized with nitrogen, and polymerization was continued for 60 minutes while maintaining an ethylene partial pressure of 0.7 MPa and a temperature of 85 ° C.
During the polymerization reaction, additional supply of hydrogen was carried out at a supply rate proportional to the ethylene consumption rate. Thus, the ethylene / 1-hexene copolymer obtained in Example 9 was 105.8 g.

[Example 10]
(1) Preparation of catalyst for olefin polymerization Silica A (pore volume: 1.58 mL / g, BET surface area: 310 m ² / g) calcined under nitrogen atmosphere to have a Tv value of 0.7 under nitrogen atmosphere: 300 mL three ports The flask was charged with 5.94 g, and 39.0 mL of dehydrated toluene was added and stirred to form a slurry. Under a nitrogen atmosphere, 16.8 mg of the metallocene compound A was placed in a separately prepared 100 mL recovery flask, and dissolved with 16.0 mL of dehydrated toluene. 16.5 mL of a 20% methylaluminoxane (MAO) / toluene solution (manufactured by Albemarle) was added to a toluene solution of metallocene compound A at room temperature and stirred for 30 minutes. While heating and stirring a 300 mL three-necked flask containing a toluene slurry of silica A in a 40 ° C. oil bath, the entire toluene solution of the reactant of metallocene compound A and methylaluminoxane was added.
After stirring at 40 ° C. for 1 hour, the mixture was allowed to stand for 10 minutes, and the supernatant was removed by decantation. After the supernatant was removed, the toluene solvent was distilled off under reduced pressure at 40 ° C., and the catalyst for olefin polymerization of Example 10 was obtained by drying under reduced pressure for 30 minutes.

(2) Production of ethylene / 1-hexene copolymer An ethylene / 1-hexene copolymer was produced using the catalyst for olefin polymerization of Example 10 obtained by the preparation of the above (1) catalyst.
That is, 30 mL of 1-hexene, 0.30 mmol of triethylaluminum, 1800 mL of diluted hydrogen of H ₂ / N ₂ = 5% by mass, and 800 mL of isobutane are added to a 1.6 L autoclave equipped with an induction stirrer, and ethylene is heated to 85 ° C. The ethylene partial pressure was maintained at 0.7 MPa by introduction. Subsequently, 0.0298 g of the catalyst for olefin polymerization of Example 10 obtained in the above (1) was injected with nitrogen, and polymerization was continued for 60 minutes while maintaining an ethylene partial pressure of 0.7 MPa and a temperature of 85 ° C.
During the polymerization reaction, additional supply of hydrogen was carried out at a supply rate proportional to the ethylene consumption rate. The amount of the ethylene / 1-hexene copolymer thus obtained in Example 10 was 76.6 g.

[Example 11]
(1) Preparation of catalyst for olefin polymerization Silica A (pore volume: 1.58 mL / g, BET surface area: 310 m ² / g) calcined under nitrogen atmosphere and having a Tv value of 0.6 under nitrogen atmosphere, 300 mL three ports The flask was charged with 6.01 g, and 39.0 mL of dehydrated toluene was added and stirred to form a slurry. Under a nitrogen atmosphere, 16.8 mg of the metallocene compound A was placed in a 100 mL eggplant flask prepared separately, and dissolved with 17.0 mL of dehydrated toluene. 17.0 mL of 20% methylaluminoxane (MAO) / toluene solution (manufactured by Albemarle) was added to a toluene solution of metallocene compound A at room temperature and stirred for 30 minutes. While heating and stirring a 300 mL three-necked flask containing a toluene slurry of silica A in a 40 ° C. oil bath, the entire toluene solution of the reactant of metallocene compound A and methylaluminoxane was added.
After stirring at 40 ° C. for 1 hour, the mixture was allowed to stand for 10 minutes, and the supernatant was removed by decantation. After removing the supernatant, the toluene solvent was distilled off under reduced pressure at 40 ° C., and the catalyst for olefin polymerization of Example 11 was obtained by drying under reduced pressure for 30 minutes.

(2) Production of ethylene / 1-hexene copolymer An ethylene / 1-hexene copolymer was produced using the catalyst for olefin polymerization of Example 11 obtained by the preparation of the above (1) catalyst.
That is, 30 mL of 1-hexene, 0.30 mmol of triethylaluminum, 1800 mL of diluted hydrogen of H ₂ / N ₂ = 5% by mass, and 800 mL of isobutane are added to a 1.6 L autoclave equipped with an induction stirrer, and ethylene is heated to 85 ° C. The ethylene partial pressure was maintained at 0.7 MPa by introduction. Subsequently, 0.0280 g of the catalyst for olefin polymerization of Example 11 obtained in the above (1) was injected with nitrogen, and polymerization was continued for 60 minutes while maintaining an ethylene partial pressure of 0.7 MPa and a temperature of 85 ° C.
During the polymerization reaction, additional supply of hydrogen was carried out at a supply rate proportional to the ethylene consumption rate. The amount of the ethylene / 1-hexene copolymer thus obtained in Example 11 was 65.0 g.

[Example 12]
(1) Preparation of catalyst for olefin polymerization Silica A (pore volume: 1.58 mL / g, BET surface area: 310 m ² / g) calcined under nitrogen atmosphere and having a Tv value of 0.6 under nitrogen atmosphere, 300 mL three ports The flask was charged with 6.18 g, and 40.0 mL of dehydrated toluene was added and stirred to form a slurry. 17.0 mg of the metallocene compound A was placed in a 100 mL eggplant flask separately prepared under a nitrogen atmosphere, dissolved in 19.5 mL of dehydrated toluene, then heated to 60 ° C., and stirred for 1 hour. After 1 hour, 17.0 mL of 20% methylaluminoxane (MAO) / toluene solution (manufactured by Albemarle) was added to a toluene solution of metallocene compound A at 60 ° C., and the mixture was stirred for 30 minutes. While heating and stirring a 300 mL three-necked flask containing a toluene slurry of silica A in a 40 ° C. oil bath, the entire toluene solution of the reactant of metallocene compound A and methylaluminoxane was added.
After stirring at 40 ° C. for 1 hour, the mixture was allowed to stand for 10 minutes, and the supernatant was removed by decantation. After the supernatant was removed, the toluene solvent was distilled off under reduced pressure at 40 ° C., and the catalyst for olefin polymerization of Example 12 was obtained by drying under reduced pressure for 30 minutes.

(2) Production of ethylene / 1-hexene copolymer An ethylene / 1-hexene copolymer was produced using the catalyst for olefin polymerization of Example 12 obtained by the preparation of the above (1) catalyst.
That is, 30 mL of 1-hexene, 0.30 mmol of triethylaluminum, 800 mL of diluted hydrogen of H ₂ / N ₂ = 5% by mass, and 800 mL of isobutane are added to a 1.6 L autoclave with induction stirring device, and the temperature is raised to 85 ° C. The ethylene partial pressure was maintained at 0.7 MPa by introduction. Subsequently, 0.0286 g of the catalyst for olefin polymerization of Example 12 obtained in the above (1) was injected with nitrogen, and polymerization was continued for 60 minutes while maintaining an ethylene partial pressure of 0.7 MPa and a temperature of 85 ° C.
During the polymerization reaction, additional supply of hydrogen was carried out at a supply rate proportional to the ethylene consumption rate. The amount of the ethylene / 1-hexene copolymer thus obtained in Example 12 was 115.9 g.

[Example 13]
(1) Preparation of catalyst for olefin polymerization Silica A (pore volume: 1.58 mL / g, BET surface area: 310 m ² / g) calcined under nitrogen atmosphere to have a Tv value of 0.5 under nitrogen atmosphere, 300 mL three ports The flask was charged with 5.70 g, and 37.0 mL of dehydrated toluene was added and stirred to form a slurry. 16.2 mg of the above metallocene compound A was placed in a 100 mL eggplant flask prepared separately under a nitrogen atmosphere, and dissolved in 16.0 mL of dehydrated toluene. 16.0 mL of a 20% methylaluminoxane (MAO) / toluene solution (manufactured by Albemarle) was added to a toluene solution of metallocene compound A at room temperature and stirred for 30 minutes. While heating and stirring a 300 mL three-necked flask containing a toluene slurry of silica A in a 40 ° C. oil bath, the entire toluene solution of the reactant of metallocene compound A and methylaluminoxane was added.
After stirring at 40 ° C. for 1 hour, the mixture was allowed to stand for 10 minutes, and the supernatant was removed by decantation. After removing the supernatant, the toluene solvent was distilled off under reduced pressure at 40 ° C., and the catalyst for olefin polymerization of Example 13 was obtained by drying under reduced pressure for 30 minutes.

(2) Production of ethylene / 1-hexene copolymer An ethylene / 1-hexene copolymer was produced by using the catalyst for olefin polymerization of Example 13 obtained by the preparation of the above (1) catalyst.
That is, 30 mL of 1-hexene, 0.30 mmol of triethylaluminum, 1800 mL of diluted hydrogen of H ₂ / N ₂ = 5% by mass, and 800 mL of isobutane are added to a 1.6 L autoclave equipped with an induction stirrer, and ethylene is heated to 85 ° C. The ethylene partial pressure was maintained at 0.7 MPa by introduction. Subsequently, 0.0229 g of the catalyst for olefin polymerization of Example 13 obtained in the above (1) was pressurized with nitrogen, and polymerization was continued for 60 minutes while maintaining an ethylene partial pressure of 0.7 MPa and a temperature of 85 ° C.
During the polymerization reaction, additional supply of hydrogen was carried out at a supply rate proportional to the ethylene consumption rate. The amount of the ethylene / 1-hexene copolymer thus obtained in Example 13 was 52.1 g.

Example 14
(1) Preparation of catalyst for olefin polymerization Silica A (pore volume: 1.58 mL / g, BET surface area: 310 m ² / g) calcined under nitrogen atmosphere to have a Tv value of 0.5 under nitrogen atmosphere, 300 mL three ports The flask was charged with 4.96 g, and 32.5 mL of dehydrated toluene was added and stirred to form a slurry. Under a nitrogen atmosphere, 27.8 mg of the metallocene compound A was placed in a separately prepared 100 mL recovery flask, and dissolved with 13.3 mL of dehydrated toluene. 17.2 mL of 20% methylaluminoxane (MAO) / toluene solution (manufactured by Albemarle) was added to a toluene solution of metallocene compound A at room temperature and stirred for 30 minutes. While heating and stirring a 300 mL three-necked flask containing a toluene slurry of silica A in a 40 ° C. oil bath, the entire toluene solution of the reactant of metallocene compound A and methylaluminoxane was added.
After stirring at 40 ° C. for 1 hour, the mixture was allowed to stand for 10 minutes, and the supernatant was removed by decantation. The slurry after decantation was washed with toluene until the dilution ratio of the residue became 1%, and then the toluene solvent was distilled off under reduced pressure at 40 ° C., and the catalyst for olefin polymerization of Example 14 was dried under reduced pressure for 30 minutes. Obtained.

(2) Production of ethylene / 1-hexene copolymer An ethylene / 1-hexene copolymer was produced using the catalyst for olefin polymerization of Example 14 obtained by the preparation of the above (1) catalyst.
That is, 30 mL of 1-hexene, 0.30 mmol of triethylaluminum, 1800 mL of diluted hydrogen of H ₂ / N ₂ = 5% by mass, and 800 mL of isobutane are added to a 1.6 L autoclave equipped with an induction stirrer, and ethylene is heated to 85 ° C. The ethylene partial pressure was maintained at 0.7 MPa by introduction. Subsequently, 0.0230 g of the catalyst for olefin polymerization of Example 14 obtained in the above (1) was injected with nitrogen, and polymerization was continued for 60 minutes while maintaining an ethylene partial pressure of 0.7 MPa and a temperature of 85 ° C.
During the polymerization reaction, additional supply of hydrogen was carried out at a supply rate proportional to the ethylene consumption rate. The amount of the ethylene / 1-hexene copolymer thus obtained in Example 14 was 84.7 g.

[Example 15]
(1) Preparation of catalyst for olefin polymerization Silica A (pore volume: 1.58 mL / g, BET surface area: 310 m ² / g) calcined under nitrogen atmosphere to have a Tv value of 1.9 under nitrogen atmosphere, 300 mL three-necked The flask was charged with 3.00 g, and 19.5 mL of dehydrated toluene was added and stirred to form a slurry. 16.5 mg of the above metallocene compound B was placed in a 100 mL eggplant flask prepared separately under a nitrogen atmosphere, and dissolved in 8.0 mL of dehydrated toluene. 8.3 mL of 20% methylaluminoxane (MAO) / toluene solution (manufactured by Albemarle) was added to a toluene solution of metallocene compound B at room temperature and stirred for 30 minutes. While heating and stirring a 300 mL three-necked flask containing a toluene slurry of silica A in an oil bath at 40 ° C., the entire toluene solution of the reactant of metallocene compound B and methylaluminoxane was added.
After stirring at 40 ° C. for 1 hour, the mixture was allowed to stand for 10 minutes, and the supernatant was removed by decantation. After removing the supernatant, the toluene solvent was distilled off under reduced pressure at 40 ° C., and the catalyst for olefin polymerization of Example 15 was obtained by drying under reduced pressure for 30 minutes.

(2) Production of ethylene / 1-hexene copolymer An ethylene / 1-hexene copolymer was produced using the catalyst for olefin polymerization of Example 15 obtained by the preparation of the above (1) catalyst.
That is, 60 mL of 1-hexene, 0.30 mmol of triethylaluminum, 1000 mL of diluted hydrogen of H ₂ / N ₂ = 5% by mass, and 800 mL of isobutane are added to a 1.6 L autoclave equipped with an induction stirrer, and ethylene is heated to 85 ° C. The ethylene partial pressure was maintained at 0.7 MPa by introduction. Subsequently, 0.0697 g of the catalyst for olefin polymerization of Example 15 obtained in the above (1) was injected with nitrogen, and polymerization was continued for 60 minutes while maintaining an ethylene partial pressure of 0.7 MPa and a temperature of 85 ° C.
During the polymerization reaction, additional supply of hydrogen was carried out at a supply rate proportional to the ethylene consumption rate. The amount of the ethylene / 1-hexene copolymer thus obtained in Example 15 was 82.6 g.

[Example 16]
(1) Preparation of catalyst for olefin polymerization: Silica B (pore volume: 1.90 mL / g, BET surface area: 490 m ² / g) calcinated under nitrogen atmosphere to a Tv value of 0.9 under nitrogen atmosphere, 500 mL three ports 11.40 g was put into a flask, and 74.0 mL of dehydrated toluene was added and stirred to form a slurry. 31.7 mg of the metallocene compound A was placed in a 200 mL eggplant flask prepared separately under a nitrogen atmosphere, and dissolved in 30.0 mL of dehydrated toluene. 32.0 mL of 20% methylaluminoxane (MAO) / toluene solution (manufactured by Albemarle) was added to a toluene solution of metallocene compound A at room temperature, and the mixture was stirred for 30 minutes. While heating and stirring a 500 mL three-necked flask containing a toluene slurry of silica B in a 40 ° C. oil bath, the entire toluene solution of the reactant of metallocene compound A and methylaluminoxane was added.
After stirring at 40 ° C. for 1 hour, the mixture was allowed to stand for 10 minutes, and the supernatant was removed by decantation. After the supernatant was removed, the toluene solvent was evaporated under reduced pressure at 40 ° C., and the catalyst for olefin polymerization of Example 16 was obtained by drying under reduced pressure for 30 minutes.

(2) Production of ethylene / 1-hexene copolymer An ethylene / 1-hexene copolymer was produced using the catalyst for olefin polymerization of Example 16 obtained by the preparation of the above (1) catalyst.
That is, 30 mL of 1-hexene, 0.30 mmol of triethylaluminum, 400 mL of diluted hydrogen of H ₂ / N ₂ = 5% by mass, and 800 mL of isobutane are added to a 1.6 L autoclave equipped with an induction stirrer, and ethylene is heated to 85 ° C. The ethylene partial pressure was maintained at 0.7 MPa by introduction. Subsequently, 0.0279 g of the catalyst for olefin polymerization of Example 16 obtained in the above (1) was injected with nitrogen, and polymerization was continued for 60 minutes while maintaining an ethylene partial pressure of 0.7 MPa and a temperature of 85 ° C.
During the polymerization reaction, additional supply of hydrogen was carried out at a supply rate proportional to the ethylene consumption rate. The amount of the ethylene / 1-hexene copolymer thus obtained in Example 16 was 50.7 g.

[Example 17]
(1) Preparation of catalyst for olefin polymerization Silica A (pore volume: 1.58 mL / g, BET surface area: 310 m ² / g) calcined under nitrogen atmosphere to a Tv value of 1.19 under nitrogen atmosphere, 500 mL three ports 11.70 g was put into a flask, and 76.0 mL of dehydrated toluene was added and stirred to form a slurry. 162 mg of the above metallocene compound A was placed in a 200 mL eggplant flask prepared separately under a nitrogen atmosphere, and dissolved with 32.0 mL of dehydrated toluene. 33.0 mL of 20% methylaluminoxane (MAO) / toluene solution (manufactured by Albemarle) was added to a toluene solution of metallocene compound A at room temperature, and stirred for 30 minutes. While heating and stirring a 500 mL three-necked flask containing a toluene slurry of silica A in a 40 ° C. oil bath, the entire toluene solution of the reactant of metallocene compound A and methylaluminoxane was added.
After stirring at 40 ° C. for 1 hour, the mixture was allowed to stand for 10 minutes, and the supernatant was removed by decantation. The slurry after decantation is washed with hexane until the dilution ratio of the residue is 1%, and then the toluene solvent is distilled off under reduced pressure at 40 ° C., and the catalyst for olefin polymerization of Example 17 is dried for 30 minutes under reduced pressure. Obtained.

(2) Production of ethylene / 1-hexene copolymer An ethylene / 1-hexene copolymer was produced using the catalyst for olefin polymerization of Example 17 obtained by the preparation of the above (1) catalyst.
That is, 20 mL of 1-hexene, 0.30 mmol of triethylaluminum, 330 mL of diluted hydrogen of H ₂ / N ₂ = 5% by mass, and 800 mL of isobutane are added to a 1.6 L autoclave with induction stirring device, and the temperature is raised to 85 ° C. The ethylene partial pressure was maintained at 0.4 MPa by introduction. Subsequently, 0.0335 g of the catalyst for olefin polymerization of Example 17 obtained in the above (1) was injected with nitrogen, and polymerization was continued for 60 minutes while maintaining an ethylene partial pressure of 0.4 MPa and a temperature of 85 ° C.
During the polymerization reaction, additional supply of hydrogen was carried out at a supply rate proportional to the ethylene consumption rate. The ethylene / 1-hexene copolymer thus obtained in Example 17 weighed 166.8 g.

Comparative Example 1
(1) Preparation of catalyst for olefin polymerization: Silica A (pore volume: 1.58 mL / g, BET surface area: 310 m ² / g) calcined under nitrogen atmosphere to have a Tv value of 2.8 under nitrogen atmosphere, 300 mL three ports The flask was charged with 5.28 g, and 32.5 mL of dehydrated toluene was added and stirred to form a slurry. 14.1 mg of the above metallocene compound A was placed in a 100 mL eggplant flask separately prepared under a nitrogen atmosphere, and dissolved with 13.3 mL of dehydrated toluene. 8.6 mL of a 20% methylaluminoxane (MAO) / toluene solution (manufactured by Albemarle) was added to a toluene solution of metallocene compound A at room temperature and stirred for 30 minutes. While heating and stirring a 300 mL three-necked flask containing a toluene slurry of silica A in a 40 ° C. oil bath, the entire toluene solution of the reactant of metallocene compound A and methylaluminoxane was added.
After stirring at 40 ° C. for 1 hour, the mixture was allowed to stand for 10 minutes, and the supernatant was removed by decantation. After removing the supernatant, the toluene solvent was distilled off under reduced pressure at 40 ° C., and the catalyst for olefin polymerization of Comparative Example 1 was obtained by drying under reduced pressure for 30 minutes.

(2) Production of ethylene / 1-hexene copolymer An ethylene / 1-hexene copolymer was produced by using the catalyst for olefin polymerization of Comparative Example 1 obtained by the preparation of the above (1) catalyst.
That is, 30 mL of 1-hexene, 0.30 mmol of triethylaluminum, 400 mL of diluted hydrogen of H ₂ / N ₂ = 5% by mass, and 800 mL of isobutane are added to a 1.6 L autoclave equipped with an induction stirrer, and ethylene is heated to 85 ° C. The ethylene partial pressure was maintained at 0.7 MPa by introduction. Subsequently, 0.1159 g of the catalyst for olefin polymerization of Comparative Example 1 obtained in the above (1) was pressured with nitrogen, and polymerization was continued for 60 minutes while maintaining an ethylene partial pressure of 0.7 MPa and a temperature of 85 ° C.
During the polymerization reaction, additional supply of hydrogen was carried out at a supply rate proportional to the ethylene consumption rate. Thus, the ethylene / 1-hexene copolymer obtained in Comparative Example 1 was 166.7 g.

Comparative Example 2
(1) Preparation of catalyst for olefin polymerization: Silica A (pore volume: 1.58 mL / g, BET surface area: 310 m ² / g) calcined under nitrogen atmosphere to have a Tv value of 2.1: 300 mL three-neck under nitrogen atmosphere The flask was charged with 4.98 g, and 32.5 mL of dehydrated toluene was added and stirred to form a slurry. 13.8 mg of the above metallocene compound A was placed in a separately prepared 100 mL recovery flask under a nitrogen atmosphere, and was dissolved with 13.3 mL of dehydrated toluene. 13.8 mL of a 20% methylaluminoxane (MAO) / toluene solution (manufactured by Albemarle) was added to a toluene solution of metallocene compound A at room temperature, and the mixture was stirred for 30 minutes. While heating and stirring a 300 mL three-necked flask containing a toluene slurry of silica A in a 40 ° C. oil bath, the entire toluene solution of the reactant of metallocene compound A and methylaluminoxane was added.
After stirring at 40 ° C. for 1 hour, the mixture was allowed to stand for 10 minutes, and the supernatant was removed by decantation. After removing the supernatant, the toluene solvent was distilled off under reduced pressure at 40 ° C., and the catalyst for olefin polymerization of Comparative Example 2 was obtained by drying under reduced pressure for 30 minutes.

(2) Production of ethylene / 1-hexene copolymer An ethylene / 1-hexene copolymer was produced using the catalyst for olefin polymerization of Comparative Example 2 obtained by the preparation of the above (1) catalyst.
That is, 30 mL of 1-hexene, 0.30 mmol of triethylaluminum, 1800 mL of diluted hydrogen of H ₂ / N ₂ = 5% by mass, and 800 mL of isobutane are added to a 1.6 L autoclave equipped with an induction stirrer, and ethylene is heated to 85 ° C. The ethylene partial pressure was maintained at 0.7 MPa by introduction. Subsequently, 0.0297 g of the catalyst for olefin polymerization of Comparative Example 2 obtained in the above (1) was pressurized with nitrogen, and polymerization was continued for 60 minutes while maintaining an ethylene partial pressure of 0.7 MPa and a temperature of 85 ° C.
During the polymerization reaction, additional supply of hydrogen was carried out at a supply rate proportional to the ethylene consumption rate. Thus, the amount of the ethylene / 1-hexene copolymer obtained in Comparative Example 2 was 73.0 g.

Comparative Example 3
(1) Preparation of catalyst for olefin polymerization Silica A (pore volume: 1.58 mL / g, BET surface area: 310 m ² / g) calcined under nitrogen atmosphere to have a Tv value of 1.9 under nitrogen atmosphere, 300 mL three-necked The flask was charged with 4.15 g, and 28.0 mL of dehydrated toluene was added and stirred to form a slurry. 23.0 mg of the above metallocene compound A was placed in a 100 mL eggplant flask prepared separately under nitrogen atmosphere, and dissolved in 11.0 mL of dehydrated toluene. At room temperature, 1.3 mL of a 20% methylaluminoxane (MAO) / toluene solution (manufactured by Albemarle) was added to a toluene solution of metallocene compound A and stirred for 30 minutes. While heating and stirring a 300 mL three-necked flask containing a toluene slurry of silica A in a 40 ° C. oil bath, the entire toluene solution of the reactant of metallocene compound A and methylaluminoxane was added.
After stirring at 40 ° C. for 1 hour, the mixture was allowed to stand for 10 minutes, and the supernatant was removed by decantation. After removing the supernatant, the toluene solvent was distilled off under reduced pressure at 40 ° C., and the catalyst for olefin polymerization of Comparative Example 3 was obtained by drying under reduced pressure for 30 minutes.

(2) Production of ethylene / 1-hexene copolymer An ethylene / 1-hexene copolymer was produced by using the catalyst for olefin polymerization of Comparative Example 3 obtained by the preparation of the above (1) catalyst.
That is, 47 mL of 1-hexene, 0.30 mmol of triethylaluminum, 1500 mL of diluted hydrogen of H ₂ / N ₂ = 5% by mass, and 800 mL of isobutane are added to a 1.6 L autoclave with induction stirring device, and the temperature is raised to 85 ° C. The ethylene partial pressure was maintained at 1.4 MPa by introduction. Next, 0.1942 g of the catalyst for olefin polymerization of Comparative Example 3 obtained in the above (1) was injected with nitrogen, and polymerization was continued for 60 minutes while maintaining an ethylene partial pressure of 1.4 MPa and a temperature of 85 ° C.
During the polymerization reaction, additional supply of hydrogen was carried out at a supply rate proportional to the ethylene consumption rate. Thus, the amount of the ethylene / 1-hexene copolymer obtained in Comparative Example 3 was 72.6 g.

Comparative Example 4
(1) Preparation of catalyst for olefin polymerization Silica A (pore volume: 1.58 mL / g, BET surface area: 310 m ² / g) calcined under nitrogen atmosphere to have a Tv value of 1.9 under nitrogen atmosphere, 300 mL three-necked The flask was charged with 3.02 g, and 19.5 mL of dehydrated toluene was added and stirred to form a slurry. Under a nitrogen atmosphere, 41.3 mg of the metallocene compound B was placed in a 100 mL recovery flask prepared separately, and dissolved in 8.0 mL of dehydrated toluene. 8.3 mL of 20% methylaluminoxane (MAO) / toluene solution (manufactured by Albemarle) was added to a toluene solution of metallocene compound B at room temperature and stirred for 30 minutes. While heating and stirring a 300 mL three-necked flask containing a toluene slurry of silica A in an oil bath at 40 ° C., the entire toluene solution of the reactant of metallocene compound B and methylaluminoxane was added.
After stirring at 40 ° C. for 1 hour, the mixture was allowed to stand for 10 minutes, and the supernatant was removed by decantation. After removing the supernatant, the toluene solvent was distilled off under reduced pressure at 40 ° C., and the catalyst for olefin polymerization of Comparative Example 4 was obtained by drying under reduced pressure for 30 minutes.

(2) Production of ethylene / 1-hexene copolymer An ethylene / 1-hexene copolymer was produced using the catalyst for olefin polymerization of Comparative Example 4 obtained by the preparation of the above (1) catalyst.
That is, 60 mL of 1-hexene, 0.30 mmol of triethylaluminum, 1500 mL of diluted hydrogen of H ₂ / N ₂ = 5% by mass, and 800 mL of isobutane are added to a 1.6 L autoclave with induction stirring device, and the temperature is raised to 85 ° C. The ethylene partial pressure was maintained at 0.7 MPa by introduction. Subsequently, 0.0330 g of the catalyst for olefin polymerization of Comparative Example 4 obtained in the above (1) was pressured with nitrogen, and polymerization was continued for 60 minutes while maintaining an ethylene partial pressure of 0.7 MPa and a temperature of 85 ° C.
During the polymerization reaction, additional supply of hydrogen was carried out at a supply rate proportional to the ethylene consumption rate. Thus, the amount of the ethylene / 1-hexene copolymer obtained in Comparative Example 4 was 59.5 g.

[Description of Table 3 and Table 4]
Table 3 summarizes the types, contents, and ratio of the components (A), (B) and (C) contained in the olefin polymerization catalyst prepared in each example and each comparative example. Table 4 summarizes the polymerization conditions and the evaluation results carried out in each example and each comparative example. In Table 3, the description of component (B) / component (A) represents the content (mol) of component (B) per mol of transition metal M in component (A), component (B) / component (C) The description of) represents the content (mol) of the component (B) per 1 g of the component (C).
The metallocene compound B was used in Example 15 and Comparative Example 4, and the silica B was used in Example 16. The silica A used in Examples 1 to 15 and Comparative Examples 1 to 4 had a pore volume of 1.58 mL / g and a BET surface area of 310 m ² / g. The silica B used in Example 16 had a pore volume of 1.90 mL / g and a BET surface area of 490 m ² / g.
In Example 12, the reaction of the metallocene compound A which is the component (A) and the methylaluminoxane which is the component (B) was carried out at 60.degree. In Example 14, the reaction product of the component (A) and the component (B) was reacted with the component (C) and then washed with toluene.

[Evaluation results]
The evaluation results of Examples 1 to 17 and Comparative Examples 1 to 4 are shown in Table 4.
Ethylene manufactured using the catalyst for olefin polymerization of Comparative Example 1 manufactured under the condition that the Tv value of the component (C) is 2.8 mass% and the component (B) / component (C) is 4.7 mmol / g The appearance of the 1-hexene copolymer was not good, as the number of FE observed in the molded product was as large as 3.5 pieces / 0.1 g.
Ethylene manufactured using the catalyst for olefin polymerization of Comparative Example 2 manufactured under the condition that the Tv value of the component (C) is 2.1 mass% and the component (B) / component (C) is 8.0 mmol / g -Although 1-hexene copolymer improved FE number observed by the shaping | molding object compared with the comparative example 1, it was as large as 2.3 piece / 0.1g, and the appearance was not excellent.
Since the Tv value of the component (C) exceeds 2.0% by mass, the ethylene / 1-hexene copolymer produced using the olefin polymerization catalyst of Comparative Example 1 and Comparative Example 2 has a high FE number. It is thought that

The comparative example manufactured on the conditions whose Tv value of component (C) is 1.9 mass%, component (B) / component (A) is 93 mol / mol, and component (B) / component (C) is 0.9 mmol / g. The ethylene / 1-hexene copolymer produced using the olefin polymerization catalyst of No. 3 had an extremely high FE number observed in the molded product of 10.5 / 0.1 g, and the appearance was not excellent.
The comparative example manufactured on condition of Tv value of component (C) 1.9 mass%, component (B) / component (A) 320 mol / mol, component (B) / component (C) 7.9 mmol / g The ethylene / 1-hexene copolymer produced using the olefin polymerization catalyst of 4 had an FE number observed in the molded article improved compared to Comparative Example 3, but was as high as 5.0 / 0.1 g, The appearance was not good.
Even if the Tv value of the component (C) is 2.0% by mass or less, the contents of the component (A), the component (B) and the component (C) are not well balanced. It is considered that in the ethylene / 1-hexene copolymer produced using the olefin polymerization catalyst, the number of FE observed in the molded article is increased.

On the other hand, the Tv value of the component (C) is 0.5 to 1.9% by mass, the component (B) / component (A) is 340 to 1633 mol / mol, and the component (B) / component (C) is 7. In the ethylene / 1-hexene copolymer produced using the catalyst for olefin polymerization of Examples 1 to 17 produced under the conditions of 7 to 10.1 mmol / g, the FE number observed for the molded article is 1.0 The number of pieces / 0.1 g or less was small, and the appearance was excellent.
Both suppression of surface hydroxyl group density point by Tv value control and suppression of modification reaction of active species and component (A) and suppression of fouling by content ratio control of component (A), component (B), component (C) It was considered that the number of FE observed in the molded article decreased in the ethylene / 1-hexene copolymer produced using the olefin polymerization catalyst of Examples 1 to 17 because of the success.

  From the above results, it has become clear that according to the catalyst for olefin polymerization of the present invention, it is possible to produce an olefin polymer having few fish eyes and excellent in appearance after molding.

Claims (8)

A catalyst for olefin polymerization, comprising component (A), component (B), and component (C), wherein said component (A) is a metallocene compound represented by the following general formula (1):
The component (B) is an aluminoxane compound,
The component (C) is a mass (m1) after heating from room temperature to 200 ° C. under nitrogen, a mass (m1) after heating from room temperature to 200 ° C. under nitrogen from 200 ° C. to 1100 ° C. It is an inorganic oxide support whose ratio (Tv) of the value (m1-m2) which deducted the mass (m2) after heating up to 0.4-2.0 mass%,
The content of the component (B) per mol of the transition metal M in the component (A) is in the range of 330 to 12500 mol, and the content of the component (B) per 1 g of the component (C) is 5 A catalyst for olefin polymerization, which is in the range of 0 to 12.0 mmol;
[In Formula (1), M shows the transition metal selected from the group which consists of Ti, Zr, and Hf. X1 and X2 each independently represent a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing oxygen or nitrogen, or a hydrocarbon group having 1 to 20 carbon atoms 1 shows a substituent selected from the group consisting of an amino group and an alkoxy group having 1 to 20 carbon atoms.
Q represents an atom selected from the group consisting of a carbon atom, a silicon atom, and a germanium atom. R1 and R2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, m is 1 or 2, and when m is 2, plural Qs may be the same. The plurality of R 1 may be the same or different, and the plurality of R 2 may be the same or different. R1 and R2 may form a ring together with one or more Q.
R3, R4, R5, R6, R10, R11, R12 and R13 each independently represent a hydrogen atom, a halogen, a hydrocarbon group having 1 to 50 carbon atoms, a silicon number of 1 to 6, and the carbon number is A silicon-containing hydrocarbon group having 1 to 50 carbon atoms, a halogen-containing hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms containing an element selected from the group consisting of nitrogen, phosphorus, oxygen and sulfur, And a substituent selected from the group consisting of a hydrocarbon group-substituted silyl group having 1 to 50 carbon atoms.
Among R3 to R6, adjacent substituents may form a ring together with a carbon atom of a conjugated 5-membered ring to which the substituent is bonded. Among R10 to R13, adjacent substituents may form a ring together with a carbon atom of a conjugated 5-membered ring to which the substituent is bonded. ] The component (C) is an inorganic oxide support having a pore volume of 1.20 to 2.50 mL / g and a BET surface area of 280 to 800 m ² / g. Olefin polymerization catalysts.   In the general formula (1), a conjugate in which only one adjacent set of substituents among R 3, R 4, R 5, R 6, R 10, R 11, R 12 and R 13 is bound to these substituents The catalyst for olefin polymerization according to claim 1 or 2, which is a metallocene compound forming a ring together with a 5-membered ring carbon atom.   The component (A) according to claim 1, the component (B) according to claim 1, the component (C) according to claim 1, per 1 mol of transition metal M in the component (A) A process for producing a catalyst for olefin polymerization, wherein the component (B) is in the range of 330 to 12500 mol and the component (B) per 1 g of the component (C) is in the range of 5.0 to 12.0 mmol. . The component (C) is an inorganic oxide support having a pore volume of 1.20 to 2.50 mL / g and a BET surface area of 280 to 800 m ² / g. Process for producing a catalyst for olefin polymerization.   In the general formula (1), a conjugate in which only one adjacent set of substituents among R 3, R 4, R 5, R 6, R 10, R 11, R 12 and R 13 is bound to these substituents The method for producing a catalyst for olefin polymerization according to claim 4 or 5, which is a metallocene compound forming a ring together with a 5-membered ring carbon atom.   The method for producing a catalyst for olefin polymerization according to any one of claims 4 to 6, wherein the component (C) is brought into contact after the component (A) and the component (B) are brought into contact with each other. .   An olefin weight polymerizing olefin by using the catalyst for olefin polymerization according to any one of claims 1 to 3 or the catalyst for olefin polymerization produced by the method according to any one of claims 4 to 6 Manufacturing method of union.