JP6711340B2 - Method for producing ethylene-based polymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst, and more particularly to an olefin polymerization catalyst capable of producing an ethylene polymer having a sufficient number and length of long chain branches introduced therein and having a large amount of highly crystalline components.

As a method of improving the moldability of metallocene-based polyethylene, which is generally poor in moldability, a method of broadening the composition distribution or introducing long chain branching is known.
For example, Patent Document 1 discloses a method of broadening a copolymer composition distribution by a polymerization reaction by using a specific metallocene. Further, Patent Documents 2 to 4 disclose that by using a specific metallocene compound as a catalyst component, a long chain branch is introduced into polyethylene, and an ethylene polymer having a large strain hardening degree of extensional viscosity can be obtained. There is.

However, in Patent Document 1, there is no description regarding long chain branching, while in Patent Document 2, there is no description regarding copolymerization composition distribution, and a wide copolymerization composition distribution and a highly developed long chain branching are made compatible. At present, metallocene-based polyethylene with improved moldability has not yet been developed.
Further, the ethylene polymers of Patent Documents 2 to 4 have improved molding processability as compared with conventional long-chain branched polyethylene, but the branching index of long-chain branch is still lower than that of high-pressure low-density polyethylene. Therefore, further improvement in molding processability has been demanded.

JP, 2005-120385, A JP, 2011-137146, A JP, 2012-214780, A JP, 2013-22771, A

In view of the above problems of the prior art, the object of the present invention is to introduce a long chain branch of a sufficient number and length in order to improve the molding processability of the metallocene polyethylene, and ethylene having a high crystal component. An object of the present invention is to provide an olefin polymerization catalyst capable of producing a base polymer.
In the present invention, polyethylene is a generic term for an ethylene homopolymer and a copolymer of ethylene and an α-olefin, and is also referred to as an ethylene polymer.

As a result of intensive studies to solve the above problems, the present inventor has introduced a sufficient number and length of long chain branching by using an olefin polymerization catalyst containing a specific amount of a hydrocarbon compound. It was found that an ethylene-based polymer having a large amount of high crystal component can be produced, and has completed the present invention.

That is, according to the present invention, there is provided a method for producing an ethylene polymer using an olefin polymerization catalyst containing the following components (A), (B) and (C):
Component (A), relative to the solid catalyst component 1 part by weight comprising (B) and (C), tridecane, tetralin, mineral oil, liquid paraffin, and at least one hydrocarbon compound selected from the group consisting of polybutene 0 0.05 to 60 parts by weight, and a step of obtaining the olefin polymerization catalyst by containing the hydrocarbon compound in contact with the solid catalyst component outside the polymerization reactor,
Using the olefin polymerization catalyst, a molecular weight of branching index g′ of 100,000 to 1,000,000 measured with a gel permeation chromatography (GPC) measuring device combining a differential refractometer, a viscosity detection system and a light scattering detector. And a step of obtaining the ethylene-based polymer having a minimum value (gc) of 0.35 to 0.85 between the two, a method for producing an ethylene-based polymer is provided.
Component (A): a bridged cyclopentadienylindenyl compound containing a transition metal element represented by the following general formula ( 4 )

[In the general formula (4), M ^1c Represents a transition metal of Ti, Zr or Hf. X ^1c And X ^2c Are each independently 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, a hydrocarbon group having 1 to 20 carbon atoms or a substituted amino group having 1 to 20 carbon atoms, or An alkoxy group having 1 to 20 carbon atoms is shown. Q ^1c And Q ^2c Represents a carbon atom, a silicon atom or a germanium atom. R ^1c Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and 4 R ^1c Is bound to Q ^1c And Q ^2c And may form a ring together with. m ^c Is 0 or 1 and m ^c If is 0, Q ^1c Is R ^2c Is directly bonded to the conjugated 5-membered ring containing. R ^2c Is a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms and containing 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and oxygen. It shows a hydrocarbon group having 1 to 20 carbon atoms or a silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms. R ^4c Are each independently a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, or a t-butyl group, and four R ^4c The sum of the number of carbon atoms is 4 or less. R ^3c Represents a substituted aryl group represented by the following general formula (4-a).

(Y in the formula (4-a) ^1c Represents an atom of Group 14, Group 15 or Group 16 of the periodic table. R ^5c , R ^6c , R ^7c , R ^8c And R ^9c Are each independently 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, and a hydrocarbon group having 1 to 20 carbon atoms. Substituted amino group, C1-C20 alkoxy group, C1-C18 silicon-containing hydrocarbon group containing C1-C6, C1-C20 halogen-containing hydrocarbon group, or C1-C20. Represents a hydrocarbon group-substituted silyl group represented by R ^5c , R ^6c , R ^7c , R ^8c And R ^9c May form a ring together with the atoms bonded to adjacent Rs. n ^c Is 0 or 1 and n ^c If is 0, Y ^1c The substituent R ^5c Does not exist. p ^c Is 0 or 1 and p ^c If is 0, R ^8c And R ^8c There is no carbon atom bonded to ^7c R and the carbon atom to which ^9c The carbon atom to which is bonded is directly bonded. Y ^1c Is a carbon atom, R ^5c , R ^6c , R ^7c , R ^8c , R ^9c At least one of them is not a hydrogen atom. )]
Component (B): at least one compound selected from the group consisting of organoaluminum oxy compounds, borane compounds, and borate compounds
Component (C): silica
Further, according to the present invention, in the general formula (4), R ^4c Each independently represent a hydrogen atom, a methyl group or a t-butyl group, and four R ^4c When any one of the above is a t-butyl group, the other is a hydrogen atom, and a method for producing an ethylene-based polymer is provided.
Further, according to the present invention, in the general formula (4), R ^4c Each independently represent a hydrogen atom or a methyl group, which provides a method for producing an ethylene-based polymer.
Further, according to the present invention, there is provided a method for producing an ethylene polymer, wherein the component (B) is alumoxane.

The ethylene according to the present invention, the ratio of moles of metal of the component (C) the components for one gram (B), characterized in that a 0.001 to 0.010 (mol / g) Provided is a method for producing a polymer.
Further, according to the present invention, the solid catalyst, after contacting said component (A) and the component (B), the ethylene weight, characterized in that it is obtained by contacting the component (C) A method of making a coalescence is provided.

Further, according to the present invention, the relative solid catalyst component 1 part by weight, the production method of the ethylene polymer is characterized by formed by incorporating the 1-60 parts by weight of the hydrocarbon compound.
Also, according to the present invention, the hydrocarbon compound, tridecane, tetralin, manufacturing method of the ethylene-based polymer is provided, characterized in that at least one selected from the group consisting of liquid paraffin, and polybutene ..

By using the olefin polymerization catalyst of the present invention, it is possible to obtain a metallocene-based polyethylene having a sufficient number and length of long-chain branches and having a large amount of high crystalline components, as compared with conventional olefin polymerization catalysts. ..

FIG. 1 is a graph showing a baseline and a section of a chromatogram used in a gel permeation chromatography (GPC) method. FIG. 2 is a graph showing a relationship between a molecular weight distribution curve calculated from GPC-VIS measurement (branch structure analysis) and a branching index (g′) and a molecular weight (M). FIG. 3 is a graph showing the elution temperature distribution by temperature rising elution fractionation (TREF).

Hereinafter, the olefin polymerization catalyst of the present invention and the method for producing an olefin polymer using the same will be described.

1. Olefin Polymerization Catalyst Component The olefin polymerization catalyst of the present invention is an olefin polymerization catalyst containing the following components (A), (B) and (C), and contains the components (A), (B) and (C). It is characterized by containing 0.04 to 100 parts by weight of a hydrocarbon compound with respect to 1 part by weight of the solid catalyst component.
Component (A): Metallocene compound containing transition metal element Component (B): Compound that reacts with the metallocene compound of component (A) to form a cationic metallocene compound Component (C): Inorganic compound carrier Olefin polymerization catalyst of the present invention By including the components (A) to (C), it is possible to introduce a sufficient number and length of long chain branches into the ethylene polymer. Further, by incorporating a specific amount of a hydrocarbon compound into the olefin polymerization catalyst, an ethylene polymer containing a large amount of highly crystalline components can be obtained.
Hereinafter, each component will be described in detail for each item.

(1) Component (A)
The component (A) used in the present invention is a metallocene compound containing a transition metal element represented by the following general formula (1). Among these, the metallocene compound represented by the following general formula (2) is preferable, and the bridged cyclopentadienyl compound (metallocene compound) represented by the following general formula (3) is more preferable.

[In the general formulas (1) and (2), A ¹ and A ² represent a ligand having a conjugated five-membered ring structure (A ¹ and A ² may be the same or different in the same compound), Q represents a bonding group bridging two conjugated five-membered ring ligands at arbitrary positions, and M represents a metal atom selected from Group 4 of the periodic table. X and Y represent a hydrogen atom bonded to M, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group, respectively. ]

[In the general formula (3), M represents a transition metal of Ti, Zr, or Hf. X and Y are each independently 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, and a hydrocarbon group having 1 to 20 carbon atoms. An amino group or an alkoxy group having 1 to 20 carbon atoms is shown. Q ³¹ and Q ³² represent a carbon atom, a silicon atom or a germanium atom. R ³⁶ and R ³⁷ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and two R ^{36 s} and two R ^{37 s} together with the bonded Q ³¹ and Q ^32. It may form a ring. m is 0 or 1, and when m is 0, Q ³¹ is directly bonded to the conjugated 5-membered ring containing R ³¹ and R ³² . Two R ^{31 s} , two R ^{33 s} , and two R ^{34 s} are each a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, and a silicon-containing hydrocarbon having 1 to 18 carbon atoms containing 1 to 6 silicon atoms. Represents an atom or group selected from a 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, or a hydrocarbon group-substituted silyl group having 1 to 40 carbon atoms. However, at least one of them is not a hydrogen atom. Two R ^<32> is respectively independently a C1-C20 hydrocarbon group, a C1-C18 silicon-containing hydrocarbon group containing a C1-C6, and a C1-C20 halogen-containing hydrocarbon. A group, a hydrocarbon group having 1 to 40 carbon atoms containing oxygen or sulfur, or a silyl group substituted with a hydrocarbon group having 1 to 40 carbon atoms is shown. Among the plurality of ^{R 31,} R ^32, R ^{33, R 34,} together ^{R 31} adjacent, either a pair of ^{R 31} and ^{R 32 which R 32} with each other or adjacent neighboring only, adjacent ^{R 33} together, the adjacent any pair of R ³³ and R ³⁴ to R ³⁴ each other or adjacent only to do, may form a ring together with the bond to which carbon atoms. ]

Among these, as the component (A), a bridged cyclopentadienylindenyl compound (metallocene compound) represented by the following general formula (4) is particularly preferable.

[In the general formula (4), M ^1c represents a transition metal of Ti, Zr, or Hf. X ^1c and X ^2c are each independently 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, and a hydrocarbon having 1 to 20 carbon atoms. A group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms is shown. Q ^1c and Q ^2c represent a carbon atom, a silicon atom or a germanium atom. R ^1c independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and four R ^{1c s} may form a ring together with Q ^1c and Q ^2c which are bonded. .. m ^c is 0 or 1, and when m ^c is 0, Q ^1c is directly bonded to the conjugated 5-membered ring containing R ^2c . R ^2c and R ^4c are each independently a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, and 1 to 1 carbon atoms. 20 represents a halogen-containing hydrocarbon group, a C 1-20 hydrocarbon group containing oxygen, or a C 1-20 hydrocarbon group-substituted silyl group. R ^3c represents a substituted aryl group represented by the following general formula (4-a).

(In formula (4-a), Y ^1c represents an atom of Group 14, Group 15 or Group 16 of the periodic table. R ^5c , R ^6c , R ^7c , R ^8c and R ^9c are each independently hydrogen. Atom, chlorine atom, bromine atom, hydrocarbon group having 1 to 20 carbon atoms, hydrocarbon group having 1 to 20 carbon atoms containing oxygen or nitrogen, hydrocarbon group substituted amino group having 1 to 20 carbon atoms, 1 to carbon atoms An alkoxy group having 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms; R ^5c , R ^6c , R ^7c , R ^8c and R ^9c may form a ring together with the atoms bonded to adjacent Rs with each other, and n ^c is 0 or 1. If ^{n c} is ^0, there is no substituent ^{R 5c} to ^{Y 1c} .p ^c is 0 or 1, if ^{p c} is ^0, the carbon atom ^{to which R 8c} and ^{R 8c} is attached is absent , The carbon atom to which R ^7c is bound and the carbon atom to which R ^9c is bound are directly bound to each other, and when Y ^1c is a carbon atom, at least one of R ^5c , R ^6c , R ^7c , R ^8c and R ^9c. Is not a hydrogen atom.)]

In the general formula (4), M ^1c represents a transition metal of Ti, Zr, or Hf, preferably Zr or Hf, and more preferably Zr.
In addition, as X ^1c and X ^2c in the general formula (4), for example, hydrogen atom, chlorine atom, bromine atom, iodine atom, or methyl group, ethyl group, n-propyl group, i-propyl group, n -Butyl group, i-butyl group, t-butyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, phenyl group, benzyl group, methoxymethyl group, ethoxymethyl group, n-propoxy group Methyl group, i-propoxymethyl group, n-butoxymethyl group, i-butoxymethyl group, t-butoxymethyl 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, 2-furyl group, 2-tetrahydrofuryl group, dimethylaminomethyl group, diethylaminomethyl group, di-propylaminomethyl group, bis(dimethylamino)methyl group, bis(di-propylamino)methyl Group, (dimethylamino)(phenyl)methyl group, methylimino group, ethylimino group, 1-(methylimino)ethyl group, 1-(phenylimino)ethyl group, 1-[(phenylmethyl)imino]ethyl group, methoxy group, Ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, t-butoxy group, phenoxy group, dimethylamino group, diethylamino group, di-n-propylamino group, di-propylamino group Group, di-n-butylamino group, di-i-butylamino group, di-t-butylamino group, diphenylamino group and the like.
Specific examples of preferable X ^1c and X ^2c include chlorine atom, bromine atom, methyl group, n-butyl group, i-butyl group, methoxy group, ethoxy group, i-propoxy group, n-butoxy group, phenoxy group, Examples thereof include a dimethylamino group and a di i-propylamino group, and among these, a chlorine atom, a methyl group and a dimethylamino group are particularly preferable.

In formula (4), Q ^1c and Q ^2c represent a carbon atom, a silicon atom or a germanium atom. Preferred Q ^1c and Q ^2c are carbon atom or silicon atom, and more preferably silicon atom.

In formula (4), R ^1c is, for example, hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n- Examples thereof include a pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group and phenyl group. When R ^1c forms a ring together with Q ^1c and Q ^2c , a cyclobutylidene group, a cyclopentylidene group, a cyclohexylidene group, a silacyclobutyl group, a silacyclopentyl group, a silacyclohexyl group, etc. Is mentioned.
Specific examples of preferable R ^1c include a hydrogen atom, a methyl group, an ethyl group, a phenyl group, an ethylene group, and a cyclobutylidene group when Q ^1c and/or Q ^2c is a carbon atom, and Q ^1c or/ And when Q ^2c is a silicon atom, examples thereof include a methyl group, an ethyl group, a phenyl group, and a silacyclobutyl group.

Further, in the general formula (4), m ^c is 0 or 1, and when m ^c is 0, Q ^1c is directly bonded to the conjugated 5-membered ring containing R ^2c .

In the general formula (4), R ^2c and R ^4c are, for example, hydrogen atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, phenyl group, benzyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methyl Phenyl group, 3,5-dimethylphenyl group, 4-t-butylphenyl group, 3,5-di-t-butylphenyl group, bis(trimethylsilyl)methyl group, bis(t-butyldimethylsilyl)methyl group, bromomethyl Group, chloromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-bromopropyl group, 3-bromopropyl group, 2-bromocyclopentyl group, 2,3-dibromocyclopentyl group, 2-bromo-3-iodocyclopentyl group Group, 2,3-dibromocyclohexyl group, 2-chloro-3-iodocyclohexyl group, 2-chlorophenyl group, 4-chlorophenyl group, 2,3,4,5,6-pentafluorophenyl group, 4-trifluoromethyl group Phenyl group, furyl group, tetrahydrofuryl group, 2-methylfuryl group, trimethylsilyl group, tri-t-butylsilyl group, di-t-butylmethylsilyl group, t-butyldimethylsilyl group, triphenylsilyl group, diphenylmethylsilyl group, Examples thereof include a phenyldimethylsilyl group.

R ^2c and R ^4c are each a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, A hydrocarbon group having 1 to 20 carbon atoms or a silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms containing oxygen is preferable because the polymerization activity is particularly increased.
Specific preferred examples of R ^2c and R ^4c include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group. , A cyclohexyl group, a phenyl group, a 2-methylfuryl group, and a trimethylsilyl group. Among these, a hydrogen atom, a methyl group, an n-butyl group, a t-butyl group, a phenyl group, and a trimethylsilyl group are more preferable, and a hydrogen atom. , Methyl group, t-butyl group, phenyl group and trimethylsilyl group are particularly preferable.

In formula (4-a), R ^3c represents a substituted aryl group having a structure represented by the above formula (4-a), preferably a phenyl (Ph) group having a specific substituent, or a furyl group. , Thienyl groups are shown.
Examples of R ^3c include 4-trimethylsilylphenyl group, 4-(t-butyldimethylsilyl)phenyl group, 3,5-bistrimethylsilylphenyl group, 4-chlorophenyl group, 4-bromophenyl group, 3,5- Dichlorophenyl group, 2,4,6-trichlorophenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, 4-isopropoxyphenyl group, 4-n-butoxyphenyl group, 2-furyl group, 2-(5- Methyl)furyl group, 2-(5-t-butyl)furyl group, 2-(5-trimethylsilyl)furyl group, 2-(4,5-dimethyl)furyl group, 2-benzofuryl group, 2-thienyl group, 2 Examples thereof include a -(5-methyl)thienyl group, a 2-(5-t-butyl)thienyl group, a 2-(5-trimethylsilyl)thienyl group, and a 2-(4,5-dimethyl)thienyl group.

Specific examples of the metallocene compound represented by the above general formula (4) are shown in the following general formula (5) and Tables 1 to 4, and the following general formula (6) and Tables 5 to 8, which are used in the present invention. The metallocene compound that can be used is not limited to these.

In the specific examples of the metallocene compound represented by the above general formula (6) and Tables 6 to 9 below, the number indicating the position of the substituent R ^4c on the cyclopentadienyl ring of the metallocene compound is represented by the following formula: As in (7).

In addition, compounds in which zirconium in the above compounds is replaced with titanium or hafnium, and the like are also mentioned as preferable specific examples.

Further, among the specific compounds exemplified in the above table, preferable ones as the component (A) are shown below.
1c-10c, 12c-65c, 67c-80c, 95c-143c, 144c-303c etc. in Tables 1-8 are mentioned.
Further, a compound in which zirconium in the above compound is replaced by titanium or hafnium and the like are also mentioned as the preferred component (A).

Further, among the specific compounds exemplified in the above table, particularly preferable ones as the component (A) are shown below.
1c-4c, 7c, 8c, 12c-38c, 44c-47c, 52c-59c, 62c, 63c, 67c-80c, 116c-123c, 127c-136c, 142c, 143c, 144c-146c in Tables 1-8. 148c, 152c to 155c, 157c, 161c to 164c, 166c, 170c to 173c, 175c, 179c to 182c, 184c, 188c to 191c, 193c, 224c to 226c, 228c, 232c to 235c, 237c, 241c to 244c, 246c, 246c. , 250c to 253c, 255c, 259c to 262c, 264c, 268c to 271c, 273c.
Further, a compound in which zirconium in the above compound is replaced by titanium or hafnium and the like are also mentioned as the preferred component (A).

Further, among the specific compounds exemplified in the above table, those preferable as the component (A) are shown below from the viewpoint of particularly high polymerization activity.
1c-8c, 12c-38c, 44c-47c, 52c-63c, 67c-80c, 116c-123c, 127c-136c, 142c, 143c, 144c-303c etc. in Tables 1-8 are mentioned.
Further, a compound in which zirconium in the above compound is replaced by titanium or hafnium and the like are also mentioned as the preferred component (A).

Further, among the specific compounds exemplified in the above table, those preferable as the component (A) are shown below from the viewpoint of particularly excellent moldability.
1c-4c, 7c-10c, 12c-59c, 62c-65c, 67c-80c, 95c-143c, 144c-146c, 148c, 152c-155c, 157c, 161c-164c, 166c, 170c in Tables 1-8. ~173c, 175c, 179c to 182c, 184c, 188c to 191c, 193c, 224c to 226c, 228c, 232c to 235c, 237c, 241c to 244c, 246c, 250c to 253c, 255c, 259c to 262c, 264c, 268c to 271c. 273c and the like.
Further, a compound in which zirconium in the above compound is replaced with titanium or hafnium, or the like is also mentioned as a preferable component (A).

(2) Component (B)
The component (B) used in the present invention is a compound which reacts with the metallocene compound of the component (A) to form a cationic metallocene compound.

As the component (B), for example, an organoaluminum oxy compound, a borane compound, a borate compound, or a mixture thereof can be used. Further, as the component (B), two or more kinds of borane compounds and borate compounds can be mixed and used.
Each component will be described in detail below.

(I) Organoaluminum Oxy Compound As one of the components (B), an organoaluminum oxy compound can be mentioned.
The organoaluminum oxy compound has an Al-O-Al bond in the molecule, and the number of bonds is usually 1 to 100, preferably 1 to 50. Such an organoaluminum oxy compound is usually a product obtained by reacting an organoaluminum compound with water.
The reaction between organic aluminum and water is usually carried out in an inert hydrocarbon (solvent). As the inert hydrocarbon, pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene and other aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons can be used, but aliphatic hydrocarbons or Preference is given to using aromatic hydrocarbons.

As the organoaluminum compound used for the preparation of the organoaluminum oxy compound, any of the compounds represented by the following general formula (8) can be used, and two or more kinds can be mixed and used.
^{_{R 6 t AlX 3 3-t}} ··· formula (8)
(In the general formula (8), R ⁶ represents a hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group or an aralkyl group having 1 to 18 carbon atoms, preferably 1 to 12, and X ³ represents a hydrogen atom or a hydrogen atom. Represents a halogen atom, and t represents an integer of 1≦t≦3.)

Among the compounds represented by the general formula (8), trialkylaluminum is preferably used. The alkyl group of trialkylaluminum may be any of methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, etc. Particularly preferred is a group.

The reaction ratio of water and the organoaluminum compound (water/Al molar ratio) is preferably 0.25/1 to 1.2/1, particularly preferably 0.5/1 to 1/1, and the reaction temperature is , Usually in the range of −70 to 100° C., preferably −20 to 20° C. The reaction time is generally selected 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 water of crystallization contained in copper sulfate hydrate, aluminum sulfate hydrate and the like, and components capable of generating water in the reaction system can be used. Among the above-mentioned organoaluminum oxy compounds, those obtained by reacting alkylaluminum with water are usually called aluminoxane, and particularly methylaluminoxane (including those substantially consisting of methylaluminoxane (MAO)). Is suitable as an organic aluminum oxy compound.
As a matter of course, as the organoaluminum oxy compound, two or more kinds of the above organoaluminum oxy compounds may be used in combination, and the solution of the organoaluminum oxy compound may be a solution or a dispersion of the above-mentioned inert hydrocarbon solvent. You may use what was said.

(Ii) Borane compound and borate compound Further, other specific examples of the component (B) include a borane compound and a borate compound. More specifically, the borane compound is represented by triphenylborane, tri(o-tolyl)borane, tri(p-tolyl)borane, tri(m-tolyl)borane, tri(o-fluorophenyl)borane, tris( p-fluorophenyl)borane, tris(m-fluorophenyl)borane, tris(2,5-difluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(4-trifluoromethylphenyl)borane, tris (3,5-ditrifluoromethylphenyl)borane, tris(2,6-ditrifluoromethylphenyl)borane, tris(pentafluorophenyl)borane, tris(perfluoronaphthyl)borane, tris(perfluorobiphenyl), tris( Examples thereof include perfluoroanthryl)borane and tris(perfluorobinaphthyl)borane.

Among these, tris(3,5-ditrifluoromethylphenyl)borane, tris(2,6-ditrifluoromethylphenyl)borane, tris(pentafluorophenyl)borane, tris(perfluoronaphthyl)borane, tris(perfluoro) Biphenyl)borane, tris(perfluoroanthryl)borane and tris(perfluorobinaphthyl)borane are more preferable, and tris(2,6-ditrifluoromethylphenyl)borane, tris(pentafluorophenyl)borane, tris( Perfluoronaphthyl)borane and tris(perfluorobiphenyl)borane are exemplified as preferable compounds.

Further, when specifically expressing the borate compound, the first example is a compound represented by the following general formula (9).
^{[L 1 -H] + [BR} 7 R 8 X 4 X 5] - ··· formula (9)

In the general formula (9), L ¹ is a neutral Lewis base, H is a hydrogen atom, and [L ¹ -H] is Bronsted acid such as ammonium, anilinium, or phosphonium.

Examples of ammonium include trialkyl-substituted ammonium such as trimethylammonium, triethylammonium, tripropylammonium, tributylammonium and tri(n-butyl)ammonium, and dialkylammonium such as di(n-propyl)ammonium and dicyclohexylammonium.

Examples of the anilinium include N,N-dimethylanilinium, N,N-diethylanilinium, N,N-2,4,6-pentamethylanilinium and other N,N-dialkylaniliniums. Furthermore, examples of the phosphonium include triarylphosphonium, tributylphosphonium, tributylphosphonium, tri(methylphenyl)phosphonium, tri(dimethylphenyl)phosphonium, and the like, and trialkylphosphonium.

Further, in the general formula (9), R ⁷ and R ⁸ are the same or different aromatic or substituted aromatic hydrocarbon groups containing 6 to 20 carbon atoms, preferably 6 to 16 carbon atoms, and are mutually linked by a bridging group. It may be linked, and the substituent of the substituted aromatic hydrocarbon group is preferably an alkyl group represented by a methyl group, an ethyl group, a propyl group, an isopropyl group or the like, or a halogen such as fluorine, chlorine, bromine or iodine. .. Further, X ⁴ and X ⁵ are a hydride group, a halide group, a hydrocarbon group containing 1 to 20 carbon atoms, and a substituted carbon group containing 1 to 20 carbon atoms in which one or more hydrogen atoms are replaced by halogen atoms. It is a hydrogen group.

Specific examples of the compound represented by the general formula (9) include tributylammonium tetra(pentafluorophenyl)borate, tributylammonium tetra(2,6-ditrifluoromethylphenyl)borate, tributylammonium tetra(3,5-ditrifluoro). Methylphenyl)borate, tributylammonium tetra(2,6-difluorophenyl)borate, tributylammonium tetra(perfluoronaphthyl)borate, dimethylanilinium tetra(pentafluorophenyl)borate, dimethylanilinium tetra(2,6-ditrifluoro) Methylphenyl)borate, dimethylanilinium tetra(3,5-ditrifluoromethylphenyl)borate, dimethylanilinium tetra(2,6-difluorophenyl)borate, dimethylanilinium tetra(perfluoronaphthyl)borate, triphenylphosphonium tetra (Pentafluorophenyl)borate, triphenylphosphonium tetra(2,6-ditrifluoromethylphenyl)borate, triphenylphosphonium tetra(3,5-ditrifluoromethylphenyl)borate, triphenylphosphonium tetra(2,6-difluorophenyl) ) Borate, triphenylphosphonium tetra(perfluoronaphthyl)borate, trimethylammonium tetra(2,6-ditrifluoromethylphenyl)borate, triethylammonium tetra(pentafluorophenyl)borate, triethylammonium tetra(2,6-ditrifluoromethyl) Phenyl)borate, triethylammonium tetra(perfluoronaphthyl)borate, tripropylammonium tetra(pentafluorophenyl)borate, tripropylammonium tetra(2,6-ditrifluoromethylphenyl)borate, tripropylammonium tetra(perfluoronaphthyl) Examples thereof include borate, di(1-propyl)ammonium tetra(pentafluorophenyl)borate and dicyclohexylammonium tetraphenylborate.

Among these, tributylammonium tetra(pentafluorophenyl)borate, tributylammonium tetra(2,6-ditrifluoromethylphenyl)borate, tributylammonium tetra(3,5-ditrifluoromethylphenyl)borate, tributylammonium tetra(perfluoro) Naphthyl)borate, dimethylanilinium tetra(pentafluorophenyl)borate, dimethylanilinium tetra(2,6-ditrifluoromethylphenyl)borate, dimethylanilinium tetra(3,5-ditrifluoromethylphenyl)borate, dimethylanilinium Tetra(perfluoronaphthyl)borate is preferred.

A second example of the borate compound is represented by the following general formula (10).
^{[L 2] + [BR 7} R 8 X 4 X 5] - ··· formula (10)

In the general formula (10), L ² is carbocation, methyl cation, ethyl cation, propyl cation, isopropyl cation, butyl cation, isobutyl cation, tert-butyl cation, pentyl cation, tropinium cation, benzyl cation, trityl cation, Examples thereof include sodium cation and proton. Further, R ⁷ , R ⁸ , X ⁴ and X ⁵ are the same as defined in the general formula (9).

Specific examples of the compound represented by the general formula (10) include trityl tetraphenyl borate, trityl tetra(o-tolyl)borate, trityl tetra(p-tolyl)borate, trityl tetra(m-tolyl)borate, trityl tetra. (O-Fluorophenyl)borate, trityltetra(p-fluorophenyl)borate, trityltetra(m-fluorophenyl)borate, trityltetra(3,5-difluorophenyl)borate, trityltetra(pentafluorophenyl)borate, trityl Tetra(2,6-ditrifluoromethylphenyl)borate, trityltetra(3,5-ditrifluoromethylphenyl)borate, trityltetra(perfluoronaphthyl)borate, tropiniumtetraphenylborate, tropiniumtetra(o-tolyl) Borate, tropinium tetra(p-tolyl)borate, tropinium tetra(m-tolyl)borate, tropinium tetra(o-fluorophenyl)borate, tropinium tetra(p-fluorophenyl)borate, tropinium tetra(m-) Fluorophenyl)borate, tropinium tetra(3,5-difluorophenyl)borate, tropinium tetra(pentafluorophenyl)borate, tropinium tetra(2,6-ditrifluoromethylphenyl)borate, tropinium tetra(3,5) - ditrifluoromethylphenyl) borate, tropicity tetra (perfluoro-naphthyl) _{borate, NaBPh 4, NaB (o-} CH 3 -Ph) 4, NaB (p-CH 3 -Ph) 4, NaB (m-CH 3 - _{Ph) 4, NaB (o-} F-Ph) 4, NaB (p-F-Ph) 4, NaB (m-F-Ph) 4, NaB (3,5-F 2 -Ph) 4, NaB (C _{6 F 5) 4, NaB (} 2,6- (CF 3) 2 -Ph) 4, NaB (3,5- (CF 3) 2 -Ph) 4, NaB (C 10 F 7) 4, HBPh 4 · 2 diethyl ether, HB(3,5-F ₂ -Ph) ₄ .2 diethyl ether, HB(C ₆ F ₅ ) 4 .2 diethyl ether, HB(2,6-(CF ₃ ) ₂ -Ph) ₄・2 diethyl _{ether, HB (3,5- (CF 3)} 2 -Ph) 4 · 2 diethyl _{ether, HB (C 10 H 7)} 4 · 2 diethyl ether Can be illustrated.

Among these, trityl tetra(pentafluorophenyl)borate, trityl tetra(2,6-ditrifluoromethylphenyl)borate, trityl tetra(3,5-ditrifluoromethylphenyl)borate, trityl tetra(perfluoronaphthyl)borate, Tropinium tetra(pentafluorophenyl)borate, tropinium tetra(2,6-ditrifluoromethylphenyl)borate, tropinium tetra(3,5-ditrifluoromethylphenyl)borate, tropinium tetra(perfluoronaphthyl)borate, _{NaB (C 6 F 5) 4} , NaB (2,6- (CF 3) 2 -Ph) 4, NaB (3,5- (CF 3) 2 -Ph) 4, NaB (C 10 F 7) 4, _{HB (C 6 F 5) 4} · 2 diethyl _{ether, HB (2,6- (CF 3)} 2 -Ph) 4 · 2 diethyl _{ether, HB (3,5- (CF 3)} 2 -Ph) 4 · 2 diethyl _{ether, HB (C 10 H 7)} 4 · 2 diethyl ether.

More preferably, among these, trityl tetra(pentafluorophenyl)borate, trityl tetra(2,6-ditrifluoromethylphenyl)borate, tropinium tetra(pentafluorophenyl)borate, tropinium tetra(2,6-ditrifluoro) methylphenyl) _{borate, NaB (C 6 F 5)} 4, NaB (2,6- (CF 3) 2 -Ph) 4, HB (C 6 F 5) 4 · 2 diethyl ether, HB (2,6- ( _{CF 3) 2 -Ph) 4 ·} 2 diethyl _{ether, HB (3,5- (CF 3)} 2 -Ph) 4 · 2 diethyl _{ether, HB (C 10 H 7) 4} · 2 diethyl ether.

(3) Component (C)
The component (C) used in the present invention is an inorganic compound carrier, and a metal, a metal oxide, a metal chloride, a metal carbonate, a carbonaceous material, or a mixture thereof can be used.

Suitable metals that can be used as the component (C) include, for example, iron, aluminum, nickel and the like.

Examples of the metal oxide include single oxides or complex oxides of elements of Groups 1 to 14 of the periodic table, and examples thereof include 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 Examples thereof include various natural or synthetic single or complex oxides such as ₃ ·CuO, Al ₂ O ₃ ·Fe ₂ O ₃ , Al ₂ O ₃ ·NiO, and SiO ₂ ·MgO.
In the present application, the above formulas are not molecular formulas but only compositions, 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 a small amount of impurities.

As the metal chloride, for example, chlorides of alkali metals and alkaline earth metals are preferable, and specifically, MgCl ₂ , CaCl _{2 and the} like are particularly preferable. The metal carbonate is preferably an alkali metal or alkaline earth metal carbonate, and specific examples thereof include magnesium carbonate, calcium carbonate, barium carbonate and the like. Examples of the carbonaceous material include carbon black and activated carbon.

Any of the above-mentioned inorganic carriers can be preferably used in the present invention, but it is particularly preferable to use a metal oxide, and among them, silica (SiO ₂ ) and alumina (Al ₂ O ₃ ) are preferably used.

The above-mentioned inorganic compound carrier is usually baked at 200 to 800° C., preferably 400 to 600° C. in air or in an inert gas such as nitrogen or argon to adjust the amount of surface hydroxyl groups to 0.8 to 1.5 mmol. After being adjusted to /g, it is preferably used as the component (C).
The properties of the inorganic compound carrier used as the component (C) are not particularly limited, but usually the average particle size is 5 to 200 μm, preferably 10 to 150 μm, and the average pore size is 20 to 1000 Å, preferably 50. a, ~ 500, specific surface area 150~1000m ² / g, preferably 200-700 ² / g, a pore volume of 0.3~2.5cm ³ / g, preferably 0.5~2.0cm ³ / It is preferable to use an inorganic compound carrier having an apparent specific gravity of 0.20 to 0.50 g/cm ³ , preferably 0.25 to 0.45 g/cm ³ .

The above-mentioned inorganic compound carriers can of course be used as they are, but as a pretreatment, these carriers are treated with trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tripropylaluminum, tributylaluminum, trioctylaluminum, tridecylaluminum. After contacting with an organoaluminum compound such as diisobutylaluminum hydride or an organoaluminum oxy compound containing an Al—O—Al bond, it can be used as the component (C).

Further, a layered silicate can be used as a component which also serves as the component (B) and the component (C). The layered silicate is a silicate compound having a crystal structure in which planes formed by ionic bonds or the like are stacked in parallel with each other with weak bonding force. Most of the layered silicates are naturally produced mainly as the main components of clay minerals, but these layered silicates are not limited to those of natural origin, and may be synthetic products.
Among these, smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite, and teniolite, vermiculite, and mica are preferable.

In general, a natural product of a layered silicate is often non-ion exchangeable (non-swelling), and in that case, in order to have preferable ion exchangeability (or swelling), It is preferable to perform a treatment for imparting swelling property. Among such treatments, the following chemical treatments are particularly preferable. Here, as the chemical treatment, both surface treatment for removing impurities adhering to the surface and treatment for affecting the crystal structure and chemical composition of the layered silicate can be used.
Specifically, (a) acid treatment using hydrochloric acid, sulfuric acid, etc., (b) alkali treatment using NaOH, KOH, NH _3, etc., (c) selected from Groups 2 to 14 of the periodic table Salt treatment with a salt comprising at least one anion selected from the group consisting of a cation containing at least one atom and an anion derived from a halogen atom or an inorganic acid, (d) alcohol, hydrocarbon Examples include treatment of compounds with organic substances such as formamide and aniline.
These treatments may be performed alone or in combination of two or more.

The particle properties of the layered silicate can be controlled by pulverization, granulation, sizing, fractionation, etc. before, during, and after all the steps. The method can be any purposeful. In particular, if the granulation method is described, for example, spray granulation method, tumbling granulation method, compression granulation method, stirring granulation method, briquetting method, compacting method, extrusion granulation method, fluidized bed granulation method. Method, emulsion granulation method, submerged granulation method and the like. Particularly preferable granulation methods are the spray granulation method, the rolling granulation method and the compression granulation method among the above.

The above-mentioned layered silicate can be used as it is, but these layered silicates are used as trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, diisobutyl. It can be used in combination with an organic aluminum compound such as aluminum hydride or an organic aluminum oxy compound containing an Al-O-Al bond.

(4) Hydrocarbon compound Examples of the hydrocarbon compound used in the present invention include aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, and silicon-containing hydrocarbons, preferably aliphatic hydrocarbons and It is an aromatic hydrocarbon. The olefin polymerization catalyst of the present invention, by containing a hydrocarbon compound, inhibits the monomer from reaching the highly copolymerizable active species present inside the catalyst pores and delays the expression of the polymerization activity. It is considered possible to obtain an ethylene-based polymer having a large amount of highly crystalline components in which low-copolymerizable active species on the surface are generated.

The carbon number of the hydrocarbon compound is preferably 1 to 40, and specific examples include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, Cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, 2-hexene, 3-methyl-2-pentene, 3-methyl-2-heptene, 2-octene, 3-decaene, cyclohexene, toluene, xylene, trimethylbenzene, Examples thereof include various olefin low polymers such as indene, tetrahydroindene, tetralin, mineral oil, liquid paraffin and polybutene.
Among these, preferably, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, cyclohexane, cycloheptane, cyclooctane, toluene, xylene, trimethylbenzene, tetralin, mineral oil. , Liquid paraffin and polybutene, and more preferably hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, toluene, tetralin, mineral oil, liquid paraffin and polybutene.
The reason why the amount of highly crystalline components increases by including a hydrocarbon compound in the olefin polymerization catalyst is not clear because it is not determined in terms of the polymerization reaction mechanism, but it is not clear that the olefin polymerization catalyst before contacting the monomer is a hydrocarbon. When charged in a polymerization reactor containing a compound, the catalyst pores are filled with the hydrocarbon compound, which prevents the monomer from reaching the highly copolymerizable active species present inside the pores. It is presumed that by delaying the onset of the polymerization activity, it is possible to obtain an ethylene-based polymer having a large amount of highly crystalline components in which low copolymerizable active species on the catalyst surface are produced. In this case, the concentration of the monomer in the vicinity of the active species decreases, the initial polymerization rate decreases, and the internal pressure due to polymer formation in the catalyst pores becomes smaller than in the case where the hydrocarbon compound is not contained, and the catalyst carrier structure destruction that normally occurs It is considered that the fact that the exposure of new active species due to the above-mentioned phenomenon is less likely to be involved also contributes to the increase of the high crystal component. In addition, in the present invention, the reason why the amount of the high crystal component increases is not limited to the above reason.

2. Method for Preparing Olefin Polymerization Catalyst (1) Preparation of Solid Catalyst Component The method of contacting the components (A) to (C) when obtaining the olefin polymerization catalyst of the present invention is not particularly limited, and for example, the following method may be used. It can be arbitrarily adopted.

(I) After contacting the component (A) with the component (B), the component (C) is contacted.
(II) After contacting the component (A) and the component (C), the component (B) is contacted.
(III) After contacting the component (B) and the component (C), the component (A) is contacted.

Among these contact methods, (I) is preferable.
In any of the contact methods, aromatic hydrocarbons (usually having 6 to 12 carbon atoms) such as benzene, toluene, xylene, and ethylbenzene, heptane, hexane, decane, dodecane are generally used in an inert atmosphere such as nitrogen or argon. , Cyclohexane or the like, or a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon (usually having 5 to 12 carbon atoms), or the like, and a method of bringing each component into contact with or without stirring.
This contact is usually at a temperature of −100° C. to 200° C., preferably −50° C. to 100° C., more preferably −50 to 40° C. for 5 minutes to 50 hours, preferably 30 minutes to 24 hours, and further preferably It is desirable to carry out for 30 minutes to 12 hours.

When the component (A), the component (B) and the component (C) are contacted with each other, as described above, an aromatic hydrocarbon solvent in which a certain component is soluble or hardly soluble and a certain component are insoluble or insoluble. Any sparingly soluble aliphatic or alicyclic hydrocarbon solvent can be used.
Among these, as the solvent, it is preferable to use aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene in which the component (A) and the component (B) are soluble, and toluene is preferable from the viewpoint of economy and safety. Most preferred. These solvents can be appropriately used as a mixed solvent for the purpose of adjusting the solubility of the component (A) and the component (B).

When the contact reaction between the components is carried out stepwise, it may be used as it is as a solvent for the contact reaction in the latter step without removing the solvent used in the former step.
In addition, after the first-stage catalytic reaction using a soluble solvent, a liquid inert hydrocarbon in which a certain component is insoluble or sparingly soluble (for example, pentane, hexane, decane, dodecane, cyclohexane, benzene, toluene, xylene, and other aliphatic hydrocarbons). Hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon) and recover the desired product as a solid, or once the soluble solvent is partially or entirely removed by a means such as drying to obtain the desired product. After removing the product as a solid, a subsequent catalytic reaction of the desired product can also be carried out using any of the inert hydrocarbon solvents described above.
In the present invention, the catalytic reaction of each component may be carried out multiple times.

Further, the olefin polymerization catalyst of the present invention, after contacting the component (A), the component (B) and the component (C), and before being treated with a hydrocarbon compound, distillation under reduced pressure, distillation by heating, removal of entrained gas. It is preferable to remove the solvent used in the above-mentioned catalytic reaction by filtration, decantation, etc. to obtain a solid catalyst component containing the component (A), the component (B) and the component (C) as a powder. The solvent used in the above catalytic reaction is usually less than 0.04 part by weight, preferably less than 0.03 part by weight, more preferably less than 0.02 part by weight, still more preferably 0.01 part by weight, based on 1 part by weight of the solid catalyst component. It is desirable that the removal is performed by the above method so as to be less than 1.

In the present invention, the use ratios of the component (A), the component (B) and the component (C) are not particularly limited, but the following ranges are preferable.

In the component (B), the number of moles (mol/g) of the metal in the compound (B) per gram of the component (C) is usually 0.001 to 0.01, preferably 0.003 to 0.008, and The range of 0.003 to 0.0065 is preferable.

The amount of component (C) used is 1 g per 0.0001 to 5 mmol of transition metal in component (A), preferably 1 g per 0.001 to 0.5 mmol, and more preferably 0.01 to 0.1 mmol. Per gram.

Component (A), component (B), and component (C) are brought into contact with each other by any of the contact methods (I) to (III) described above, and then the solvent is removed, whereby olefin polymerization is performed. The catalyst can be obtained as a solid catalyst. The solvent is removed under normal pressure or reduced pressure at 0 to 200° C., preferably 20 to 150° C., more preferably 20 to 60° C. for 1 minute to 50 hours, preferably 10 minutes to 10 hours, more preferably 30 minutes. It is desirable to carry out in about 2 hours.

(2) Preparation of Catalyst for Olefin Polymerization The method of incorporating the hydrocarbon compound into the solid catalyst component containing the components (A), (B) and (C) is not particularly limited, and for example, the following method is arbitrarily adopted. It is possible.

(I) Add a hydrocarbon compound to the solid catalyst component (ii) Add a mixture of a low boiling point hydrocarbon compound and a high boiling point hydrocarbon compound to the solid catalyst component, and then distill the low boiling point hydrocarbon compound under reduced pressure. (Iii) Add the solid catalyst component to the hydrocarbon compound (iv) Add the solid catalyst component to the mixed liquid of the low boiling point hydrocarbon compound and the high boiling point hydrocarbon compound, and then add the low boiling point hydrocarbon compound. Evaporate under reduced pressure

Here, the low boiling point hydrocarbon compound means a hydrocarbon compound having a boiling point of about 0 to 120° C., preferably 30 to 80° C., butane, pentane, hexane (including each isomer. ) And the like, preferably pentane, hexane (including each isomer) and the like are used. Further, the high boiling point hydrocarbon compound means a hydrocarbon compound having a boiling point of about 80 to 400°C, preferably 100 to 400°C, more preferably 150 to 400°C, and further preferably 20. Liquid at 0°C, particularly preferably liquid at 0°C, having a decomposition temperature of 80°C or higher, preferably 100°C or higher, more preferably 120°C or higher, and heptane, octane, decane, undecane, tridecane, dodecane. , Toluene, xylene, indane, indene, decalin, tetralin, mineral oil, liquid paraffin, polybutene, etc., preferably decane, undecane, dodecane, tridecane, tetralin, mineral oil, liquid paraffin, polybutene and the like are used.

Among these contacting methods, (i) and (ii) are preferable. In any contacting method, a method of adding a hydrocarbon compound to a solid catalyst component is usually employed with or without stirring in an inert atmosphere such as nitrogen or argon.
During this addition, the contact is usually at a temperature of -10°C to 60°C, preferably 0°C to 40°C for 1 minute to 1 hour, preferably 1 minute to 30 minutes, more preferably 1 minute to 15 minutes. It is desirable to contact the solid catalyst component with the hydrocarbon compound.
Further, the vacuum distillation of (ii) and (iv) is carried out at 0 to 200° C., preferably 20 to 150° C., more preferably 20 to 60° C. for 1 minute to 50 hours, preferably 10 minutes to 10 hours, and further It is desirable to carry out for 30 minutes to 2 hours.

In the present invention, the method of incorporating the hydrocarbon compound into the solid catalyst component containing the above-mentioned components (A), (B) and (C) is not particularly limited, but in order to further enhance the effect of the olefin polymerization catalyst of the present invention. The method is preferably carried out by contacting the hydrocarbon compound with the solid catalyst component outside the polymerization reactor. Here, the outside of the polymerization reactor means 10% or less, preferably 5% or less, more preferably 1% or less of the olefin concentration of the polymerization reaction conditions under which the olefin polymerization catalyst of the present invention is used for producing an olefin polymer. More preferably, it is an environment where olefin monomers are absent.

The amount of the hydrocarbon compound used is 0.04 to 100 parts by weight, preferably 0.05 to 60 parts by weight, based on 1 part by weight of the solid catalyst component containing the components (A), (B) and (C). , And more preferably 0.2 to 60 parts by weight. When the amount of the hydrocarbon compound used is less than 0.04 parts by weight, it is not possible to obtain an ethylene-based polymer having a sufficient amount of highly crystalline components (a component which elutes at 85° C. or higher in TREF), and 100 parts by weight. If it exceeds, it is not economically preferable because an olefin polymerization catalyst having a sufficient catalytic activity cannot be obtained.

The appearance of the olefin polymerization catalyst of the present invention may be slurry, mud, or powder. To obtain a higher effect, the content of the hydrocarbon compound may be increased, but the content of the hydrocarbon compound can be set to a relatively small amount by setting it together with suitable selection of the polymerization process and the polymerization conditions. However, it is possible to obtain a high effect.
When a slurry or mud is required as the appearance, by adding about 1 to 100 parts by weight, preferably about 1.5 to 60 parts by weight of a hydrocarbon compound to 1 part by weight of the solid catalyst component. The slurry-like or mud-like olefin polymerization catalyst of the present invention is obtained, which is easy to handle. Further, the olefin polymerization catalyst of the present invention in the form of a slurry that is easy to handle is obtained by more preferably containing about 2 to 50 parts by weight, further preferably about 3 to 20 parts by weight.

When powdery appearance is required, the hydrocarbon compound is added in an amount of 0.04 parts by weight or more and less than about 1 part by weight, preferably 0.08 to 0.8 parts by weight, based on 1 part by weight of the solid catalyst component. A powdery book which is easy to handle by containing 0.1 to 0.7 parts by weight, more preferably 0.15 to 0.6 parts by weight, particularly preferably 0.2 to 0.5 parts by weight. An olefin polymerization catalyst of the invention is obtained. The powder bulk density (g/cm ³ ) of the olefin polymerization catalyst of the present invention thus obtained is usually equal to or higher than the powder bulk density of the solid catalyst component before containing the hydrocarbon compound, and the particle fluidity is Is also excellent. Here, the powder bulk density and the particle fluidity can be evaluated by, for example, the method described in JP 2007-39603 A or the like.

3. Method for producing ethylene polymer (polymerization method)
The above-mentioned olefin polymerization catalyst can be used for homopolymerization of ethylene or copolymerization of ethylene and α-olefin.

As the α-olefin which is a comonomer, those having 3 to 30 carbon atoms, preferably 3 to 8 carbon atoms can be used, and specifically, propylene, 1-butene, 1-hexene, 1-octene and 4-methyl. -1-Pentene etc. are illustrated. It is also possible to copolymerize two or more kinds of α-olefins with ethylene. The copolymerization may be any of alternating copolymerization, random copolymerization and block copolymerization. When ethylene is copolymerized with another α-olefin, the amount of the other α-olefin can be arbitrarily selected within the range of 90 mol% or less of all monomers, but generally 40 mol%. The following is selected in the range of preferably 30 mol% or less, more preferably 10 mol% or less.
It is also possible to use a small amount of a comonomer other than ethylene or α-olefin. In this case, styrenes such as styrene, 4-methylstyrene and 4-dimethylaminostyrene, 1,4-butadiene, 1,5- It has a polymerizable double bond such as dienes such as hexadiene, 1,4-hexadiene and 1,7-octadiene, cyclic compounds such as norbornene and cyclopentene, oxygen-containing compounds such as hexenol, hexenoic acid and methyl octenoate. A compound can be mentioned.

In the present invention, the polymerization reaction can be carried out in the presence of the above-mentioned supported catalyst, preferably by slurry polymerization or gas phase polymerization.
In the case of slurry polymerization, propane, butane, pentane, hexane, heptane, and other aliphatic hydrocarbons, benzene, toluene, xylene, and other aromatic hydrocarbons, cyclohexane, methylcyclohexane, etc. Ethylene or the like is polymerized in the presence or absence of an inert hydrocarbon solvent selected from alicyclic hydrocarbons and the like.
As the inert hydrocarbon solvent used for slurry polymerization, aliphatic hydrocarbons such as propane, isobutane, isopentane, hexane, cyclopentane, and methylcyclopentane, alicyclic hydrocarbons are preferable, and propane, isobutane, isopentane, hexane, etc. Are more preferred, and medium boiling aliphatic hydrocarbons such as isobutane and isopentane are more preferred.
Needless to say, liquid monomers such as liquid ethylene and liquid propylene, 1-butene, 1-hexene, 1-octene 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 flow of ethylene or a comonomer is introduced, circulated or circulated. The polymerization conditions are a temperature of 0 to 250° C., preferably 20 to 110° C., more preferably 60 to 100° C., and a pressure of atmospheric pressure to 10 MPa, preferably atmospheric pressure to 4 MPa, more preferably 0.5 to 2 MPa. The polymerization time is usually 5 minutes to 10 hours, preferably 5 minutes to 5 hours.
The expected catalyst activity level is 3 to 3000 g-PE/g-Cat/h, preferably 5 to 2000 g-PE/g-Cat/h, more preferably 7 to 1500 g-PE/g-Cat/h, and further. It is preferably 7 to 1000 g-PE/g-Cat/h, particularly preferably 10 to 650 g-PE/g-Cat/h.

The molecular weight of the produced polymer can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but by adding hydrogen to the polymerization reaction system, the molecular weight can be adjusted more effectively. You can Further, it is possible to carry out without any trouble even if a component for removing water, that is, a scavenger is added to the polymerization system. Examples of the scavenger include trimethylaluminum, triethylaluminum, organoaluminum compounds such as triisobutylaluminum, the organoaluminum oxy compounds, modified organoaluminum compounds containing branched alkyl, diethylzinc, organozinc compounds such as dibutylzinc, and diethyl. Organomagnesium compounds such as magnesium, dibutylmagnesium and ethylbutylmagnesium, and Grignard compounds such as ethylmagnesium chloride and butylmagnesium chloride are used. Among these, triethylaluminum, triisobutylaluminum and ethylbutylmagnesium are preferable, and triethylaluminum is particularly preferable. The present invention can also be applied to a multi-stage polymerization system of two or more stages in which the polymerization conditions such as hydrogen concentration, amount of monomer, polymerization pressure, and polymerization temperature are different from each other without any trouble.

4. Physical properties of ethylene polymer (characteristics)
The density of the ethylene polymer produced using the olefin polymerization catalyst of the present invention is preferably 0.85 to 0.97 g/cm ³ , more preferably 0.88 to 0.96 g/cm ³ , and further It is preferably 0.89 to 0.95 g/cm ³ .
The MFR (melt flow rate, 190° C., 2.16 kg load) of the ethylene-based polymer produced using the olefin polymerization catalyst of the present invention is preferably 0.001 to 1000 g/10 minutes, more preferably Is 0.005 to 100 g/10 minutes, more preferably 0.01 to 20 g/10 minutes.

Further, the ethylene-based polymer produced by the present invention has a long-chain branched structure, a crystal structure, and the like which are improved as compared with a normal ethylene-based polymer, and has a great feature that it has excellent moldability. ..
Generally, polyethylene is processed into a product as a film, a sheet, a blow-molded body, or a foam-molded body. At this time, it is often the case that the long-chain branched structure or crystal structure of polyethylene has a great influence on the moldability. Are known.
That is, ordinary polyethylene having a narrow molecular weight distribution or composition distribution has poor melt strength and thus poor moldability, whereas polyethylene having a high crystalline component or a long chain branching component has strain hardening (strain hardening during melt elongation). ) That is, it is considered that polyethylene having a characteristic that the elongational viscosity sharply increases on the high strain side and showing this characteristic remarkably has excellent moldability.
The catalyst of the present invention not only produces long-chain branching with high activity, but also by adding a hydrocarbon compound to the catalyst, imparts a high crystalline component that is favorable for mechanical strength and contributes to improvement of moldability. Made it possible.
In addition, in this specification, a highly crystalline component means a component which elutes at 85° C. or higher in temperature rising elution fractionation (TREF). When the content of the component is 5.0 wt% or more, the strain hardening becomes remarkable.

The long-chain branched structure has a molecular weight of 100,000 to 100,000 with a branching index g'measured by a gel permeation chromatography (GPC) measuring device in which a differential refractometer, a viscosity detecting system, and a light scattering detector described later are combined. The ethylene-based polymer produced by the olefin polymerization catalyst of the present invention, which is evaluated by the minimum value (gc) in the range of 10,000, preferably has a gc of 0.35 to 0.85.

The molecular weight distribution is evaluated by Mw/Mn measured by GPC described below, and the ethylene polymer produced by the olefin polymerization catalyst of the present invention preferably has Mw/Mn of 4.5 to 12. ..

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples as long as the gist thereof is not exceeded.
The measuring method used in the examples is as follows. The catalyst synthesis step and the polymerization step were all performed in a purified nitrogen atmosphere, and the solvent used was one that had been dehydrated and deoxygenated by nitrogen bubbling.

1. Various evaluation (measurement) methods (1) MFR:
MFR was measured at 190° C. under a load of 2.16 kg according to JIS K6760. The FR (flow rate ratio) was calculated from the ratio of MFR 10 kg and MFR (=MFR 10 kg/MFR) that were similarly measured under the conditions of 190° C. and 10 kg load.

(2) Density:
According to JIS K7112, the density was measured by a density gradient tube method after heat-treating the strand obtained at the time of MFR measurement at 100° C. for 1 hour and further leaving it at room temperature for 1 hour.

(3) Measurement of molecular weight distribution:
In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are those measured by the gel permeation chromatography (GPC) method. The conversion from the retention capacity to the molecular weight is performed using a calibration curve prepared in advance using standard polystyrene. The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation. F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000. A calibration curve is prepared by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg/mL BHT) so that each of them will be 0.5 mg/mL. For the calibration curve, a cubic expression obtained by approximation by the least square method is used. The following numerical values are used for the viscosity formula [η]=K×M ^α used for conversion into the molecular weight.
PS: K=1.38×10 ⁻⁴ , α=0.7
PE: K=3.92×10 ⁻⁴ , α=0.733
PP: K=1.03×10 ⁻⁴ , α=0.78

The GPC measurement conditions are as follows.
Device: Waters GPC (ALC/GPC 150C)
Detector: MIRAN 1A IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: Showa Denko AD806M/S (3)
Mobile phase solvent: o-dichlorobenzene Measurement temperature: 140°C
Flow rate: 1.0 ml/min Injection volume: 0.2 ml
Sample preparation: The sample is prepared using ODCB (containing 0.5 mg/mL BHT) to prepare a 1 mg/mL solution, which is dissolved at 140° C. in about 1 hour. The baseline and section of the obtained chromatogram are set as illustrated in FIG.

(4) Measurement of the amount of components eluted at 85°C or higher:
A sample is dissolved in orthodichlorobenzene (containing 0.5 mg/mL BHT) at 140°C to form a solution. After introducing this into a TREF column at 140° C., it is cooled to 100° C. at a temperature lowering rate of 8° C./min, subsequently cooled to −15° C. at a temperature lowering rate of 4° C./min, and held for 60 minutes. After that, orthodichlorobenzene (containing 0.5 mg/mL BHT) as a solvent was flown through the column at a flow rate of 1 mL/min, and the components dissolved in orthodichlorobenzene at −15° C. in the TREF column were eluted for 10 minutes, Next, the column is heated linearly to 140° C. at a heating rate of 100° C./hour to obtain an elution curve. At this time, the amount of components eluted at 85° C. or higher was defined as ≧85° C. soluble amount (unit: wt %).
FIG. 3 shows an example of the analysis result by the above TREF.

Equipment (TREF part)
TREF column: 4.3 mmφ x 150 mm stainless steel column Column packing material: 100 μm surface inactivated glass beads Heating method: Aluminum heat block Cooling method: Peltier element (Peltier element is cooled by water)
Temperature distribution: ±0.5°C
Temperature Controller: Chino Co., Ltd. Digital Program Controller KP1000
(Bulb oven)
Heating method: Air bath type oven Temperature during measurement: 140°C
Temperature distribution: ±1℃
Valve: 6-way valve, 4-way valve (sample injection part)
Injection method: Loop injection method Injection amount: Loop size 0.1 ml
Inlet heating method: Aluminum heat block Measurement temperature: 140℃
(Detection unit)
Detector: Fixed wavelength infrared detector FOXBORO MIRAN 1A
Detection wavelength: 3.42 μm
High temperature flow cell: LC-IR micro flow cell, optical path length 1.5 mm, window shape 2φ x 4 mm oblong, synthetic sapphire window plate Measurement temperature: 140°C
(Pump part)
Liquid sending pump: SSC-3461 pump manufactured by Senshu Scientific Co., Ltd. Measurement conditions Solvent: Orthodichlorobenzene (containing 0.5 mg/mL BHT)
Sample concentration: 5mg/mL
Sample injection volume: 0.1 mL
Solvent flow rate: 1 mL/min

(5) Calculation of branching index (gc):
(I) Branched Structure Analysis by GPC-Viscometer (GPC-VIS) As a GPC device equipped with a differential refractometer (RI) and a viscosity detector (Viscometer), Alliance GPCV2000 manufactured by Waters was used. Also, as the light scattering detector, a multi-angle laser light scattering detector (MALLS) Wyatt Technology DAWN-E was used. The detector was connected in the order of MALLS, RI, and Viscometer. The mobile phase solvent is 1,2,4-trichlorobenzene (antioxidant Irganox 1076 added at a concentration of 0.5 mg/mL). The flow rate is 1 mL/min. For the column, two Tohso GMHHR-H(S) HTs were connected and used. The temperature of the column, the sample injection part, and each detector is 140°C. The sample concentration was 1 mg/mL. The injection volume (sample loop volume) is 0.2175 mL. In order to obtain the absolute molecular weight (M) obtained from MALLS, the radius of gyration (Rg) and the intrinsic viscosity ([η]) obtained from Viscometer, the data processing software ASTRA (version 4.73.04) attached to MALLS is used. The calculation was performed with reference to the following documents.

References:
1. Developments in polymer characterisation, vol. 4. Essex: Applied Science; 1984. Chapter1.
2. Polymer, 45, 6495-6505 (2004).
3. Macromolecules, 33, 2424-2436 (2000).
4. Macromolecules, 33, 6945-6952 (2000).

(Ii) Calculation of Branching Index (gc) etc. The branching index (g′) is calculated by measuring the sample with the above Viscometer to obtain the limiting viscosity (η _branch ) and the limiting viscosity (( _branch )) separately obtained by measuring the linear polymer ( It is calculated as the ratio (η _branch / η _lin) and eta _lin).
The introduction of long chain branching into a polymer molecule results in a smaller radius of gyration as compared to a linear polymer molecule of the same molecular weight. Since the intrinsic viscosity decreases as the radius of gyration decreases, the ratio (η _branch /η) of the intrinsic viscosity (η _branch ) of the branched polymer to the intrinsic viscosity (η _lin ) of a linear polymer having the same molecular weight as the long-chain branch is introduced. _lin ) becomes smaller. Therefore, when the branching index (g′=η _branch /η _lin ) becomes a value smaller than 1, it means that the branch is introduced, and as the value becomes smaller, the number of long chain branches introduced increases. Means to go. In this specification, in particular, the absolute minimum molecular weight obtained from MALLS is calculated as gc, which is the minimum value of g′ in the molecular weight of 100,000 to 1,000,000.
FIG. 2 shows an example of the analysis result by the GPC-VIS. The left side of FIG. 2 shows the molecular weight distribution curve measured based on the molecular weight (M) obtained from MALLS and the concentration obtained from RI, and the right side of FIG. 1 shows the branching index (g′) in the molecular weight (M). .. Here, as the linear polymer, a linear polyethylene Standard Reference Material 1475a (National Institute of Standards & Technology) was used.

(II) Materials used 1-(a) Synthesis of metallocene compound Metallocene compound A: Dimethylsilylene (4-(4-trimethylsilyl-phenyl)- as a metallocene complex according to the method disclosed in JP 2013-22771 A. Indenyl)(cyclopentadienyl)zirconium dichloride was synthesized.

(Example 1)
(1) Preparation of catalyst Under a nitrogen atmosphere, 30 g of silica was placed in a 500 ml three-necked flask, and dehydrated toluene was slurried in 195 ml. Metallocene compound A (410 mg) was placed in a separately prepared 200 ml eggplant-shaped flask under a nitrogen atmosphere and dissolved with dehydrated toluene (49.7 ml). At room temperature, 82.8 ml of a 20% methylaluminoxane/toluene solution manufactured by Albemarle was added to a toluene solution of metallocene compound A, and the mixture was stirred for 30 minutes. A toluene solution of the reaction product of metallocene compound A and methylaluminoxane was added in total while heating and stirring a 300 ml three-necked flask containing a toluene slurry of silica in an oil bath at 40°C. After stirring at 40° C. for 1 hour, the toluene solvent was distilled off under reduced pressure while heating at 40° C., and dried under reduced pressure for 120 minutes to obtain a solid catalyst component. 12.2 ml of dehydrated tetralin (Kanto Chemical Co., Inc., Deer grade) was added to 53.8 g of the obtained solid catalyst component to obtain a tetralin-containing catalyst.

(2) Production of ethylene/1-hexene copolymer An ethylene/1-hexene copolymer was produced using the catalyst obtained in the above (1) Preparation of catalyst.
That is, 30 ml of 1-hexene, 0.20 mmol of triethylaluminum, 2000 ml of hydrogen and 800 ml of isobutane were added to a 2 L autoclave equipped with an induction stirrer, the temperature was raised to 75°C, and ethylene was introduced to maintain the ethylene partial pressure at 1.4 MPa. .. Next, 0.08 g of the catalyst obtained in the preparation of the catalyst of the above (1) was injected with nitrogen, the polymerization was continued for 60 minutes while maintaining the ethylene partial pressure of 1.4 MPa and the temperature of 75°C. During the polymerization reaction, 1-hexene was additionally supplied at a supply rate proportional to the ethylene consumption rate. The amount of 1-hexene additionally supplied was 0.5 mL. The ethylene/1-hexene copolymer thus obtained was 21.6 g. Table 9 shows the polymerization conditions, and Table 10 shows the polymerization results.

(Example 2)
To the solid catalyst component prepared by the same synthesis method as in Example 1, 15.7 ml of dehydrated tridecane (Kanto Kagaku Co., Ltd., Deer grade) was added to obtain a dodecane-containing catalyst. An ethylene/1-hexene copolymer was produced in the same manner as in Example 1 except that 0.078 g of this catalyst was used. As a result, 23.5 g of ethylene/1-hexene copolymer was produced. Table 9 shows the polymerization conditions, and Table 10 shows the polymerization results.

(Reference example 3)
18.3 ml of dehydrated hexane was added to the solid catalyst component prepared by the same synthetic method as in Example 1 to obtain a hexane-containing catalyst. An ethylene/1-hexene copolymer was produced in the same manner as in Example 1 except that 0.081 g of this catalyst was used and the amount of 1-hexene additionally supplied was 1.5 mL. As a result, 30.4 g of ethylene/1-hexene copolymer was produced. Table 9 shows the polymerization conditions, and Table 10 shows the polymerization results.

(Comparative Example 1)
A solid catalyst component prepared in the same manner as in Example 1 except that toluene used as a solvent was distilled off under reduced pressure, 0.082 g was used as the catalyst as it was, and the amount of 1-hexene additionally supplied was 4.0 mL, except that An ethylene/1-hexene copolymer was produced in the same manner as in Example 1. As a result, 53.7 g of ethylene/1-hexene copolymer was produced. Table 9 shows the polymerization conditions, and Table 10 shows the polymerization results.

(Example 4)
A solid catalyst component was prepared in the same manner as in Example 1 except that 78.7 ml of a 20% methylaluminoxane/toluene solution manufactured by Albemarle was added. 7.7 ml of liquid paraffin (manufactured by Moresco, trade name: Moresco White P-120, average molecular weight: 365, density: 0.853 g/cm ³ ) dehydrated by nitrogen bubbling in a 200 ml eggplant flask and 195 ml of dehydrated hexane. Was added, and the mixture was stirred at room temperature for 5 minutes. 30 g of the solid catalyst component obtained under a nitrogen atmosphere was placed in a separately prepared 500 ml three-necked flask, and the total amount of the mixed solution of liquid paraffin and hexane was added while stirring. After stirring for 10 minutes, the mixture was heated to 40° C. and hexane was distilled off under reduced pressure to obtain a liquid paraffin-containing catalyst. An ethylene/1-hexene copolymer was produced in the same manner as in Example 1 except that 0.102 g of this catalyst was used and the amount of 1-hexene additionally supplied was 4.0 mL. As a result, 45.3 g of ethylene/1-hexene copolymer was produced. Table 9 shows the polymerization conditions, and Table 10 shows the polymerization results.

(Example 5)
Instead of liquid paraffin, 14.3 ml of polybutene dehydrated by nitrogen bubbling (manufactured by JX Nikko Nisseki Energy Co., Ltd., trade name: LV-7, average molecular weight: 300, density: 0.830 g/cm ³ ) was used. A catalyst was prepared in the same manner as in Example 4 except for the above. An ethylene/1-hexene copolymer was produced in the same manner as in Example 1 except that 0.115 g of this catalyst was used and the amount of 1-hexene additionally supplied was 3.5 mL. As a result, 44.9 g of an ethylene/1-hexene copolymer was produced. Table 9 shows the polymerization conditions, and Table 10 shows the polymerization results.

(Example 6)
To 0.08 g of the solid catalyst component prepared in the same manner as in Example 4, 0.3 ml of dehydrated polybutene prepared in the same manner as in Example 5 and 6 ml of hexane were added to prepare a polybutene/hexane-containing catalyst. An ethylene/1-hexene copolymer was produced in the same manner as in Example 1 except that the entire amount of this catalyst was used and the additionally supplied amount of 1-hexene was 5.0 mL. As a result, 52.0 g of ethylene/1-hexene copolymer was produced. Table 9 shows the polymerization conditions, and Table 10 shows the polymerization results.

(Example 7)
A polybutene/hexane-containing catalyst was prepared in the same manner as in Example 6 except that 0.87 ml of dehydrated polybutene was added. An ethylene/1-hexene copolymer was produced in the same manner as in Example 1 except that the total amount of this catalyst was used and the additionally supplied amount of 1-hexene was 2.0 mL. As a result, 34.9 g of an ethylene/1-hexene copolymer was produced. Table 9 shows the polymerization conditions, and Table 10 shows the polymerization results.

(Comparative example 2)
A polybutene/hexane-containing catalyst was prepared in the same manner as in Example 6 except that 5.12 ml of dehydrated polybutene was added. An ethylene/1-hexene copolymer was produced in the same manner as in Example 1 except that the entire amount of this catalyst was used and the amount of 1-hexene additionally supplied was 0.5 mL. As a result, 16.5 g of ethylene/1-hexene copolymer was produced. Table 9 shows the polymerization conditions, and Table 10 shows the polymerization results.

(Comparative example 3)
A solid catalyst component prepared in the same manner as in Example 4 except that toluene used as a solvent was distilled off under reduced pressure, and 0.08 g of the solid catalyst component was directly used as a catalyst, except that the amount of 1-hexene additionally supplied was 5.0 mL. An ethylene/1-hexene copolymer was produced in the same manner as in Example 1. As a result, 59.2 g of ethylene/1-hexene copolymer was produced. Table 9 shows the polymerization conditions, and Table 10 shows the polymerization results.

(Reference example 8)
A solid catalyst component was prepared in the same manner as in Example 1 except that 31.0 ml of a 20% methylaluminoxane/toluene solution manufactured by Albemarle was added. 1.6 ml of dehydrated toluene was added to 27.7 g of the obtained solid catalyst component to prepare a toluene-containing catalyst. An ethylene/1-hexene copolymer was produced in the same manner as in Example 1 except that 0.083 g of this catalyst was used and the amount of 1-hexene additionally supplied was 0.5 mL. As a result, 16.2 g of ethylene/1-hexene copolymer was produced. Table 9 shows the polymerization conditions, and Table 10 shows the polymerization results.

(Reference example 9)
A solid catalyst component was prepared in the same manner as in Example 1 except that 38.3 ml of a 20% methylaluminoxane/toluene solution manufactured by Albemarle was added. 1.9 ml of dehydrated toluene was added to 32.9 g of the obtained solid catalyst component to prepare a toluene-containing catalyst. An ethylene/1-hexene copolymer was produced in the same manner as in Example 1 except that 0.083 g of this catalyst was used and the amount of 1-hexene additionally supplied was 1.0 mL. As a result, 25.2 g of ethylene/1-hexene copolymer was produced. Table 9 shows the polymerization conditions, and Table 10 shows the polymerization results.

(Reference example 10)
To the solid catalyst component prepared in the same manner as in Example 1, 0.2 ml of dehydrated toluene was added to prepare a toluene-containing catalyst. An ethylene/1-hexene copolymer was produced in the same manner as in Example 1 except that 0.082 g of this catalyst was used and the amount of 1-hexene additionally supplied was 3.0 mL. As a result, 49.4 g of ethylene/1-hexene copolymer was produced. Table 9 shows the polymerization conditions, and Table 10 shows the polymerization results.

(Reference example 11)
A catalyst was prepared in the same manner as in Example 1 except that 334 mg of dimethylsilylenebisindenyl zirconium dichloride (metallocene compound B) was used instead of 410 mg of metallocene compound A. An ethylene/1-hexene copolymer was produced in the same manner as in Example 7 except that the additionally supplied amount of 1-hexene was 5.5 mL. As a result, 75.9 g of ethylene/1-hexene copolymer was produced. Table 9 shows the polymerization conditions, and Table 10 shows the polymerization results.
(Comparative example 4)
Preparation was carried out in the same manner as in Reference Example 11, and the solid catalyst component obtained by distilling off the toluene used as the solvent under reduced pressure was directly used as the catalyst in an amount of 0.058 g, and the amount of 1-hexene supplied was 10.2 mL. An ethylene/1-hexene copolymer was produced in the same manner as in Example 1. As a result, 99.5 g of ethylene/1-hexene copolymer was produced. Table 9 shows the polymerization conditions, and Table 10 shows the polymerization results.

[Evaluation results]
Examples 1 to 2 and Reference Examples 3, 9 and 10 have various carbonizations to the solid catalyst component having the same solid catalyst component and the use ratio (component (B)/component (C) = 0.0048 mol/g). It contains a hydrogen compound. In any of the examples, the amount of ≧85° C. soluble component by TREF was 5.3 to 7.6 wt% (compared with 4.4 wt% of Comparative example 1 using the same solid catalyst component as it was as a catalyst). 5.0 wt% or more), a sufficient number and length of long chain branches were introduced, the copolymer composition distribution was broadened, and an ethylene-based polymer having a large amount of highly crystalline components was obtained. It's clear.
Similarly, in Examples 4 to 7, the solid catalyst component having the same solid catalyst component and the use ratio (component (B)/component (C) = 0.0076 mol/g) was added to the liquid paraffin or the hydrocarbon compound. Although polybutene was added, the amount of soluble components ≧85° C. by TREF was 5.2 to 7.% as compared with 3.8 wt% of Comparative Example 3 using the same solid catalyst component as it was as a catalyst. It has increased to 5 wt% (5.0 wt% or more), a sufficient number and length of long-chain branches have been introduced, and the copolymer composition distribution has expanded to obtain an ethylene polymer with many high crystalline components. It is clear that
Further, in Examples 1 to 2, 4 to 7 and Reference Examples 3 and 8 to 10, the metallocene compound A is used as the component (A), but in Reference Example 11 using the metallocene compound B as the component (A). Also, as compared with Comparative Example 4 evaluated under the same conditions except that the hydrocarbon compound was not added, the soluble amount of ≧85° C. increased from 1.1 wt% (Comparative Example 4) to 5.3 wt% (Reference Example 11). Increased, showing the effect of the present invention.
Reference Example 8 contains the same amount of the same hydrocarbon compound as Reference Example 9, but since component (B)/component (C) of Reference Example 8 is smaller, the soluble amount of ≧85° C. Was larger, and the effect of inclusion of the hydrocarbon compound became more remarkable.
In addition, in particular, comparing Examples 6 and 7 and Comparative Example 2 in which polybutene/hexene was used as the hydrocarbon compound, there was a tendency that the ≧85° C. soluble content increased as the polybutene increased. However, in Comparative Example 2 in which the amount of the hydrocarbon compound exceeded 100 parts by weight, the polymerization activity was significantly reduced.

According to the olefin polymerization catalyst of the present invention, it is possible to produce an ethylene-based polymer that introduces a sufficient number and length of long-chain branches and has a large amount of highly crystalline components (the amount of components eluted at 85° C. or higher in TREF). Becomes And the moldability of metallocene polyethylene can be improved. Therefore, the method for producing an olefin polymer (particularly an ethylene polymer) using the olefin polymerization catalyst of the present invention is industrially very useful.

Claims (8)

A method for producing an ethylene polymer using an olefin polymerization catalyst containing the following components (A), (B) and (C):
Component (A), relative to the solid catalyst component 1 part by weight comprising (B) and (C), tridecane, tetralin, mineral oil, liquid paraffin, and at least one hydrocarbon compound selected from the group consisting of polybutene 0 0.05 to 60 parts by weight, and a step of obtaining the olefin polymerization catalyst by containing the hydrocarbon compound in contact with the solid catalyst component outside the polymerization reactor,
Using the olefin polymerization catalyst, a molecular weight of branching index g′ of 100,000 to 1,000,000 measured with a gel permeation chromatography (GPC) measuring device combining a differential refractometer, a viscosity detection system and a light scattering detector. And a step of obtaining the ethylene polymer having a minimum value (gc) of 0.35 to 0.85 between them, the method for producing an ethylene polymer.
Component (A): a bridged cyclopentadienylindenyl compound containing a transition metal element represented by the following general formula ( 4 )
[In the general formula (4), M ^1c represents a transition metal of Ti, Zr, or Hf. X ^1c and X ^2c are each independently 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, and a hydrocarbon having 1 to 20 carbon atoms. A group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms is shown. Q ^1c and Q ^2c represent a carbon atom, a silicon atom or a germanium atom. R ^1c independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and four R ^{1c s} may form a ring together with Q ^1c and Q ^2c which are bonded. .. m ^c is 0 or 1, and when m ^c is 0, Q ^1c is directly bonded to the conjugated 5-membered ring containing R ^2c . R ^2c is a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, A C1-C20 hydrocarbon group containing oxygen or a C1-C20 hydrocarbon group-substituted silyl group is shown. R ^4c independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, or a t-butyl group, and four R ^4c The sum of the number of carbon atoms is 4 or less. R ^3c represents a substituted aryl group represented by the following general formula (4-a).
(In formula (4-a), Y ^1c represents an atom of Group 14, Group 15 or Group 16 of the periodic table. R ^5c , R ^6c , R ^7c , R ^8c and R ^9c are each independently hydrogen. Atom, chlorine atom, bromine atom, hydrocarbon group having 1 to 20 carbon atoms, hydrocarbon group having 1 to 20 carbon atoms containing oxygen or nitrogen, hydrocarbon group substituted amino group having 1 to 20 carbon atoms, 1 to carbon atoms An alkoxy group having 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms; R ^5c , R ^6c , R ^7c , R ^8c and R ^9c may form a ring together with the atoms bonded to adjacent Rs with each other, and n ^c is 0 or 1. If ^{n c} is ^0, there is no substituent ^{R 5c} to ^{Y 1c} .p ^c is 0 or 1, if ^{p c} is ^0, the carbon atom ^{to which R 8c} and ^{R 8c} is attached is absent , The carbon atom to which R ^7c is bound and the carbon atom to which R ^9c is bound are directly bound to each other, and when Y ^1c is a carbon atom, at least one of R ^5c , R ^6c , R ^7c , R ^8c and R ^9c. Is not a hydrogen atom.)]
Component (B): at least one compound selected from the group consisting of organoaluminum oxy compounds, borane compounds, and borate compounds Component (C): silica In the general formula (4), R ^4c Each independently represent a hydrogen atom, a methyl group or a t-butyl group, and four R ^4c The method for producing an ethylene-based polymer according to claim 1, wherein when any one of the above is a t-butyl group, the other is a hydrogen atom. In the general formula (4), R ^4c Each independently represent a hydrogen atom or a methyl group, The method for producing an ethylene-based polymer according to claim 1 or 2, wherein The component (B), the manufacturing method of the ethylene polymer according to any one of claims 1-3, characterized in that the alumoxane. Moles percentage of the metal of the component (C) the component to 1 gram (B) is 0.001 to 0.010 (mol / g) any of the claims 1-4, characterized in that the 1 The method for producing an ethylene-based polymer as described in the item. The solid catalyst component, after contacting said component (A) and the component (B), any one of the claims 1-5, characterized in that it is manufactured by contacting the component (C) The method for producing an ethylene-based polymer as described in the item. Relative to the solid catalyst component 1 part by weight, the production method of the ethylene polymer according to any one of claims 1 to 6, characterized in that formed by incorporating the 1-60 parts by weight of a hydrocarbon compound .. Said hydrocarbon compound, tridecane, tetralin, liquid paraffin, and ethylene-based polymer The method according to any one of claims 1 to 7, characterized in that at least one selected from the group consisting of polybutene ..