JP5606144B2 - Method for producing polyolefin - Google Patents

Description

  The present invention relates to a method for producing a polyolefin. More specifically, the present invention relates to a method for producing a polyolefin capable of controlling stereoregularity.

  Stereoregular polyolefins are used in a wide range of fields because they have excellent properties such as mechanical strength and heat resistance. Polyolefin properties are greatly affected by its stereoregularity, and the stereoregularity control of polyolefin is achieved, for example, by adding an electron donor or adjusting the addition amount of other chemical substances such as alkali metal compounds described later. Done.

The stereoregularity is controlled by adding a silane compound in Patent Document 1, an alkali metal compound and an alkaline earth metal compound in Patent Document 2, and a polyene compound and a transition metal compound having a specific mixing ratio in Patent Document 3.
However, since equipment for adding these compounds is required, not only does the production cost increase, but complete separation and purification of these compounds may be difficult. There was a risk of it occurring.

  Non-Patent Document 1 teaches that the stereoregularity changes depending on the concentration of olefin, and it is necessary to lower the olefin concentration in order to lower the stereoregularity. The same is disclosed in Non-Patent Documents 2 and 3.

For example, in solution polymerization, when the propylene concentration in the reaction solution is to be lowered, the propylene concentration in the reaction solution can be lowered by lowering the reaction pressure and lowering the solubility of propylene in the solvent.
In industrial polymerization reactions, it is necessary to remove reaction heat, and a method of cooling and condensing gas phase components in the reaction field with a refrigerant is used. However, when the reaction pressure is reduced as described above, Since the condensation temperature is also lowered, there is a problem that the temperature of the refrigerant used for cooling requires a refrigerant lower in temperature than when the reaction pressure is high, resulting in an increase in manufacturing cost.

JP-A-7-173223 JP 2002-308923 A JP-A-8-3111119

J. Am. Chem. Soc. 1994, 116, 9329-9330 J. Am. Chem. Soc. 1999, 121, 564-573 Macromolecules 1995, 28, 6667-6676

  An object of the present invention is to provide a method for producing a polyolefin in which stereoregularity can be controlled.

According to the present invention, the following polyolefin production methods are provided.
1. In a method for producing a polyolefin in which an α-olefin having 3 or more carbon atoms is polymerized in the presence of a metallocene catalyst,
A polyolefin having a condensation temperature at 1 MPaG within the range of ± 20 ° C. of the condensation temperature at 1 MPaG of the α-olefin, and a total reaction field pressure of 0.5 MPaG to 4.5 MPaG without being a catalyst poison. Production method.
2. 2. The method for producing a polyolefin according to 1, wherein the compound that does not become the catalyst poison and the condensation temperature at 1 MPaG is in the range of ± 20 ° C. of the condensation temperature at 1 MPaG of the α-olefin is paraffin having 3 or more carbon atoms.
3. 1 or 2 in which the partial pressure in the reaction field of the compound in which the condensation temperature at 1 MPaG is in the range of ± 20 ° C. of the condensation temperature at 1 MPaG of the α-olefin is 0.001 to 4.5 MPa without becoming the catalyst poison. A method for producing the polyolefin according to the description.
4). The method for producing a polyolefin according to any one of 1 to 3, wherein a partial pressure in the reaction field of the α-olefin having 3 or more carbon atoms is 0.001 to 4.5 MPa.
5. The manufacturing method of polyolefin in any one of 1-4 whose superposition | polymerization temperature is 0-150 degreeC.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of polyolefin which can control stereoregularity can be provided.

It is a figure which shows the relationship between the propylene density | concentration and the stereoregularity of the obtained polypropylene.

  The method for producing a polyolefin of the present invention is a method for producing a polyolefin in which an α-olefin having 3 or more carbon atoms is polymerized in the presence of a metallocene catalyst, and does not become a catalyst poison, and the condensation temperature at 1 MPaG is the condensation at 1 MPaG of the α-olefin. A compound having a temperature in the range of ± 20 ° C. is added, and the total pressure in the reaction field is set to 0.5 MPaG to 4.5 MPaG.

For example, in the case of solution polymerization in which polymerization of α-olefin is performed in a polymerization solvent, the total pressure and partial pressure of the reaction field mean the total pressure and partial pressure of the reaction system gas phase part, respectively.
Further, MPaG is a gauge pressure based on the atmospheric pressure, and has a relationship of XX [MPaG] = XX + 0.1013 [MPaA] with MPaA (absolute pressure) based on the vacuum pressure.

In the polyolefin production method of the present invention, in order to control the stereoregularity of the resulting polyolefin, the polymerization reaction rate is adjusted by changing the olefin concentration in the reaction field. At the time of olefin polymerization, a compound having a condensation temperature in 1 MPaG that does not become a catalyst poison according to the concentration of olefin is in a specific range, and the total pressure in the reaction field is maintained in a specific range.
By setting the total pressure of the reaction field within a specific range, it is possible to produce a polyolefin having a desired stereoregularity without changing the refrigerant used for removing the polymerization reaction heat.

In the method for producing a polyolefin according to the present invention, the total pressure in the reaction field is 0.5 MPaG to 4.5 MPaG, preferably 1.0 MPaG to 3.5 MPaG.
When the total pressure in the reaction field is less than 0.5 MPaG, the reaction temperature and the condensation temperature are lowered, and there is a possibility that the reaction rate is lowered and the heat removal efficiency is lowered. On the other hand, when the total pressure in the reaction field exceeds 4.5 MPaG, the reaction temperature and the condensation temperature increase, and the catalyst may be deactivated.

A compound that does not become a catalyst poison and has a condensation temperature at 1 MPaG in the range of ± 20 ° C. of the condensation temperature of α-olefin at 1 MPaG (hereinafter sometimes referred to simply as an additive compound) is preferably not a catalyst poison and is 1 MPaG. Is a compound having a condensation temperature in the range of ± 10 ° C. of the condensation temperature at 1 MPaG of α-olefin.
When the compound to be added is not within the range of ± 20 ° C. of the condensation temperature at 1 MPaG of the α olefin, the added compound condenses at a temperature different from that of the α olefin when the reaction heat is removed, so that the reaction heat is efficiently generated. It is not a compound that removes. For example, when nitrogen is added, the nitrogen does not become a catalyst poison, and the pressure in the reaction field can be adjusted. However, when the latent heat of vaporization type is selected as a means for removing reaction heat, it is condensed in the heat exchanger. Because it is difficult, a larger heat exchanger and a refrigerant having a lower temperature are required.

A compound which does not become a catalyst poison and whose condensation temperature at 1 MPaG is within the range of ± 20 ° C. of the condensation temperature of α-olefin at 1 MPaG is preferably a paraffin having 3 or more carbon atoms because it is inexpensive and easy to separate and recycle. More preferably, it is a paraffin having n to n + 2 carbon atoms, where n is the carbon number of the α-olefin as a raw material monomer, and more preferably a paraffin having the same carbon number as that of the α-olefin.
The paraffin to be added may be only one kind or a mixture of two or more kinds.
The upper limit of the carbon number of the paraffin having 3 or more carbon atoms is not particularly limited, but is 12.

The partial pressure in the reaction field of the compound which does not become a catalyst poison and the condensation temperature at 1 MPaG is in the range of ± 20 ° C. of the condensation temperature at 1 MPaG of α-olefin is preferably 0.001 to 4.5 MPa, more preferably. Is 0.01 to 2.0 MPa, more preferably 0.1 to 1.0 MPa.
If the partial pressure of the additive compound in the reaction field is less than 0.001 MPa, the partial pressure of the α-olefin in the reaction field may not be substantially adjusted. On the other hand, when the partial pressure of the additive compound in the reaction field is more than 4.5 MPa, the condensation temperature increases and the catalyst used for the reaction may be deactivated.

The α-olefin having 3 or more carbon atoms, which is a raw material monomer, is preferably propylene.
When the raw material monomer is an α-olefin (ethylene) having less than 3 carbon atoms, the resulting polymer has no stereoregularity.
The upper limit of the carbon number of the α-olefin having 3 or more carbon atoms is not particularly limited, but is 10.

The partial pressure of the α-olefin having 3 or more carbon atoms is preferably 0.001 to 4.5 MPa, more preferably 0.1 to 4.0 MPa, and further preferably 0.5 to 3.0 MPa.
When the partial pressure of the α-olefin is less than 0.001 MPa, the reaction rate is slow, and there is a possibility that the reaction time and the amount of catalyst used may increase when trying to obtain a certain amount of polyolefin. On the other hand, when the partial pressure of α-olefin exceeds 4.5 MPa, the condensation temperature is too high and the catalyst used for the reaction may be deactivated.

The concentration of the α-olefin having 3 or more carbon atoms in the reaction field is preferably 0.01 to 99.99 wt%, more preferably 10 wt% or more.
When the α-olefin concentration is less than 0.01 wt%, the reaction rate is too low, and there is a risk that the reaction time and the amount of catalyst used will increase when a certain amount of polymer is to be obtained.

The metallocene catalyst is not particularly limited, and a known metallocene catalyst can be used, but a polymerization catalyst disclosed in WO2006 / 117893A1 is preferable. .
Specifically, (A) a transition metal compound, (B) a solid boron compound that forms an ion pair with the component (A), (C) an organoaluminum compound, and (D) an α-olefin, an internal olefin, a polyene Is a polymerization catalyst obtained by contacting one or more compounds selected from (hereinafter sometimes referred to as the polymerization catalyst of the present invention).

(A) As a transition metal compound, a metallocene complex etc. which have a chelate type complex, an unbridged ligand, or a bridged ligand are mentioned.
Examples of the chelate-type complex include N, N′-bis (2,6-diisopropylphenyl) -1,2-dimethylethylenediiminonickel dibromide, N, N′-bis (2,6-diisopropylphenyl)- 1,2-dimethylethylenediiminopalladium dibromide and the like.
Examples of the metallocene complex having a non-bridged ligand include biscyclopentadienylzirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, and bisindene. And nilzirconium dichloride.

  A metallocene complex in which a ligand forms a crosslinked structure via a crosslinking group has a higher polymerization activity than a metallocene complex in which a crosslinked structure is not formed. Accordingly, among metallocene complexes, metallocene complexes in which a ligand forms a crosslinked structure via a crosslinking group are preferred, mono-bridged metallocene complexes and bi-bridged metallocene complexes are more preferred, and bi-bridged metallocene complexes are most preferred.

  Examples of mono-bridged metallocene complexes include dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) zirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (tert-butylamide) Zirconium dichloride, dimethylsilylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-naphthyl) Indenyl) zirconium dichloride, dimethylsilylene bis (2-methylindenyl) zirconium dichloride, ethylenebis (2-methylindenyl) zirconium dichloride, and the like.

〔式中、Ｍは周期律表第３〜１０族又はランタノイド系列の金属元素を示し、Ｅ^１及びＥ^２はそれぞれ置換シクロペンタジエニル基、インデニル基、置換インデニル基、ヘテロシクロペンタジエニル基、置換ヘテロシクロペンタジエニル基、アミド基、ホスフィド基、炭化水素基及び珪素含有基の中から選ばれた配位子であって、Ａ^１及びＡ^２を介して架橋構造を形成しており、またそれらは互いに同一でも異なっていてもよく、Ｘはσ結合性の配位子を示し、Ｘが複数ある場合、複数のＸは同じでも異なっていてもよく、他のＸ、Ｅ^１、Ｅ^２又はＹと架橋していてもよい。Ｙはルイス塩基を示し、Ｙが複数ある場合、複数のＹは同じでも異なっていてもよく、他のＹ、Ｅ^１、Ｅ^２又はＸと架橋していてもよく、Ａ^１及びＡ^２は２つの配位子を結合する２価の架橋基であって、炭素数１〜２０の炭化水素基、炭素数１〜２０のハロゲン含有炭化水素基、珪素含有基、ゲルマニウム含有基、スズ含有基、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ_２−、−Ｓｅ−、−ＮＲ^１−、−ＰＲ^１−、−Ｐ（Ｏ）Ｒ^１−、−ＢＲ^１−又は−ＡｌＲ^１−を示し、Ｒ^１は水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基又は炭素数１〜２０のハロゲン含有炭化水素基を示し、それらは互いに同一でも異なっていてもよい。ｑは１〜５の整数で〔（Ｍの原子価）−２〕を示し、ｒは０〜３の整数を示す。〕 Examples of the bibridged metallocene complex include bibridged metallocene complexes represented by the general formula (I).

[In the formula, M represents a group 3-10 of the periodic table or a lanthanoid series metal element, and E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, respectively. A ligand selected from a substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group, and a silicon-containing group, which forms a cross-linked structure via A ¹ and A ² And they may be the same as or different from each other, X represents a σ-binding ligand, and when there are a plurality of X, the plurality of X may be the same or different, and other X, E ¹ , E ² or Y may be cross-linked. Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, may be cross-linked with other Y, E ¹ , E ² or X, and A ¹ and A ² are A divalent bridging group that binds two ligands, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, and a tin-containing group _{, -O -, - CO -,} - S -, - SO 2 -, - Se -, - NR 1 -, - PR 1 -, - P (O) R 1 -, - BR 1 - or -AlR ¹ - R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same as or different from each other. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3. ]

In the general formula (I), M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series, and specific examples include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium, and Examples of the lanthanoid metal include titanium, zirconium, and hafnium from the viewpoint of olefin polymerization activity.
E ¹ and E ² are respectively substituted cyclopentadienyl group, indenyl group, substituted indenyl group, heterocyclopentadienyl group, substituted heterocyclopentadienyl group, amide group (—N <), phosphine group (—P <), Hydrocarbon group [>CR-,> C <] and silicon-containing group [>SiR-,> Si <] (where R is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing group. A ligand selected from among (A) is shown, and a crosslinked structure is formed through A ¹ and A ² .
E ¹ and E ² may be the same as or different from each other.
As E ¹ and E ² , a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group are preferable because the polymerization activity becomes higher.

X represents a σ-bonding ligand, and when there are a plurality of X, the plurality of X may be the same or different and may be cross-linked with other X, E ¹ , E ² or Y. .
Specific examples of X include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, and carbon. Examples thereof include a silicon-containing group having 1 to 20 carbon atoms, a phosphide group having 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms.
On the other hand, Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E ¹ , E ² or X. Specific examples of the Lewis base of Y include amines, ethers, phosphines, thioethers and the like.

（Ｄは、炭素、ケイ素又はスズ、Ｒ^２及びＲ^３はそれぞれ水素原子又は炭素数１〜２０の炭化水素基で、それらは互いに同一でも異なっていてもよく、また互いに結合して環構造を形成していてもよい。ｅは１〜４の整数を示す。） Next, A ¹ and A ² are divalent bridging groups for bonding two ligands, which are a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, silicon containing group, a germanium-containing group, a tin-containing _{group, -O -, - CO -,} - S -, - SO 2 -, - Se -, - NR 1 -, - PR 1 -, - P (O) R 1 - , -BR ¹ -or -AlR ^1- , wherein R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and they are the same as each other But it can be different.
Examples of such a crosslinking group include those represented by the following formula.

(D is carbon, silicon or tin, R ² and R ³ are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same as or different from each other, and are bonded to each other to form a ring structure. (E may represent an integer of 1 to 4)

Specific examples of the crosslinking group include methylene group, ethylene group, ethylidene group, propylidene group, isopropylidene group, cyclohexylidene group, 1,2-cyclohexylene group, vinylidene group (CH ₂ ═C =), dimethylsilylene. A group, a diphenylsilylene group, a methylphenylsilylene group, a dimethylgermylene group, a dimethylstannylene group, a tetramethyldisilylene group, a diphenyldisilylene group, and the like.
Among these, an ethylene group, an isopropylidene group, and a dimethylsilylene group are preferable because the polymerization activity becomes higher.

Ｘ^１は、σ結合性の配位子を示し、Ｘ^１が複数ある場合、複数のＸ^１は同じでも異なっていてもよく、他のＸ^１又はＹ^１と架橋していてもよい。
このＸ^１の具体例としては、一般式（Ｉ）のＸの説明で例示したものと同じものを挙げることができる。
Ｙ^１は、ルイス塩基を示し、Ｙ^１が複数ある場合、複数のＹ^１は同じでも異なっていてもよく、他のＹ^１又はＸ^１と架橋していてもよい。
このＹ^１の具体例としては、一般式（Ｉ）のＹの説明で例示したものと同じものを挙げることができる。
Ｒ^４〜Ｒ^９はそれぞれ水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、炭素数１〜２０のハロゲン含有炭化水素基、珪素含有基又はヘテロ原子含有基を示すが、その少なくとも一つは水素原子でないことが必要である。
また、Ｒ^４〜Ｒ^９は互いに同一でも異なっていてもよく、隣接する基同士が互いに結合して環を形成していてもよい。
なかでも、重合活性がより高くなるため、Ｒ^６とＲ^７は環を形成していること及びＲ^８とＲ^９は環を形成していることが好ましい。
Ｒ^４及びＲ^５としては、酸素、ハロゲン、珪素等のヘテロ原子を含有する基が重合活性が高くなり好ましい。
この二架橋ビスシクロペンタジエニル誘導体を配位子とするメタロセン錯体は、配位子間の架橋基にケイ素を含むものが好ましい。 Among such bibridged metallocene complexes represented by the general formula (I), a metallocene complex having a bibridged biscyclopentadienyl derivative represented by the general formula (II) as a ligand has a polymerization activity. Since it becomes higher, it is preferable.
In the general formula (II), M, A ¹ , A ² , q and r are the same as described above.

X ¹ represents a σ-bonding ligand, and when plural X ^1, a plurality of X ¹ may be the same or different, may be crosslinked with other X ¹ or Y ^1.
Specific examples of X ¹ include the same ones as exemplified in the description of X in the general formula (I).
Y ¹ represents a Lewis base, if Y ¹ is plural, Y ¹ may be the same or different, may be crosslinked with other Y ¹ or X ^1.
Specific examples of Y ¹ include the same examples as those exemplified in the description of Y in the general formula (I).
R ^{4 to} R ⁹ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a heteroatom-containing group. One must not be a hydrogen atom.
R ^{4 to} R ⁹ may be the same as or different from each other, and adjacent groups may be bonded to each other to form a ring.
Especially, since polymerization activity becomes higher, it is preferable that R ⁶ and R ⁷ form a ring and R ⁸ and R ⁹ form a ring.
As R ⁴ and R ⁵ , a group containing a heteroatom such as oxygen, halogen, or silicon is preferable because of high polymerization activity.
The metallocene complex having the bibridged biscyclopentadienyl derivative as a ligand preferably contains silicon in the bridging group between the ligands.

Specific examples of the bibridged metallocene complex represented by the general formula (I) include (1,2′-ethylene) (2,1′-ethylene) -bis (indenyl) zirconium dichloride, (1,2′-methylene). ) (2,1′-methylene) -bis (indenyl) zirconium dichloride, (1,2′-isopropylidene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2′-ethylene) ) (2,1′-ethylene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (4,5-benzoindenyl) zirconium dichloride (1,2'-ethylene) (2,1'-ethylene) -bis (4-isopropylindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene ) -Bis (5,6-dimethylindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) -bis (4,7-diisopropylindenyl) zirconium dichloride, (1,2 ' -Ethylene) (2,1'-ethylene) -bis (4-phenylindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) -bis (3-methyl-4-isopropylindene Nyl) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) -bis (5,6-benzoindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-isopropyl Ridene) -bis (indenyl) zirconium dichloride, (1,2'-methylene) (2,1'-ethylene) -bis (indenyl) zirconium dichloride, (1,2 '-Methylene) (2,1'-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (indenyl) zirconium dichloride, (1,2 '-Dimethylsilylene) (2,1'-dimethylsilylene) bis (3-methylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-n-butyl) Indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-isopropylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′- Dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-dimethyl) Silylene) (2,1′-dimethylsilylene) bis (3-phenylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4,5-benzoindenyl) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (4-isopropylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) Bis (5,6-dimethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4,7-diisopropylisopropylenyl) zirconium dichloride, (1,2 '-Dimethylsilylene) (2,1'-dimethylsilylene) bis (4-phenylindenyl) zirconium dichloro (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-methyl-4-isopropylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′- Dimethylsilylene) bis (5,6-benzoindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2'-dimethylsilylene) ) (2,1′-isopropylidene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-isopropylindenyl) zirconium Dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-n-butylindenyl) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) Ridene) -bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-phenylindenyl) zirconium dichloride, (1,2'- Dimethylsilylene) (2,1′-methylene) -bis (indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) -bis (3-methylindenyl) zirconium dichloride, (1 , 2′-dimethylsilylene) (2,1′-methylene) -bis (3-isopropylindenyl) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene ) -Bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2'-diphenyl) Silylene) (2,1′-methylene) -bis (indenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-methylene) -bis (3-methylindenyl) zirconium dichloride, (1, 2'-Diphenylsilylene) (2,1'-methylene) -bis (3-isopropylindenyl) zirconium Chloride, (1,2'-diphenylsilylene) (2,1'-methylene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -Bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) ) (2,1′-dimethylsilylene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2 ′ Dimethylsilylene) (2,1′-ethylene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1′-methylene) ( 3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3 ′ -Methylcyclopentadienyl) zirconium dichloride, (1,2'-methylene) (2,1'-methylene) (3-methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1 , 2′-methylene) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirco Um dichloride, (1,2′-isopropylidene) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-dimethyl) Silylene) (2,1′-dimethylsilylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2, 1'-isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-ethylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene (2,1′-methylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1′-isopropyl Redene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-methylene) (3,4 Dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-isopropylidene) (2,1′-isopropylidene) (3,4-dimethylcyclope Tantadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5-ethylcyclopentadienyl) ( 3'-methyl-5'-ethylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-methyl-5-ethylcyclopentadienyl) (3 '-Methyl-5'-ethylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-methyl-5-isopropylcyclopentadienyl) (3'-Methyl-5'-isopropylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilyl) Len) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1 '-Dimethylsilylene) (3-methyl-5-phenylcyclopentadienyl) (3'-methyl-5'-phenylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'- Isopropylidene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) Ridene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride , (1,2'-dimethylsilylene) (2,1'-isopropylidene) (3-methyl-5-n-butylcyclopentadienyl) (3'-methyl-5'-n-butylcyclopentadienyl) ) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) (3-methyl-5-phenylcyclopentadienyl) (3'-methyl-5'-phenylcyclopentadienyl) zirconium Dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-ethylene) (3-methyl-5-isopropylcyclopentadienyl) (3'-methyl-5'-isopropylcycline) Pentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-ethylene) (3-methyl-5-n-butylcyclopentadienyl) (3'-methyl-5'-n-butylcyclo Pentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadiene) Enyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) (3-methyl-5-ethylcyclopentadienyl) (3'-methyl-5'-ethylcyclopentadienyl) zirconium Dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) (3-methyl-5-isopropylcyclopentadienyl) (3'-methyl- 5'-isopropylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) (3-methyl-5-n-butylcyclopentadienyl) (3'-methyl- 5′-n-butylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl- 5′-phenylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1′-methylene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5′- Isopropylcyclopentadienyl) zirconium dichloride, (1,2'-ethylene) (2,1'-isopropylidene) (3-methyl-5-isopropylcyclope) Tadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-methylene) (3-methyl-5-isopropylcyclopentadienyl) ( 3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) (3-methyl-5-isopropylcyclopentadienyl) (3 ′ -Methyl-5'-isopropylcyclopentadienyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-dimethylsilylene) bisindenylzirconium dichloride, (1,1'-diphenylsilylene) (2 , 2′-dimethylsilylene) bisindenylzirconium dichloride, (1,1′-dimethylsilylene) (2,2 '-Dimethylsilylene) bisindenylzirconium dichloride, (1,1'-diisopropylsilylene) (2,2'-dimethylsilylene) bisindenylzirconium dichloride, (1,1'-dimethylsilylene) (2,2'- Diisopropylsilylene) bisindenylzirconium dichloride, (1,1′-dimethylsilyleneindenyl) (2,2′-dimethylsilylene-3-trimethylsilylindenyl) zirconium dichloride, (1,1′-diphenylsilyleneindenyl) ( 2,2′-diphenylsilylene-3-trimethylsilylindenyl) zirconium dichloride, (1,1′-diphenylsilyleneindenyl) (2,2′-dimethylsilylene-3-trimethylsilylindenyl) zirconium dichloride, (1,1 '-Dimethylsilyleneind ) (2,2′-diphenylsilylene-3-trimethylsilylindenyl) zirconium dichloride, (1,1′-diisopropylsilyleneindenyl) (2,2′-dimethylsilylene-3-trimethylsilylindenyl) zirconium dichloride, ( 1,1'-dimethylsilyleneindenyl) (2,2'-diisopropylsilylene-3-trimethylsilylindenyl) zirconium dichloride, (1,1'-diisopropylsilyleneindenyl) (2,2'-diisopropylsilylene-3- Trimethylsilylindenyl) zirconium dichloride, (1,1′-dimethylsilyleneindenyl) (2,2′-dimethylsilylene-3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1′-diphenylsilyleneindenyl) (2 , 2'-di Enylsilylene-3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1′-diphenylsilyleneindenyl) (2,2′-dimethylsilylene-3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) Indenyl) (2,2′-diphenylsilylene-3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1′-diisopropylsilyleneindenyl) (2,2′-dimethylsilylene-3-trimethylsilylmethylindenyl) zirconium Dichloride, (1,1′-dimethylsilyleneindenyl) (2,2′-diisopropylsilylene-3-trimethylmethylsilylindenyl) zirconium dichloride, (1,1′-diisopropylsilyleneindenyl) (2,2′- Isopropyl silylene -3-methyl silyl) zirconium dichloride and the like, and zirconium in these compounds may include those obtained by substituting titanium or hafnium.
Of course, it is not limited to these.
Further, it may be an analogous compound of another group or a lanthanoid series metal element.
In the above compound, (1,1 ′ −) (2,2′−) may be (1,2 ′ −) (2,1′−), or (1,2 ′ −) (2 , 1'-) may be (1, 1'-) (2, 2'-).

Examples of the solid organoboron compound that forms an ion pair with the component (A) as the component (B) include a coordination complex compound composed of an anion and a cation in which a plurality of groups are bonded to a metal.
There are various coordination complex compounds composed of an anion and a cation in which a plurality of groups are bonded to a metal. For example, a compound represented by the general formula (III) or (IV) can be preferably used.
([L ¹ −H] ^{s +} ) _t ([BZ ¹ Z ² Z ³ Z ⁴ ] ⁻ ) ₁ ... (III)
([L ² ] ^{s +} ) _t ([BZ ¹ Z ² Z ³ Z ⁴ ] ⁻ ) ₁ ... (IV)
[In Formula (III) or (IV), L ² is M ¹ , R ¹⁰ R ¹¹ M ² or R ¹² ₃ C described later, L ¹ is a Lewis base, M ¹ is Group ¹ of the periodic table and 8 Metal selected from group 12 to group 12, M ² is a metal selected from group 8 to group 10 of the periodic table, and Z ^{1 to} Z ⁴ are a hydrogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, 1 carbon atom, respectively. -20 alkyl group, C6-C20 aryl group, alkylaryl group, arylalkyl group, substituted alkyl group, organic metalloid group or halogen atom.
R ¹⁰ and R ¹¹ each represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ¹² represents an alkyl group.
s is the ionic valence of L ¹ -H and L ² and is an integer of 1 to 7, t is an integer of 1 or more, and l = t × s). ]

M ¹ is a metal selected from groups 1 and 8 to 12 of the periodic table, specific examples are Ag, Cu, Na, Li and other atoms, and M ² is selected from groups 8 to 10 of the periodic table. Specific examples of metals that can be used include atoms such as Fe, Co, and Ni.
Specific examples of Z ^{1 to} Z ⁴ include, for example, a dimethylamino group and a diethylamino group as a dialkylamino group, a methoxy group, an ethoxy group, an n-butoxy group and the like as an alkoxy group, a phenoxy group as an aryloxy group, and 2, 6 -As a C1-C20 alkyl group, such as a dimethylphenoxy group and a naphthyloxy group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, n-octyl group, 2-ethylhexyl group, A phenyl group, p-tolyl group, benzyl group, pentafluorophenyl group, 3,5-di (trifluoromethyl) phenyl group, 4-tertiary-butyl as an aryl group, alkylaryl group or arylalkyl group of formula 6-20 Phenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4 Dimethylphenyl group, 1,2-dimethylphenyl group, etc., F, Cl, Br, I as halogen, tetramethylantimony group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexylantimony group, diphenylboron group as organic metalloid group Etc.
Specific examples of the substituted cyclopentadienyl group represented by each of R ¹⁰ and R ¹¹ include a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group.

Specific examples of anions in which a plurality of groups are bonded to a metal include B (C ₆ F ₅ ) ₄ ⁻ , B (C ₆ HF ₄ ) ₄ ⁻ , B (C ₆ H ₂ F ₃ ) ₄ ⁻ , B _{(C 6 H 3 F 2)} 4 -, B (C 6 H 4 F) 4 -, B (C 6 CF 3 F 4) 4 -, B (C 6 H 5) 4 -, BF 4 - and the like It is done.
The metal ^{_{cation, Cp 2 Fe +, (MeCp}} ) 2 Fe +, (tBuCp) 2 Fe +, (Me 2 Cp) 2 Fe +, (Me 3 Cp) 2 Fe +, (Me 4 Cp) 2 ^{_{Fe +, (Me 5 Cp)}} 2 Fe +, Ag +, Na +, Li + and the like, also as the other cation, pyridinium, 2,4-dinitro -N, N-diethyl anilinium, diphenyl ammonium , Nitrogen-containing compounds such as p-nitroanilinium, 2,5-dichloroaniline, p-nitro-N, N-dimethylanilinium, quinolinium, N, N-dimethylanilinium, N, N-diethylanilinium, Carbeniu such as phenyl carbenium, tri (4-methylphenyl) carbenium, tri (4-methoxyphenyl) carbenium ^{_{Compound, CH 3 PH 3 +, C}} 2 H 5 PH 3 +, C 3 H 7 PH 3 +, (CH 3) 2 PH 2 +, (C 2 H 5) 2 PH 2 +, (C 3 H 7) ^{_{2 PH 2 +, (CH 3}} ) 3 PH +, (C 2 H 5) 3 PH +, (C 3 H 7) 3 PH +, (CF 3) 3 PH +, (CH 3) 4 P +, ( Alkylphosphonium ions such as C ₂ H ₅ ) ₄ P ⁺ , (C ₃ H ₇ ) ₄ P ⁺ , and C ₆ H ₅ PH ₃ ⁺ , (C ₆ H ₅ ) ₂ PH ₂ ⁺ , (C ₆ H ₅ ) ₃ PH ⁺ , (C ₆ H ₅ ) ₄ P ⁺ , (C ₂ H ₅ ) ₂ (C ₆ H ₅ ) PH ⁺ , (CH ₃ ) (C ₆ H ₅ ) PH ₂ ⁺ , (CH ₃ ) _{2 ^{(C 6 H 5) PH +}} , (C 2 H 5) 2 (C 6 H 5) 2 P + aryl phosphonium such as One, and the like.
Coordination complex compounds by any combination of the above metal cations and anions

Among the compounds of the general formulas (III) and (IV), specifically, the following can be used particularly preferably.
Examples of the compound of the general formula (III) include triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, triethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) ) Tri (n-butyl) ammonium borate, triethylammonium hexafluoroarsenate, pyridinium tetrakis (pentafluorophenyl) borate, pyrrolonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, Examples include tetrakis (pentafluorophenyl) methyldiphenylammonium borate.
On the other hand, the compound of the general formula (IV) includes, for example, ferrocenium tetraphenylborate, dimethylferrocenium tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, decamethyl ferrotetrakis (pentafluorophenyl) borate. Cenium, tetrakis (pentafluorophenyl) acetylferrocenium borate, tetrakis (pentafluorophenyl) formylferrocenium borate, tetrakis (pentafluorophenyl) cyanoferrocenium borate, silver tetraphenylborate, tetrakis (pentafluorophenyl) Examples thereof include silver borate, trityl tetraphenylborate, tetrakis (pentafluorophenyl) trityl borate, and silver tetrafluoroborate.

Preferred coordination complex compounds are those comprising a non-coordinating anion and a substituted triarylcarbenium, and examples of the non-coordinating anion include compounds represented by the general formula (V). Can do.
(BZ ¹ Z ² Z ³ Z ⁴ ) ⁻ (V)
[Wherein, Z ^{1 to} Z ⁴ are each a hydrogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms (including a halogen-substituted aryl group). , An alkylaryl group, an arylalkyl group, a substituted alkyl group and an organic metalloid group or a halogen atom. ]

On the other hand, examples of the substituted triarylcarbenium include compounds represented by the general formula (VI).
[CR ¹³ R ¹⁴ R ¹⁵ ] ⁺ ... (VI)
R ¹³ , R ¹⁴ and R ¹⁵ in the general formula (VI) are each an aryl group such as a phenyl group, a substituted phenyl group, a naphthyl group and an anthracenyl group, and they may be the same or different from each other. However, at least one of them is a substituted phenyl group, a naphthyl group or an anthracenyl group.
The substituted phenyl group can be represented by, for example, general formula (VII).
C ₆ H _5-k R ¹⁶ _k (VII)
R ¹⁶ in the general formula (VII) represents a hydrocarbyl group having 1 to 10 carbon atoms, an alkoxy group, an aryloxy group, a thioalkoxy group, a thioaryloxy group, an amino group, an amide group, a carboxyl group, and a halogen atom, and k is It is an integer of 1-5.
When k is 2 or more, the plurality of R ¹⁶ may be the same or different.

  Specific examples of the non-coordinating anion represented by the general formula (V) include tetra (fluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, Tetrakis (pentafluorophenyl) borate, tetrakis (trifluoromethylphenyl) borate, tetra (toluyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate , Tridecahydride-7,8-dicarboundeborate and the like.

  Specific examples of the substituted triarylcarbenium represented by the general formula (VI) include tri (toluyl) carbenium, tri (methoxyphenyl) carbenium, tri (chlorophenyl) carbenium, tri (fluorophenyl) carbenium, tri ( Xylyl) carbenium, [di (toluyl), phenyl] carbenium, [di (methoxyphenyl), phenyl] carbenium, [di (chlorophenyl), phenyl] carbenium, [toluyl, di (phenyl)] carbenium, [methoxyphenyl, di (Phenyl)] carbenium, [chlorophenyl, di (phenyl)] carbenium and the like.

The catalyst of the present invention uses an organoaluminum compound as the component (C) in addition to the components (A) and (B).
(C) As an organoaluminum compound, the compound represented by general formula (VIII) is mentioned.
R ²⁰ _v AlJ _3-v (VIII)
[Wherein, R ²⁰ represents an alkyl group having 1 to 10 carbon atoms, J represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom, and v represents 1 to 3 carbon atoms. (It is an integer)

Specific examples of the compound represented by the general formula (VIII) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, Examples thereof include diisobutylaluminum hydride, diethylaluminum hydride, and ethylaluminum sesquichloride.
These organoaluminum compounds may be used alone or in combination of two or more.

（式中、Ｒ^２１は、炭素数１〜２０、好ましくは１〜１２のアルキル基，アルケニル基，アリール基，アリールアルキル基等の炭化水素基又はハロゲン原子を示し、ｗは平均重合度を示し、通常２〜５０、好ましくは２〜４０の整数である。尚、各Ｒ^２１は同じでも異なっていてもよい。）

（式中、Ｒ^２１及びｗは前記一般式（IX）におけるものと同じである。） Moreover, as an organoaluminum compound of (C) component, the chain | strand-shaped aluminoxane represented by general formula (IX) and the cyclic | annular aluminoxane represented by general formula (X) can be mentioned.

(Wherein R ²¹ represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group, arylalkyl group or the like having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms or a halogen atom, and w represents an average degree of polymerization. In general, it is an integer of 2 to 50, preferably 2 to 40. In addition, each R ²¹ may be the same or different.

(Wherein R ²¹ and w are the same as those in the general formula (IX)).

The compounds represented by the general formulas (IX) and (X) include linear or cyclic tetramethyl dialumoxane, tetraisobutyl dialumoxane, methylalumoxane, ethylalumoxane, butylalumoxane, isobutylalumoxane. And alumoxane.
Examples of the method for producing aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but the means thereof is not particularly limited and may be reacted according to a known method.
These aluminoxanes may be used alone or in combination of two or more.

The component (D) is one or more compounds selected from α-olefins, internal olefins, and polyenes.
Examples of the internal olefin include 2-butene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, 2-octene, 3-octene, 4-octene and 5-decene.
Examples of the polyene include diene compounds such as 1,3-butadiene, 1,5-hexadiene, and 1,7-octadiene.
Examples of the α-olefin include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, Examples include octadecene and 1-eicosene.
Among these compounds, one kind or two or more kinds can be used.
The component (D) is preferably an α-olefin, particularly an α-olefin having 3 to 30 carbon atoms, from the viewpoint of improving the catalytic activity.
Here, when an α-olefin having a boiling point of 50 ° C. or higher under normal pressure (1-pentene or higher) is used for the preparation of the catalyst, the reaction vessel used for the catalyst preparation does not need pressure resistance, and at the time of storage after the catalyst preparation. The possibility that the poly α-olefin (prepolymerized polymer) precipitates is reduced, and troubles such as clogging of the pump when the prepared catalyst is transferred can be prevented.

When the component (D) is a liquid, the hydrocarbon solvent of the component (E) is not an essential component.
However, by contacting the components (A) to (D) in the presence of the hydrocarbon solvent of the component (E), it is easy to produce a prepolymerized polymer described later such as control of the intrinsic viscosity and preparation of a homogeneous catalyst. Become.

Examples of the hydrocarbon solvent include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, decalin and tetralin, pentane, hexane and heptane. And aliphatic hydrocarbons such as octane, halogenated hydrocarbons such as chloroform and dichloromethane, and the like can be used. These solvents may be used alone or in combination of two or more.
As the hydrocarbon solvent of component (E), it is preferable to use an aliphatic hydrocarbon solvent or an alicyclic hydrocarbon solvent from the viewpoint of safety and health.

A typical example of the method for preparing the polymerization catalyst of the present invention will be described.
For example, after adding (D) one or more compounds selected from α-olefin, internal olefin, and polyene, (C) an organoaluminum compound to a hydrocarbon solvent, (A) a transition metal compound, and (B) A solid organoboron compound that forms an ion pair with the component (A) is added and brought into contact.
In this case, when the component (D) is a polymerizable compound, it is a prepolymerization treatment. There is no restriction | limiting in the addition order of (D) component and (C) component, and the addition order of (A) component and (B) component. At this time, 0.005 to 1.0 MPa of hydrogen can also coexist.

The temperature at the time of contact (preliminary polymerization) is usually -20 to 200 ° C, preferably -10 to 150 ° C, more preferably 0 to 80 ° C. The contact (preliminary polymerization) time is usually 10 minutes to 30 days, preferably 1 hour to 15 days.
The component (A) and the component (B) react while dissolving in a solvent to form an active site. For this reason, the effect of homogenizing the catalyst system on the improvement of the catalyst activity is great. Therefore, if the contact (preliminary polymerization) time is too short, the activity improving effect is not sufficient. On the other hand, if the contact (preliminary polymerization) time is too long, the catalytic activity may be lowered.

The ratio (molar ratio) of component (A) / component (B) is preferably 1/100 to 1/1, more preferably 1/10 to 1/1.
When the (A) component / (B) component is less than 1/100, the (B) component is wasted, and when it exceeds 1/1, sufficient activity may not be exhibited.
Moreover, the use ratio (molar ratio) of the component (A) / (C) is preferably 1 / 10,000 to 1/1, more preferably 1 / 2,500 to 1/5.
When the component (A) / component (C) is less than 1 / 10,000, the component (C) is wasted, and when it exceeds 1/5, sufficient activity may not be exhibited.

(D) As a usage-amount of (D) component, (D) component / (A) component [molar ratio] is 10-100,000, Preferably it is 100-100,000.
When this ratio is less than 10, the polymerization activity may not be exhibited, and when it exceeds 100,000, the polymerization activity may decrease.
When the α-olefin is used as the component (D), the intrinsic viscosity of the poly α-olefin (preliminarily polymerized polymer) produced by the prepolymerization is preferably 0.05 dL / g or more and less than 15 dL / g.
This upper limit value is more preferably less than 10 dL / g, still more preferably less than 5 dL / g.
If the intrinsic viscosity exceeds 15 dL / g, the viscosity of the polymerization catalyst solution increases, which may hinder the supply of the polymerization catalyst solution to the polymerization system.
The intrinsic viscosity [η] is measured at a temperature of 135 ° C. in a decalin solvent using a VMR-053 type automatic viscometer manufactured by Ryogo Co., Ltd.

In the above catalyst preparation method, when an aromatic hydrocarbon is used as a solvent, a homogeneous polymerization catalyst is usually obtained, but the component (B) / component (A) (molar ratio) is 5 or more and the concentration of the component (A). Is 10 μmol / mL or more, a heterogeneous catalyst is likely to be generated.
Moreover, when an alicyclic hydrocarbon or an aliphatic hydrocarbon is used as a solvent, the solubility of the component (A) and the component (B) is low, so that the produced catalyst tends to be uneven.

The polymerization of α-olefin is not particularly limited, and can be performed by, for example, bulk polymerization or solution polymerization.
The polymerization temperature is preferably 0 to 150 ° C, more preferably 50 to 100 ° C, and further preferably 60 to 90 ° C.
When the polymerization temperature is less than 0 ° C., the reaction rate decreases, and there is a possibility that the reaction time and the amount of catalyst used may increase when a certain amount of polymer is to be obtained. On the other hand, when the polymerization temperature is higher than 150 ° C., not only the catalyst may be deactivated and the reaction may be stopped, but also the vapor pressure of the monomer is increased and the reactor pressure needs to be set high. Equipment costs may increase.

Polymerization solvents include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane; aliphatic hydrocarbons such as pentane, hexane, heptane and octane: chloroform and dichloromethane Halogenated hydrocarbons such as can be used. In addition to these, α-olefin as a raw material monomer may be used as a solvent.
These polymerization solvents may be used alone or as a mixed solvent of two or more.

Hydrogen may be supplied to the reaction field in order to adjust the molecular weight of the resulting polyolefin.
In addition, an additive compound (for example, paraffin) to be supplied at the time of polymerization may be newly supplied, or may be separated from the reaction solution taken out from the reaction field and supplied after being recycled.

The reaction solution after completion of the polymerization reaction contains polyolefin, solvent, propylene, propane and the like.
The reaction solution may be heated and / or reduced in pressure to remove residual amounts of solvent, propylene, propane and the like until 200 wtppm or less to purify the polyolefin.
The above-mentioned removal of the solvent, propylene, propane and the like may be performed a plurality of times under different conditions of temperature and pressure.

The removed solvent, propylene, propane and the like may be reused after being purified or purified by distillation.
The solvent to be reused, propylene, propane and the like may be passed through an adsorbent filled in a container in order to remove impurities contained in the fluid. In addition, when distilling and purifying the solvent, propylene, propane, etc. to be reused, the paraffin concentration in the reaction field can be adjusted by adjusting the amount of paraffin returned to the reactor.

  When distilling and purifying the solvent, propylene, propane, etc. to be reused, water is added to remove water-soluble substances derived from the polymerization catalyst, etc., and the added water can be removed from the system by oil-water separation. . In addition, it is also possible to remove light components such as hydrogen and nitrogen contained in the raw material accompanying distillation purification of the solvent to be reused, propylene, propane and the like.

The polyolefin obtained by the production method of the present invention can be granulated with, for example, an underwater cut granulator to form pellets.
In order to prevent adhesion of pellets to the water used for granulation, 500 to 3000 wtppm of silicon oil may be added.

The granulated pellet can be dehydrated with a centrifugal dehydrator or the like, and then transferred to a silo using an air feeding system using compressed air.
Compressed air can be air cooled until the melting point of the pellets or lower, and the air transport system is selected so that the melting point of the pellets is not exceeded during the pellet transport, and the transport speed in the air transport system is 5 m / second or less. It is good to adjust so that it may become speed. Although the pressure of compressed air changes with distance to transfer and height, it is good to use compressed air of about 0.1-0.5 MPaG.

  The silo may be blown with nitrogen or air for the purpose of removing moisture adhering to or impregnating the pellets. Nitrogen and air to be blown may be heated in advance so as not to exceed the melting point of the pellet.

Example 1
Using a reactor with a total volume of 70 L, the amount of liquid retained was adjusted so that the liquid volume was 50 L.
To the reactor, propylene was 5.63 kg / h, propane was 5.66 kg / h, heptane was 5.34 kg / h as a solvent, hydrogen as a molecular weight regulator was 0.52 g / h, and diluted catalyst was 4.56 g / h ( The catalyst was diluted with meta-xylene to a concentration of 4 mmol / L (weight including meta-xylene), and TIBA (triisobutylaluminum) 1.54 g / h was continuously fed as a co-catalyst.
At this time, the concentration of propylene in heptane was 0.556 mol / L, and the partial pressure in the gas phase portion was 196 kPa. Propane was supplied so that the total pressure in the gas phase was maintained at 1.7 MPaG, the concentration of propane in heptane was 4.78 mol / L, and the partial pressure in the gas phase was 1509 kPa. The remaining 96 kPa (= 1801-196-1509) is the partial pressure of heptane and hydrogen.
The polyolefin obtained had a weight of 5.00 kg / h and a stereoregularity of 40%.
In the continuous polymerization, the supply amount of heptane was adjusted so that the polyolefin concentration in the reaction field was 30 wt%.

  The heat removal of the polymerization reaction was of the latent heat of vaporization type, and vapors of propylene, propane, heptane, etc. evaporated from the polymerization solvent were cooled to 38 ° C. with a heat exchanger. Circulating cooling water at 30 ° C. was used for cooling. The heat removal amount in the heat exchanger was 8.8 MJ / h, the condensate amount in the heat exchanger was 22.4 kg / h, and the non-condensable gas amount was 3.5 kg / h. These liquids and gases were increased in pressure and then supplied again to the reactor.

Comparative Example 1
A polyolefin was produced in the same manner as in Example 1 except that propane was not supplied.
The concentration of propylene in heptane (reaction field) was 0.637 mol / L, and the partial pressure in the gas phase was 287 kPa. Since propane was not supplied, the total pressure in the gas phase part of the polymerization vessel was 0.4 MPaG. The stereoregularity of the obtained polyolefin was 40%.

  Unlike Example 1, 30 ° C. circulating cooling water was not sufficient for heat removal, so -23 ° C. chlorofluorocarbon was used as a refrigerant, and a vapor such as propylene and heptane evaporated from the polymerization solvent was used as a heat exchanger. At -15.5 ° C. The heat removal amount in the heat exchanger was 8.8 MJ / h as in Example 1, the amount of condensate in the heat exchanger was 12.4 kg / h, and the amount of non-condensed gas was 11.5 kg / h. . These liquids and gases were pressurized and then supplied again to the reactor.

Example 2
By changing the supply amount of propylene and propane, the propylene concentration in the polymerization solvent is 4.3 mol / L, the partial pressure in the gas phase part of propylene is 1560 kPa, the propane concentration in the polymerization solvent is 0.41 mol / L, and A polyolefin was produced in the same manner as in Example 1 except that the partial pressure in the gas phase portion was 128 kPa and the catalyst supply amount was 0.59 g / h. The total pressure in the gas phase part was maintained at 1.7 MPaG as in Example 1.
The polyolefin obtained had a weight of 5.00 kg / h and a stereoregularity of 50%.

  Heat removal of the polymerization reaction was of the latent heat of vaporization type, and vapors such as propylene and heptane evaporated from the polymerization solvent were cooled to 38 ° C. with a heat exchanger. Circulating cooling water at 30 ° C. was used for cooling. The heat removal amount in the heat exchanger was 8.8 MJ / h, the amount of condensate in the heat exchanger was 21.8 kg / h, and the amount of non-condensed gas was 9.6 kg / h. These liquids and gases were pressurized and then supplied again to the reactor.

Example 3
Polymerization of propylene was carried out in the same manner as in Example 1 except that the reaction temperature was 70 ° C., the amount of propylene supplied was changed, and the propylene concentration in the polymerization solvent was changed to the concentration shown in Table 1. Regularity (mmmm) was evaluated. The results are shown in Table 1.
The propane supply amount was changed so that the total pressure in the gas phase was 1.7 MPaG. The catalyst supply amount was also adjusted so that the polyolefin production amount was 5.00 kg / h.
The relationship between the propylene concentration and the stereoregularity of the obtained polypropylene is shown in FIG.

  FIG. 1 shows that the stereoregularity is improved as the propylene concentration in the polymerization solvent increases.

  By using the production method of the present invention to polymerize an α-olefin having 3 or more carbon atoms, the stereoregularity can be controlled to produce a polyolefin.

Claims (5)

In a method for producing a polyolefin in which an α-olefin having 3 or more carbon atoms is polymerized by solution polymerization in the presence of a metallocene catalyst,
Removes heat from the polymerization reaction in a latent heat of vaporization type reactor.
Paraffin having 3 or more carbon atoms is added as a compound in which the condensation temperature at 1 MPaG does not become a catalyst poison and is within the range of ± 20 ° C. of the condensation temperature at 1 MPaG of the α-olefin, and the total pressure in the reaction field is 0.5 MPaG to 4.5 MPaG, the partial pressure of the reaction field of the paraffin having 3 or more carbon atoms is 0.001 to 4.5 MPa, the concentration of the α-olefin in the reaction field is changed to 0.01 to 99.99 wt%, A method for producing a polyolefin, wherein the stereoregularity of the polyolefin is controlled. The method for producing a polyolefin according to claim 1, wherein the stereoregularity (mmmm) of the polyolefin is controlled in the range of 39.3% to 50% .   The method for producing a polyolefin according to claim 1 or 2, wherein a partial pressure in the reaction field of the α-olefin having 3 or more carbon atoms is 0.001 to 4.5 MPa.   The method for producing a polyolefin according to any one of claims 1 to 3, wherein the polymerization temperature is 0 to 150 ° C.   The method for producing a polyolefin according to claim 1, wherein the α-olefin having 3 or more carbon atoms is propylene.

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