JP7588468B2 - Process for producing α-olefins for polymerization - Google Patents

Description

The present invention relates to a method for producing α-olefins used in olefin polymerization reactions. Preferably, the present invention relates to a method for producing α-olefins suitable for a specific high-performance olefin polymerization catalyst. Furthermore, the present invention relates to a method for continuously producing olefins for polymerization.

A method of using a transition metal compound having a cyclopentadienyl ligand or a substituted cyclopentadienyl ligand, a so-called metallocene compound, as an olefin polymerization catalyst is widely known. In particular, metallocene compounds having a basic structure with a ligand in which a cyclopentadienyl group and a fluorenyl group are bridged are useful.

The applicant has disclosed that among these, a specific hafnocene compound having a specific structure and containing hafnium as the central metal is useful for producing ethylene-based copolymers because it has the characteristics of high activity and excellent copolymerizability (Patent Document 1).

International Publication No. 2015/122414

In the course of the present inventors' investigations, it was found that, although there is a tendency for the influence of ethylene to be small when using commercially available polymerization olefins used in the mass production of olefin polymers, in some lots of α-olefins, sufficient polymerization activity may not be exhibited in the polymerization reaction using the above catalyst. For example, it was confirmed that this problem tends to become apparent in polymerization methods in which a large amount of α-olefins is continuously supplied, such as continuous polymerization. This is thought to be because the above-mentioned hafnocene compounds are highly sensitive to specific impurities due to their high performance and high activity, and therefore performance degradation occurs. Also, the influence may be more likely to become apparent in a continuous process than in a batch process.
Porous zeolite is often used for the purification of industrially used olefins. It is known that porous zeolite can effectively adsorb compounds containing highly polar heteroatoms such as water and lower alcohols, and that when the adsorption performance is reduced, the performance can be restored by treatment at high temperature, that is, by calcination, and is therefore a material suitable for industrialization, particularly for continuous purification of olefins.
However, according to the investigations of the present inventors, the above problems could not be solved by treating olefins with zeolite, which is thought to suggest that components such as water and lower alcohols are not the essential cause of the above problems.
Porous alumina is also known to be an excellent adsorbent for impurities. It is said that it can adsorb a wide variety of compounds.
On the other hand, due to the nature of alumina, the adsorption performance tends to decrease relatively quickly, and the effect of recovering the performance by calcination is also small.

Therefore, the objective of the present invention is to provide an olefin production method that is particularly suitable for olefin polymerization reactions using a specific olefin polymerization catalyst. In particular, the objective of the present invention is to provide an olefin production method that enables continuous olefin production over a long period of time.

In order to solve the above problems, the present inventors have conducted further studies and have found that by combining porous zeolite and porous alumina in a specific mode and contacting the combined mixture with an α-olefin, stable polymerization activity is exhibited, for example, even when the combined mixture is used for copolymerization of ethylene and an α-olefin using a metallocene compound having the above-mentioned configuration, and thus completed the present invention.
That is, the present invention has the following configurations [1] to [5].
[1] A method for producing an α-olefin for polymerization, comprising contacting an α-olefin with a porous zeolite and porous alumina under the following conditions (I) and (II): (I) the weight ratio of the porous zeolite to the porous alumina is in the range of 0.1 to 10.
(II) An α-olefin is contacted with a porous zeolite, and then the α-olefin is contacted with porous alumina.
[2] The method for producing an α-olefin for polymerization according to the above [1], wherein the porous zeolite and the porous alumina are contacted with a hydrocarbon compound selected from a saturated hydrocarbon compound and an aryl alkyl compound.
[3] The method for producing an α-olefin for polymerization according to [2] above, wherein the boiling point of the hydrocarbon compound is in the range of −60° C. to 40° C.
[4] The method for producing an α-olefin for polymerization according to any one of [1] to [3] above, wherein the condition for supplying and contacting the α-olefin with the porous zeolite and the porous alumina is a liquid hourly space velocity (LHSV) of 0.1 to 10/hour.
[5] The method for producing an α-olefin for polymerization according to any one of [1] to [4] above, wherein the contact temperature of the α-olefin with the porous zeolite and the porous alumina is in the range of −10° C. to 50° C.

The present invention includes a step of combining a porous zeolite and a porous alumina in a specific mode and contacting the porous zeolite with an α-olefin, and therefore can efficiently and stably produce an α-olefin for polymerization. This α-olefin can stably exhibit high polymerization activity, even when used in polymerization using a highly active transition metal complex such as a hafnocene compound having a specific structure. The effect obtained in a continuous polymerization process tends to be particularly large.
In the above-mentioned method for producing α-olefins, it is preferable to combine porous zeolite and porous alumina with a specific hydrocarbon compound, since this allows the production of α-olefins under stable conditions.

1 is a configuration example of a production apparatus for carrying out the α-olefin production method of the present invention.

The present invention will now be described in further detail.
In the present invention, the α-olefin used in the contact between the porous zeolite and the porous alumina (hereinafter, sometimes referred to as the raw material α-olefin) can be any commercially available α-olefin without any restrictions. However, the purity is preferably 95% or more, more preferably 97% or more, and even more preferably 99% or more. In the case of commercially available α-olefins, there are almost no α-olefins with a purity of 100%, and they often contain impurities with specific structures or impurities without specific structures. The impurities may include heavy components in addition to lower components such as water, alcohols, ketones, and thiophenes. These commercially available olefins may show polymerization activity even when used as they are, but in order to continuously and stably polymerize olefins, it is essential to produce olefins for polymerization by the method of the present invention.

The porous zeolite used in the present invention can be any commercially available zeolite without any restrictions. Specific examples include molecular sieves, as well as zeolites with a wide variety of structures such as ZS-5 and ZSM-5. Among these, Zeolum (registered trademark) manufactured by Tosoh Corporation is preferably used in the present invention. A particularly preferred example is Zeolum (registered trademark) F9 manufactured by Tosoh Corporation.
As for the porous alumina, commercially available products can be used without any restrictions. Among them, it is preferable that the porous alumina has an amorphous structure and a surface area of 200 m ² /g or more, more preferably 250 m ² /g or more.
The purity of the alumina is preferably 90% or more, more preferably 92% or more. Preferred components other than alumina include iron oxide, silicon oxide, and sodium oxide.
The weight ratio of the porous zeolite to the porous alumina is preferably in the range of 0.1 to 10, more preferably 0.2 to 8, further preferably 0.3 to 6, and even more preferably 0.3 to 5.

When the porous zeolite and porous alumina are brought into contact with an α-olefin, it is essential to first provide a step of contacting the porous zeolite. Of course, the porous zeolite and porous alumina may coexist, but the presence of the porous zeolite is key. When both are present, it is preferable that the content of the porous zeolite is 50% by weight or more, more preferably 70% by weight or more, and even more preferably 90% by weight or more, assuming that the total weight of the porous zeolite and porous alumina is 100% by weight.

A simple method for achieving this is to use a laminated structure of a layer of only porous zeolite and a layer of only porous alumina, a laminated structure of a layer of only porous zeolite and a mixed layer of porous zeolite/porous alumina, or a combination thereof, in which the α-olefin is first flowed in a direction in which it comes into contact with the porous zeolite layer. If it is downstream of the flow of the α-olefin, the content of the porous alumina may be preferably 50% by weight or more, assuming that the total weight of the porous zeolite and the porous alumina is 100% by weight. More preferably, there is a coexisting layer with a porous alumina content of 70% by weight or more, and even more preferably 90% by weight or more.
More specifically, preferred examples of the coexistence state include a method in which the layer is formed in a tubular vessel and an α-olefin is supplied and contacted therewith, and a method in which a so-called column-shaped treatment layer (reaction layer) is formed and contacted with an α-olefin.

By making the above-mentioned steps essential, it is considered that the frequency of contact of porous alumina with water, alcohol, etc. is reduced, one of the advantages of porous alumina, that is, the function of removing heavy impurities, is selectively exhibited as much as possible, and α-olefins suitable for polymerization can be produced efficiently as a whole. Alternatively, in the embodiment where alumina is in contact with zeolite, it is considered that a specific impurity adsorption effect is exhibited.
Although no results have been obtained at present to support these speculations, the inventors believe that the above-mentioned hypotheses may have led to the effects of the present invention and made it possible to solve the above-mentioned new problems.

In such a case, the feed rate of the α-olefin is preferably in the range of 0.1 to 10/hour as LHSV. The range is preferably 0.2 to 8/hour, more preferably 0.3 to 6/hour, and even more preferably 0.4 to 5/hour. Within these ranges, it is easy to control the temperature to a preferred range described later, and an olefin for polymerization can be obtained efficiently and stably. Even within these ranges, it is preferable to set the LHSV at a low level, particularly at the start of this production method, and gradually increase the rate. One of the advantages of this method is that it suppresses a sudden rise in the reaction temperature described later.
In the olefin production method of the present invention, it is preferable to carry out the process at a temperature range of -10°C to 50°C. More preferably, it is in the range of 0 to 45°C, and even more preferably, it is in the range of 10 to 40°C. If the reaction temperature is higher than this, the structure of the porous alumina or porous zeolite may change, and it may become impossible to stably exhibit sufficient effects. In a particularly severe case, the porous zeolite may be fixed to the inner wall of the column, making it impossible to regenerate the column itself. In addition, in the case of porous zeolite, the regeneration effect by calcination may be significantly reduced. On the other hand, at a temperature lower than -10°C, sufficient production capacity may not be exhibited.
The above temperature ranges are so to speak the ambient temperatures of the porous zeolite and porous alumina. When the porous zeolite and porous alumina come into contact with the commercially available α-olefins that are raw materials, heat may be generated due to a reaction with impurities contained in the α-olefins, and the temperature may be locally or temporarily outside the above temperature range. However, as long as the temperature is within the above temperature range on average, it is possible to efficiently purify the α-olefins.

In a preferred embodiment of the present invention, the porous zeolite and the porous alumina are brought into contact with a specific hydrocarbon compound. This can prevent the porous zeolite and the porous alumina from coming into direct contact with the α-olefin, and can prevent a sudden rise in the reaction temperature. In addition, the infiltration of these compounds into the porous structure can contribute to the maintenance of the porous structure (resistance to breakage). Furthermore, it can be expected that the performance degradation caused by some components contained in the air, etc., can be prevented during storage before contact with the α-olefin. As such a hydrocarbon compound, commercially available process oils can be used. Furthermore, it is preferable that the product has low volatility. Specific examples of such components include non-polar liquids such as hydrocarbons with 10 or more carbon atoms. More specifically, examples of known oils include mineral oils, which are base oils for lubricating oils and gear oils, and liquid low polymers of olefins. Commercially available lubricating oils and gear oils may contain additives with polarity, so caution is required when using such products.

The α-olefin for polymerization obtained by the process of the present invention is preferably used in combination with a specific olefin polymerization catalyst, such as a high-performance metallocene catalyst, which is easily affected by impurities. The catalyst may be used to homopolymerize an α-olefin or to produce an ethylene/α-olefin copolymer. From the viewpoint of avoiding the influence of small amounts of impurities that may remain in the α-olefin, for example, the production of an ethylene/α-olefin copolymer is a preferred embodiment.
As representative examples of the above-mentioned preferred olefin polymerization catalysts, catalysts containing various transition metal complex components (A) will be introduced below, specifically transition metal complexes (1) to (9).

(Transition Metal Complex Component (A))
The transition metal complex (1) is a compound represented by the following general formula [A1].

<R ¹ to R ⁸ >
In formula [A1], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently selected from a hydrogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group and a tin-containing group, and may be the same or different from one another, and adjacent groups may be bonded to each other to form a ring.
Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, and an arylalkyl group. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, an t-butyl group, an n-pentyl group, an neopentyl group, an n-hexyl group, an n-octyl group, an nonyl group, a dodecyl group, and an eicosyl group. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group. Examples of the alkenyl group include a vinyl group, a propenyl group, and a cyclohexenyl group. Examples of the aryl group include a phenyl group, a tolyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, a biphenyl group, an α- or β-naphthyl group, a methylnaphthyl group, an anthracenyl group, a phenanthryl group, a benzylphenyl group, a pyrenyl group, an acenaphthyl group, a phenalenyl group, an aceanthrylenyl group, a tetrahydronaphthyl group, an indanyl group, and a biphenylyl group. Examples of the arylalkyl group include a benzyl group, a phenylethyl group, and a phenylpropyl group.

<Y>
In formula [A1], Y is a divalent group bonding two ligands together. Specifically, Y is a divalent group selected from a hydrocarbon group having 1 to 20 carbon atoms, and a halogen-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group. Y is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, or a divalent silicon-containing group.
The divalent hydrocarbon group includes an alkylene group, a substituted alkylene group, and an alkylidene group, and specific examples thereof include:
Alkylene groups such as methylene, ethylene, propylene, and butylene;
substituted alkylene groups such as isopropylidene, diethylmethylene, dipropylmethylene, diisopropylmethylene, dibutylmethylene, methylethylmethylene, methylbutylmethylene, methyl-t-butylmethylene, dihexylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, ditolylmethylene, methylnaphthylmethylene, dinaphthylmethylene, 1-methylethylene, 1,2-dimethylethylene, and 1-ethyl-2-methylethylene; and cycloalkylidene groups such as cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, bicyclo[3.3.1]nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene, and dihydroindanylidene, and alkylidene groups such as ethylidene, propylidene, and butylidene.

Examples of the divalent silicon-containing group include:
Silylene; and alkylsilylene groups such as methylsilylene, dimethylsilylene, diisopropylsilylene, dibutylsilylene, methylbutylsilylene, methyl-t-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylsilylene, diphenylsilylene, ditolylsilylene, methylnaphthylsilylene, dinaphthylsilylene, cyclodimethylenesilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene, and cycloheptamethylenesilylene, particularly preferred are dialkylsilylene groups such as dimethylsilylene and dibutylsilylene.

<M>
In formula [A1], M is a Group 4 transition metal, preferably Ti, Zr or Hf, more preferably Zr or Hf, and particularly preferably Zr.
<X>
In formula [A1], each X is independently an atom or group selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, and a phosphorus-containing group, and is preferably a halogen atom or a hydrocarbon group. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine, and particularly preferably chlorine.
Specific examples of the transition metal complex (1) include the compounds listed in paragraph [0077] of JP-A-2013-224408.

(Transition Metal Complex (2))
The transition metal complex (2) is a compound represented by the following general formula [A2].

<R ^a1 to R ^a6 and R ^a11 to R ^a16 >
In formula [A2], R ^a1 , R ^a2 , R ^a3 , R ^a4 , R ^a5 , R ^a6 , R ^a11 , R ^a12 , R ^a13 , R ^a14 , R ^a15 and R ^a16 are each independently selected from a hydrogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group and a tin-containing group, and may be the same or different from each other, or two adjacent groups may be linked to each other to form a ring.
Examples of the hydrocarbon group include the hydrocarbon groups exemplified as R ^a1 to R ^a8 in the above formula [A1].
R ^a1 to R ^a6 and R ^a11 to R ^a16 are each independently preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
<Y>
In formula [A2], Y is a divalent group bonding two ligands together. Specifically, Y is a divalent group selected from a hydrocarbon group having 1 to 20 carbon atoms, and a halogen-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group. Y is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, or a divalent silicon-containing group.
Examples of these groups include the divalent groups exemplified as Y in the above formula [A1].
〈M ^a 〉
In formula [A2], M ^a is a Group 4 transition metal, preferably Ti, Zr or Hf, more preferably Zr or Hf, and particularly preferably Zr.
<X>
In formula [A2], each X is independently an atom or group selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, and a phosphorus-containing group, and is preferably a halogen atom or a hydrocarbon group. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine, and particularly preferably chlorine.
Specific examples of the transition metal complex (2) include the compounds listed in paragraph [0071] of JP-A-2013-224408.

(Transition Metal Complex (3))
The transition metal complex (3) is a compound represented by the following general formula [A3].

<R ^b1 to R ^b14 >
In formula [A3], R ^b1 , R ^b2 , R ^b3 , R ^b4 , R ^b5 , R ^b6 , R ^b7 , R ^b8 , R ^b9 , R ^b10 , R ^b11 , R ^b12 , R ^b13 and R ^b14 each independently represent a hydrogen atom, a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, and among the substituents from R ^b1 to R ^b4 , any two substituents may be bonded to each other to form a ring, among the substituents from R ^b5 to R ^b12 , any two substituents may be bonded to each other to form a ring, and R ^b13 and R ^b14 may be bonded to each other to form a ring.

Examples of the hydrocarbon group in R ^b1 to R ^b14 include a linear hydrocarbon group, a branched hydrocarbon group, a cyclic saturated hydrocarbon group, a cyclic unsaturated hydrocarbon group, and a group in which one or more hydrogen atoms of a saturated hydrocarbon group are substituted with a cyclic unsaturated hydrocarbon group. The number of carbon atoms in the hydrocarbon group is usually 1 to 20, preferably 1 to 15, and more preferably 1 to 10.

Examples of the linear hydrocarbon group include linear alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decanyl group; and linear alkenyl groups such as an allyl group.
Examples of branched hydrocarbon groups include branched alkyl groups such as an isopropyl group, a tert-butyl group, a tert-amyl group, a 3-methylpentyl group, a 1,1-diethylpropyl group, a 1,1-dimethylbutyl group, a 1-methyl-1-propylbutyl group, a 1,1-propylbutyl group, a 1,1-dimethyl-2-methylpropyl group, and a 1-methyl-1-isopropyl-2-methylpropyl group.

Examples of cyclic saturated hydrocarbon groups include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a methylcyclohexyl group; and polycyclic groups such as a norbornyl group, an adamantyl group, and a methyladamantyl group.
Examples of cyclic unsaturated hydrocarbon groups include aryl groups such as a phenyl group, a tolyl group, a naphthyl group, a biphenyl group, a phenanthryl group, and an anthracenyl group; cycloalkenyl groups such as a cyclohexenyl group; and polycyclic unsaturated alicyclic groups such as a 5-bicyclo[2.2.1]hept-2-enyl group.

Examples of the group in which one or more hydrogen atoms of a saturated hydrocarbon group are substituted with a cyclic unsaturated hydrocarbon group include groups in which one or more hydrogen atoms of an alkyl group, such as a benzyl group, a cumyl group, a 1,1-diphenylethyl group, or a triphenylmethyl group, are substituted with an aryl group.
Examples of the heteroatom-containing hydrocarbon group in R ^b1 to R ^b14 include alkoxy groups such as methoxy and ethoxy groups, aryloxy groups such as phenoxy groups, and oxygen-containing hydrocarbon groups such as furyl groups; amino groups such as N-methylamino, N,N-dimethylamino, and N-phenylamino groups, and nitrogen-containing hydrocarbon groups such as pyrryl groups; and sulfur-containing hydrocarbon groups such as thienyl groups. The number of carbon atoms in the heteroatom-containing hydrocarbon group is usually 1 to 20, preferably 2 to 18, and more preferably 2 to 15. However, silicon-containing groups are excluded from the heteroatom-containing hydrocarbon group.
Examples of the silicon-containing group for R ^b1 to R ^b14 include groups represented by the formula -SiR ₃ (wherein each of the multiple R's is independently an alkyl group or a phenyl group having 1 to 15 carbon atoms), such as a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a diphenylmethylsilyl group, or a triphenylsilyl group.

Among the substituents from R ^b1 to R ^b14 , any two substituents, for example, two adjacent substituents (e.g., R ^b1 and R ^b2 , R ^b2 and R ^b3 , R ^{b3 and R b4, R b5 and R b6} , R ^b6 and R ^b7 , R ^b7 and R ^b8 , R ^b9 and R ^b10 , R ^b10 and R ^b11 , R ^b11 and R ^b12 , R ^b13 and R ^b14 ) may be bonded to each other to form a ring. The ring formation may occur at two or more positions in the molecule.
In this specification, examples of the ring (additional ring) formed by bonding two substituents to each other include alicyclic rings, aromatic rings, and heterocyclic rings.Specific examples include cyclohexane rings, benzene rings, hydrogenated benzene rings, cyclopentene rings, heterocyclic rings such as furan rings and thiophene rings, and corresponding hydrogenated heterocyclic rings, and are preferably cyclohexane rings, benzene rings, and hydrogenated benzene rings.Furthermore, such ring structures may further have a substituent such as an alkyl group on the ring.

R ^b5 , R ^b8 , R ^b9 and R ^b12 are preferably a hydrogen atom.
R ^b6 , R ^b7 , R ^b10 and R ^b11 are preferably a hydrogen atom, a hydrocarbon group, an oxygen atom-containing hydrocarbon group or a nitrogen atom-containing hydrocarbon group, more preferably a hydrocarbon group. R ^b6 and R ^b7 may be bonded to each other to form a ring, and R ^b10 and R ^b11 may be bonded to each other to form a ring. Examples of the structure of the fluorenyl group portion as described above include those represented by the following formula.

R ^b13 and R ^b14 are preferably a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, and more preferably an aryl group or a substituted aryl group (an aryl group having a heteroatom-containing hydrocarbon group or a silicon-containing group).

<Y ^b >
In formula [A3], ^Yb is a carbon atom, a silicon atom, a germanium atom or a tin atom, and is preferably a carbon atom.

〈Mb ^, Q, j〉
In formula [A3], ^Mb is a Group 4 transition metal, preferably Ti, Zr or Hf, and more preferably Zr or Hf.
Q is a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordinating with a lone electron pair, and when j is an integer of 2 or more, Q may be selected from the same or different combinations.
Examples of the halogen atom in Q include fluorine, chlorine, bromine and iodine.
Examples of the hydrocarbon group in Q include the same groups as the hydrocarbon groups in R ^b1 to R ^b14 , and preferred are alkyl groups such as linear alkyl groups and branched alkyl groups.
Examples of the anionic ligand in Q include alkoxy groups such as methoxy and tert-butoxy; aryloxy groups such as phenoxy; carboxylate groups such as acetate and benzoate; sulfonate groups such as mesylate and tosylate; and amide groups such as dimethylamide, diisopropylamide, methylanilide, and diphenylamide.
Examples of the neutral ligand capable of coordinating with a lone electron pair in Q include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine; and ethers such as tetrahydrofuran, diethyl ether, dioxane, and 1,2-dimethoxyethane.
It is preferable that at least one of Q is a halogen atom or an alkyl group.
j is an integer of 1 to 4, preferably 2. When j is an integer of 2 or more, Q may be selected from the same or different combinations.

Specific examples of the transition metal complex (3) include the compounds listed on pages 29 to 43 of WO 2004/87775, the compounds listed on pages 9 to 37 of WO 2006/25540, the compounds listed in [0117] of WO 2015/122414, and the compounds listed in [0143] of WO 2015/122415.

(Transition Metal Complex (4))
The transition metal complex (4) is a compound represented by the following general formula [A4].

< ^Rc1 to ^Rc16 >
In formula [A4], ^Rc1 , ^Rc2 , ^Rc3 , Rc4, ^Rc5 , ^Rc6 , ^Rc7 , ^Rc8 , ^Rc9 , ^Rc10 , ^Rc11 , ^Rc12 , ^Rc13 , ^Rc14 , ^Rc15 and ^Rc16 are each independently a hydrogen atom, a hydrocarbon group, a heteroatom- ^containing hydrocarbon group or a silicon-containing group, and any two of the substituents ^Rc1 to ^Rc16 may be bonded to each other to form a ring.
Examples of the hydrocarbon group, heteroatom-containing hydrocarbon group, and silicon-containing group for R ^c1 to R ^c16 include the hydrocarbon groups, heteroatom-containing hydrocarbon groups, and silicon-containing groups exemplified as R ^b1 to R ^b14 in the above formula [A3].

Among the substituents from R ^c1 to R ^c16 , two adjacent substituents (e.g., R ^c1 and R ^c2 , R ^c2 and R ^c3 , R ^c4 and R ^c6 , R c4 and R ^c7 , R ^c5 and R ^c6 , R ^c5 and R ^c7 , R ^c6 and R ^c8 , R ^c7 and R ^c8 , R ^c9 and R ^c10 , R ^c10 and R ^c11 , R ^c11 and R ^c12 , R ^c13 and R ^c14 , R ^c14 and R ^{c15 ,} R ^c15 and R ^c16 ) may be bonded to each other to form a ring, R ^c4 and R ^c5 may be bonded to each other to form a ring, R ^c6 and R ^c7 may be bonded to each other to form a ring, R ^c1 and R ^c8 may be bonded to each other to form a ring, R ^c3 and R ^c4 may be bonded to each other to form a ring, or R ^c3 and R ^c5 may be bonded to each other to form a ring. The ring formation may occur at two or more positions in the molecule.

In this specification, examples of rings formed by bonding two substituents together (additional rings) include alicyclic rings, aromatic rings, and heterocyclic rings. Specific examples include heterocyclic rings such as a cyclohexane ring, a benzene ring, a hydrogenated benzene ring, a cyclopentene ring, a furan ring, and a thiophene ring, and corresponding hydrogenated heterocyclic rings, and preferably a cyclohexane ring, a benzene ring, and a hydrogenated benzene ring. In addition, such ring structures may further have a substituent such as an alkyl group on the ring.

R ^c1 and R ^c3 are preferably a hydrogen atom.
R ^c2 is preferably a hydrocarbon group, a heteroatom-containing hydrocarbon group, or a silicon-containing group, more preferably a hydrocarbon group, even more preferably a hydrocarbon group having 1 to 20 carbon atoms, still more preferably not an aryl group, particularly preferably a linear hydrocarbon group, a branched hydrocarbon group, or a cyclic saturated hydrocarbon group, and particularly preferably a substituent in which the carbon having a free valence (the carbon bonded to the cyclopentadienyl ring) is a tertiary carbon.

Specific examples of R ^c2 include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a tert-pentyl group, a tert-amyl group, a 1-methylcyclohexyl group, and a 1-adamantyl group. More preferred are substituents in which the carbon having a free valence is a tertiary carbon, such as a tert-butyl group, a tert-pentyl group, a 1-methylcyclohexyl group, and a 1-adamantyl group. Particularly preferred are a 1-adamantyl group and a tert-butyl group.
In the case where the transition metal complex (4) is represented by the following general formula [A4'], R ^c4 is preferably a hydrogen atom.

In this case, the transition metal complex (4) includes all enantiomers of the transition metal complex represented by the general formula [A4'], for example, the transition metal complex represented by the general formula [A4''], within the scope of the present invention.

In the notations of formulae [A4'] and [A4''], the M ^c Q _j portion is positioned in front of the page, and the bridge portion is positioned in the back of the page. That is, in these transition metal complexes, a hydrogen atom (R ^c4 ) facing the central metal is present at the α-position of the cyclopentadiene ring (based on the carbon atom substituted by the bridge portion).
On the other hand, in the above-mentioned general formula [A4], it is not specified whether the M ^c Q _j portion and the crosslinked portion are present in front of the paper or in the back of the paper. In other words, the transition metal compound (A4) represented by the general formula [A4] includes transition metal compounds of specific structures and their enantiomers.

At least one selected from R ^c4 , R ^c5 , R ^c6 and R ^c7 is preferably a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, more preferably R ^c4 and R ^c5 are a hydrogen atom or a hydrocarbon group, more preferably R ⁵ is an alkyl group such as a linear alkyl group or a branched alkyl group, a cycloalkyl group or a cycloalkenyl group, and particularly preferably an alkyl group having 1 to 10 carbon atoms. From the viewpoint of synthesis, it is also a preferred embodiment that R ^c4 and R ^c5 are both alkyl groups, and an alkyl group having 1 to 10 carbon atoms is particularly preferred. Similarly, from the viewpoint of synthesis, it is also preferred that R ^c6 and R ^c7 are hydrogen atoms. It is more preferred that R ^c5 and R ^c7 are bonded to each other to form a ring, and particularly preferably the ring is a 6-membered ring such as a cyclohexane ring.

R ^c8 is preferably a hydrocarbon group, and particularly preferably an alkyl group such as a methyl group.
In the general formula [A4], the fluorene ring portion is not particularly limited as long as it is a structure obtained from a known fluorene derivative. R ^c9 , R ^c12 , R ^c13 and R ^c16 are preferably a hydrogen atom.
R ^c10 , R ^c11 , R ^c14 and R ^c15 are preferably a hydrogen atom, a hydrocarbon group, an oxygen atom-containing hydrocarbon group or a nitrogen atom-containing hydrocarbon group, more preferably a hydrocarbon group, still more preferably a hydrocarbon group having 1 to 20 carbon atoms, examples of which include a 2,7-di-tert-butylfluorenyl group, a 3,6-di-tert-butylfluorenyl group and a 2,7-diphenyl-3,6-di-tert-butylfluorenyl group, and particularly preferably a 2,7-di-tert-butylfluorenyl group.

R ^c10 and R ^c11 may be bonded to each other to form a ring, and R ^c14 and R ^c15 may be bonded to each other to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl groups, dibenzofluorenyl groups, octahydrodibenzofluorenyl groups, 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorenyl groups, 1,1,3,3,6,6,8,8-octamethyl-2,3,6,7,8,10- Examples thereof include a hexahydro-1H-dicyclopenta[b,h]fluorenyl group and a 1',1',3',6',8',8'-hexamethyl-1'H,8'H-dicyclopenta[b,h]fluorenyl group, and particularly preferred is a 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorenyl group.

〈M ^c , Q, j〉
In formula [A4], ^Mc is a Group 4 transition metal, preferably Ti, Zr or Hf, more preferably Zr or Hf, and particularly preferably Zr.
Q is a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordinating with a lone pair of electrons.
Examples of the halogen atom, hydrocarbon group, anionic ligand, and neutral ligand capable of coordinating with a lone electron pair in Q include those exemplified as the halogen atom, hydrocarbon group, anionic ligand, and neutral ligand capable of coordinating with a lone electron pair in the above formula [A3].
j is an integer of 1 to 4, preferably 2. When j is an integer of 2 or more, Q may be selected from the same or different combinations.

Specific examples of the transition metal complex (4) include the compounds listed on pages 11 to 15 of WO 2006/68308, the compounds listed in paragraphs [0075] to [0086] of WO 2014/50816, and the compounds listed in paragraphs [0072] to [0084] of JP 2008/50816.

（式中、Ｍ^Ａは、元素の周期律表の３－１３族の１、ランタニド又はアクチニドからの金属であり、それは＋２、＋３又は＋４形式酸化状態にあり、そして５個の置換基、即ちＲ^Ａ、（Ｒ^Ｂ）_ｋ－Ｔ（但し、ｋは０、１又は２である）、Ｒ^Ｃ、Ｒ^Ｄ及びＺ^Ａ（但し、Ｒ^Ａ、Ｒ^Ｂ、Ｒ^Ｃ及びＲ^ＤはＲ基である）を有する環状の非局在化π－結合リガンド基である１個のシクロペンタジエニル（Ｃｐ）基にπ結合しており、さらに
Ｔは、ｋが１又は２であるとき、Ｃｐ環そしてＲ^Ｂに共有結合しているヘテロ原子であり、さらにｋが０のとき、ＴはＦ、Ｃｌ、Ｂｒ又はＩであり；ｋが１のとき、ＴはＯ又はＳ、又はＮ又はＰであり、そしてＲ^ＢはＴへの二重結合を有し；ｋが２のとき、ＴはＮ又はＰであり、さらに
Ｒ^Ｂは、それぞれの場合独立して、水素であるか、又はヒドロカルビル、ヒドロカルビルシリル、ハロゲン置換ヒドロカルビル、ヒドロカルビルオキシ置換ヒドロカルビル、ヒドロカルビルアミノ置換ヒドロカルビル、ヒドロカルビルシリルヒドロカルビル、ヒドロカルビルアミノ、ジ（ヒドロカルビル）アミノ、ヒドロカルビルオキシである１－８０個の非水素原子を有する基であり、各Ｒ^Ｂは任意にそれぞれの場合独立して１－２０個の非水素原子を有するヒドロカルビルオキシ、ヒドロカルビルシロキシ、ヒドロカルビルシリルアミノ、ジ（ヒドロカルビルシリル）アミノ、ヒドロカルビルアミノ、ジ（ヒドロカルビル）アミノ、ジ（ヒドロカルビル）ホスフィノ、ヒドロカルビルスルフィド、ヒドロカルビル、ハロゲン置換ヒドロカルビル、ヒドロカルビルオキシ置換ヒドロカルビル、ヒドロカルビルアミノ置換ヒドロカルビル、ヒドロカルビルシリル又はヒドロカルビルシリルヒドロカルビル又は１－２０個の非水素原子を有する非干渉基である１個以上の基により置換されていてもよく；そして
Ｒ^Ａ、Ｒ^Ｃ及びＲ^Ｄのそれぞれは、水素であるか、又はヒドロカルビル、ハロゲン置換ヒドロカルビル、ヒドロカルビルオキシ置換ヒドロカルビル、ヒドロカルビルアミノ置換ヒドロカルビル、ヒドロカルビルシリル、ヒドロカルビルシリルヒドロカルビルである１－８０個の非水素原子を有する基であり、Ｒ^Ａ、Ｒ^Ｃ及びＲ^Ｄのそれぞれは、任意にそれぞれの場合独立して１－２０個の非水素原子を有するヒドロカルビルオキシ、ヒドロカルビルシロキシ、ヒドロカルビルシリルアミノ、ジ（ヒドロカルビルシリル）アミノ、ヒドロカルビルアミノ、ジ（ヒドロカルビル）アミノ、ジ（ヒドロカルビル）ホスフィノ、ヒドロカルビルスルフィド、ヒドロカルビル、ハロゲン置換ヒドロカルビル、ヒドロカルビルオキシ置換ヒドロカルビル、ヒドロカルビルアミノ置換ヒドロカルビル、ヒドロカルビルシリル又はヒドロカルビルシリルヒドロカルビルであるか、又は１－２０個の非水素原子を有する非干渉基である１個以上の基により置換されていてもよく；又は任意に、Ｒ^Ａ、Ｒ^Ｂ、Ｒ^Ｃ及びＲ^Ｄの２個以上は、互いに共有結合してそれぞれのＲ基について１－８０個の非水素原子を有する１個以上の縮合環又は環系を形成し、１個以上の縮合環又は環系は、置換されていないか、又はそれぞれの場合独立して１－２０個の非水素原子を有するヒドロカルビルオキシ、ヒドロカルビルシロキシ、ヒドロカルビルシリルアミノ、ジ（ヒドロカルビルシリル）アミノ、ヒドロカルビルアミノ、ジ（ヒドロカルビル）アミノ、ジ（ヒドロカルビル）ホスフィノ、ヒドロカルビルスルフィド、ヒドロカルビル、ハロゲン置換ヒドロカルビル、ヒドロカルビルオキシ置換ヒドロカルビル、ヒドロカルビルアミノ置換ヒドロカルビル、ヒドロカルビルシリル又はヒドロカルビルシリルヒドロカルビル、又は１－２０個の非水素原子を有する非干渉基である１個以上の基により置換されており；
Ｚ^Ａはσ結合を介してＣｐ及びＭ^Ａの両者に結合している２価の基であり、Ｚ^Ａは硼素であるか又は元素の周期律表の１４族の一員であり、さらに窒素、燐、硫黄又は酸素からなり；
Ｘ^Ａは、環状の非局在化π結合リガンド基であるリガンドの群を除く、６０個以内の原子を有するアニオン性又はジアニオン性リガンド基であり；
Ｘ^Ａ’は、それぞれの場合独立して２０個以内の原子を有する中性のルイス塩基配位結合性化合物であり；
ｐは０、１又は２であり、そしてＸ^Ａがアニオン性リガンドであるときＭ^Ａの形式酸化状態より２少なく；Ｘ^Ａがジアニオン性リガンドであるとき、ｐは１であり；そして
ｑは０、１又は２である。）
前記遷移金属錯体（５）の具体例としては、特表２０００－５１６２２８号公報の３５～９９頁に列挙された化合物が挙げられる。 (Transition Metal Complex (5))
The transition metal complex (5) is a metal complex corresponding to the following general formula [A5], which is described in JP-A-2000-516228.

wherein M ^A is a metal from Groups 3-13 of the Periodic Table of the Elements, the Lanthanides or the Actinides, which is in the +2, +3 or +4 formal oxidation state and is π-bonded to a cyclopentadienyl (Cp) group which is a cyclic delocalized π-bonded ^ligand group having five substituents, namely R ^A , (R ^B ) _k -T, where k is 0, 1 or 2, R C , R ^D and Z ^A , where R ^A , R ^B , R ^C and R ^D are R groups; further wherein T is a heteroatom covalently bonded to the Cp ring and to R ^B when k is 1 or 2; further wherein T is F, Cl, Br or I when k is 0; further wherein T is O or S, or N or P and R ^B has a double bond to T; further wherein T is N or P when k is 1 or 2; R ^B is, independently at each occurrence, hydrogen or a group having 1-80 non-hydrogen atoms which is hydrocarbyl, hydrocarbylsilyl, halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilylhydrocarbyl, hydrocarbylamino, di(hydrocarbyl)amino, hydrocarbyloxy, each R ^B may optionally be substituted by one or more groups which, independently at each occurrence, are hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di(hydrocarbylsilyl)amino, hydrocarbylamino, di(hydrocarbyl) ^amino , di(hydrocarbyl)phosphino, hydrocarbylsulfido, hydrocarbyl, halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, ^{hydrocarbylamino} -substituted hydrocarbyl, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl or non-interfering groups having 1-20 non-hydrogen atoms; and each of ^D is hydrogen or a group having 1-80 non-hydrogen atoms which is hydrocarbyl, halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl, hydrocarbylsilylhydrocarbyl, and each of R ^A , R ^C and R ^D may optionally be substituted by one or more groups which, independently in each occurrence, are hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di(hydrocarbylsilyl)amino, hydrocarbylamino, di(hydrocarbyl)amino, di(hydrocarbyl)phosphino, hydrocarbylsulfido, hydrocarbyl, halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl having 1-20 non-hydrogen atoms, or are non-interfering groups having 1-20 non-hydrogen atoms; or optionally, R ^A , R ^B , R ^C and R two or more of ^D are covalently bonded to each other to form one or more fused rings or ring systems having 1-80 non-hydrogen atoms for each R group, and one or more of the fused rings or ring systems are unsubstituted or substituted by one or more groups which are, independently in each occurrence, hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di(hydrocarbylsilyl)amino, hydrocarbylamino, di(hydrocarbyl)amino, di(hydrocarbyl)phosphino, hydrocarbylsulfido, hydrocarbyl, halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl, or non-interfering groups having 1-20 non-hydrogen atoms;
Z ^A is a divalent group bonded to both Cp and M ^A through a σ bond, Z ^A is boron or a member of Group 14 of the Periodic Table of Elements, and further comprises nitrogen, phosphorus, sulfur, or oxygen;
^XA is an anionic or dianionic ligand group having 60 or fewer atoms, excluding the group of ligands which are cyclic delocalized π-bonded ligand groups;
X ^A ' is independently at each occurrence a neutral Lewis base coordinating compound having up to 20 atoms;
p is 0, 1 or 2 and is 2 less than the formal oxidation state of ^M when ^XA is an anionic ligand; p is 1 when ^XA is a dianionic ligand; and q is 0, 1 or 2.
Specific examples of the transition metal complex (5) include the compounds listed on pages 35 to 99 of JP-A-2000-516228.

（式中、Ｌ´はπ－結合した基であり、
Ｍ^Ｂは周期律表４族金属であり、
Ｊは窒素又は燐であり、
Ｚ^Ｂは２価の橋かけ結合基であり、
Ｒ´は不活性の１価のリガンドであり、
ｒは１又は２であり、
Ｘ^Ｂはそれぞれの場合独立してμ－橋かけ結合リガンド基を形成できるルイス塩基性リガンド基であり、所望により２個のＸ^Ｂ基は一緒に結合してもよく、そして
Ａ´はそれぞれの場合独立して水素を除いて５０個以内の原子のアルミニウム含有ルイス酸化合物であり、該化合物はμ－橋かけ結合基により金属錯体との付加物を形成し、所望により２個のＡ´基は一緒に結合しそれにより単一の２官能性ルイス酸含有化合物を形成してもよい。）
前記遷移金属錯体（６）の具体例としては、特表２００２－５２２５５１号公報の［００２５］～［００２７］に列挙された化合物が挙げられる。 (Transition Metal Complex (6))
The transition metal complex (6) is an ansabis (μ-substituted) compound of a metal of Group 4 of the periodic table and aluminum, which corresponds to the following general formula [A6] and is described in JP-A-2002-522551:

wherein L' is a π-bonded group;
M ^B is a Group 4 metal of the periodic table;
J is nitrogen or phosphorus;
^ZB is a divalent bridging group;
R' is an inert monovalent ligand;
r is 1 or 2;
^XB is independently in each occurrence a Lewis basic ligand group capable of forming a μ-bridging ligand group, optionally two ^XB groups may be linked together, and A' is independently in each occurrence an aluminum-containing Lewis acid compound of up to 50 atoms excluding hydrogen, which compound forms an adduct with the metal complex through the μ-bridging group, optionally two A' groups may be linked together thereby forming a single bifunctional Lewis acid-containing compound.
Specific examples of the transition metal complex (6) include the compounds listed in [0025] to [0027] of JP-T-2002-522551.

（式中、Ｍ^Ｄは元素周期律表の３～１３族ランタニド又はアクチニドの１つから選ばれる金属である；
Ｚ^Ｄはホウ素、又は元素周期律表の１４族の１員をもち、且つ窒素、リン、硫黄又は酸素をもつ２価の基である；
Ｘ^Ｄは水素を算入せずに６０以下の原子をもつアニオン性リガンド基であり、所望により２個のＸ基はいっしょになって２価のアニオン性リガンド基を形成している；
Ｘ^Ｄ’はそれぞれの場合独立に２０以下の原子をもつ中性ルイス塩基リガンドである；
ｐ１は０～５の数であって、Ｍ^Ｄの形式酸化状態より２少ない；
ｑ１は０、１又は２である；
Ｅはケイ素又は炭素である；
Ｒ^Ａ１はそれぞれの場合独立に水素又はＲ^Ｂ１である；
Ｒ^Ｂ１はＢＲ^Ｃ１ _２であるか、又はヒドロカルビル、ヒドロカルビルシリル、ハロゲン置換ヒドロカルビル、ヒドロカルビルオキシ置換ヒドロカルビル、ジ（ヒドロカルビル）アミノ置換ヒドロカルビル、ＢＲ^Ｃ１ _２－置換ヒドロカルビル、ヒドロカルビルシリルヒドロカルビル、ジ（ヒドロカルビル）アミノ、ヒドロカルバジイルアミノ、又はヒドロカルビルオキシ基であり、各Ｒ^Ｂ１は水素を算入せずに１～１８の原子をもち、そして所望により２個のＲ^Ｂ１基は共有結合して１以上の縮合環を形成していてもよい；
Ｒ^Ｃ１はそれぞれの場合独立にヒドロカルビル、ハロゲン置換ヒドロカルビル、ヒドロカルビルオキシ置換ヒドロカルビル、ジヒドロカルビルアミノ置換ヒドロカルビル、ヒドロカルバジイルアミノ置換ヒドロカルビル、ヒドロカルビルシリル、ヒドロカルビルシリルヒドロカルビル、又はＲ^Ｄである；
Ｒ^Ｄ１はそれぞれの場合独立にジヒドロカルビルアミノ又はヒドロカルビルオキシ基で水素を算入せずに１～２０の原子をもち、そして所望により単一のホウ素上の２個のＲ^Ｄ１基はいっしょになってホウ素に結合した両原子価をもつヒドロカルバジイルアミノ－、ヒドロカルバジイルオキシ－、ヒドロカルバジイルジアミノ－、又はヒドロカルバジイルオキシ－基を形成している；
但し少なくとも１の場合においてＲ^Ａ１はＢＲ^Ｃ１ _２、ＢＲ^Ｃ１ _２－置換ヒドロカルビル基、及びそれらが合体した誘導体から選ばれると共に、少なくとも１のＲ^Ｃ１はＲ^Ｄ１である；
Ｒ^Ｆはそれぞれの場合独立に水素、又はシリル、ヒドロカルビル、ヒドロカルビルオキシ及びそれらの組合せから選ばれる基であって、該Ｒ^Ｆは３０以下の炭素又はケイ素原子をもっている；そしてｘは１～８であるか、又は所望により（Ｒ^Ｆ _２Ｅ）_ｘが－Ｔ’Ｚ^Ｄ’－又は－（Ｔ’Ｚ^Ｄ’）_２－であり、ここでＴ’はそれぞれの場合独立にホウ素又はアルミニウムであり、そしてＺ^Ｄ’はそれぞれの場合独立に

であり；
Ｒ^ｄ１はそれぞれの場合独立に水素、ヒドロカルビル基、トリヒドロカルビルシリル基、又はトリヒドロカルビルシリルヒドロカルビル基であり、該Ｒ^ｄ１基は炭素を算入せずに２０以下の原子をもち、そして２個のこれらＲ^ｄ１基は所望によりいっしょになって環構造を形成していてもよい；そして
Ｒ^ｄ５はＲ^ｄ１又はＮ（Ｒ^ｄ１）_２である。）
前記遷移金属錯体（７）の具体例としては、特表２００３－５０１４３３号公報の［００３０］に列挙された化合物が挙げられる。 (Transition Metal Complex (7))
The transition metal complex (7) is a metal complex corresponding to the following general formula [A7-1], [A7-2] or [A7-3], which is described in JP-A-2003-501433.

(wherein M ^D is a metal selected from one of the lanthanides or actinides of Groups 3 to 13 of the Periodic Table of the Elements;
^ZD is boron or a divalent radical having a member of Group 14 of the Periodic Table of the Elements and having nitrogen, phosphorus, sulfur or oxygen;
^XD is an anionic ligand group having 60 or fewer atoms, not counting hydrogen, and optionally two X groups taken together form a divalent anionic ligand group;
X ^D ' is independently at each occurrence a neutral Lewis base ligand having 20 or fewer atoms;
p1 is a number from 0 to 5, which is two less than the formal oxidation state of M ^D ;
q1 is 0, 1 or 2;
E is silicon or carbon;
R ^A1 is independently at each occurrence hydrogen or R ^B1 ;
R ^B1 is BR ^C1 ₂ or a hydrocarbyl, hydrocarbylsilyl, halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, di(hydrocarbyl)amino-substituted hydrocarbyl, BR ^C1 ₂ -substituted hydrocarbyl, hydrocarbylsilylhydrocarbyl, di(hydrocarbyl)amino, hydrocarbadiylamino, or hydrocarbyloxy group, each R ^B1 having 1 to 18 atoms, not counting hydrogen, and optionally two R ^B1 groups may be covalently linked to form one or more fused rings;
R ^C1 is independently at each occurrence hydrocarbyl, halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, dihydrocarbylamino-substituted hydrocarbyl, hydrocarbadiylamino-substituted hydrocarbyl, hydrocarbylsilyl, hydrocarbylsilylhydrocarbyl, or R ^D ;
R ^D1 is independently in each occurrence a dihydrocarbylamino or hydrocarbyloxy group having 1 to 20 atoms, not counting hydrogen, and optionally two R ^D1 groups on a single boron taken together form a bivalent hydrocarbadiylamino-, hydrocarbadiyloxy-, hydrocarbadiyldiamino-, or hydrocarbadiyloxy- group bonded to boron;
with the proviso that in at least one instance R ^A1 is selected from BR ^C1 ₂ , BR ^C1 ₂ -substituted hydrocarbyl groups, and combined derivatives thereof, and at least one R ^C1 is R ^D1 ;
R ^F is independently at each occurrence hydrogen or a radical selected from silyl, hydrocarbyl, hydrocarbyloxy, and combinations thereof, said R ^F having up to 30 carbon or silicon atoms; and x is 1 to 8 or optionally (R ^F ₂ E) _x is -T'Z ^D '- or -(T'Z ^D ') ₂ -, where T' is independently at each occurrence boron or aluminum and Z ^D ' is independently at each occurrence

and
R ^d1 is independently at each occurrence hydrogen, a hydrocarbyl group, a trihydrocarbylsilyl group, or a trihydrocarbylsilylhydrocarbyl group, said R ^d1 group having 20 or fewer atoms, not counting carbon, and two such R ^d1 groups may optionally be joined together to form a ring structure; and R ^d5 is R ^d1 or N(R ^d1 ) ₂ .
Specific examples of the transition metal complex (7) include the compounds listed in paragraph [0030] of JP-A No. 2003-501433.

〈Ｍ ^ｅ 〉
式［Ａ８］中、Ｍ^ｅは周期表第４、５族の遷移金属原子を示し、好ましくは４族の遷移金属原子である。具体的には、チタン、ジルコニウム、ハフニウム、バナジウム、ニオブ、タンタルなどであり、より好ましくはチタン、ジルコニウム、ハフニウムであり、特に好ましくはチタンまたはジルコニウムである。
式［Ａ８］においてＮとＭ^ｅとを繋ぐ点線は、一般的にはＮがＭ^ｅに配位していることを示すが、本発明においては配位していてもしていなくてもよい。
〈ｍ１〉
式［Ａ８］において、ｍ１は１～４の整数、好ましくは２～４の整数、さらに好ましくは２を示す。 (Transition Metal Complex (8))
The transition metal complex (8) is a compound represented by the following general formula [A8].

<M ^e >
In formula [A8], ^Me represents a transition metal atom of Groups 4 and 5 of the periodic table, and is preferably a transition metal atom of Group 4. Specifically, it is titanium, zirconium, hafnium, vanadium, niobium, tantalum, etc., more preferably titanium, zirconium, or hafnium, and particularly preferably titanium or zirconium.
In the formula [A8], the dotted line connecting N and ^Me generally indicates that N is coordinated to ^Me , but in the present invention, it may or may not be coordinated.
<m1>
In formula [A8], m1 is an integer of 1 to 4, preferably an integer of 2 to 4, and more preferably 2.

<R ^e1 ~R ^e5 >
In formula [A8], R ^e1 to R ^e5 may be the same or different and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, , a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring.
Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.
Examples of the hydrocarbon group include the hydrocarbon groups exemplified as R ^b1 to R ^b14 in the above formula [A3], and particularly,
A methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a neopentyl group, an n-hexyl group, or the like, having 1 to 30 carbon atoms, preferably 1 to 20 linear or branched alkyl groups;
aryl groups having 6 to 30, preferably 6 to 20, carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, or an anthracenyl group;
These aryl groups may have a substituent such as a halogen atom, an alkyl group or an alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, or an aryl group or an aryloxy group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms. Substituted aryl groups having 1 to 5 substituted aryl groups are preferred.

From the viewpoint of olefin polymerization catalyst activity and of providing a high molecular weight olefin polymer, R ^e1 is preferably a group selected from a linear or branched hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms.

Examples of the heterocyclic compound residue include residues of nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine, oxygen-containing compounds such as furan and pyran, and sulfur-containing compounds such as thiophene, as well as groups in which these heterocyclic compound residues are further substituted with a substituent having 1 to 30, preferably 1 to 20 carbon atoms, such as an alkyl group or an alkoxy group.
Examples of the oxygen-containing group include an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, and a carboxylic anhydride group.
Examples of the nitrogen-containing group include an amino group, an imino group, an amido group, an imido group, a hydrazino group, a hydrazono group, a nitro group, a nitroso group, a cyano group, an isocyano group, a cyanate ester group, an amidino group, a diazo group, and an amino group in the form of an ammonium salt.
Examples of the boron-containing group include a boranediyl group, a boranetriyl group, and a diboranyl group.
Examples of the sulfur-containing group include a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group, a thioether group, a thiocyanate ester group, an isocyanate ester group, a sulfone ester group, a sulfonamide group, a thiocarboxyl group, a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, and a sulfenyl group.
Phosphorus-containing groups include phosphido groups, phosphoryl groups, thiophosphoryl groups, phosphato groups, and the like.
Examples of silicon-containing groups include silyl groups, siloxy groups, hydrocarbon-substituted silyl groups, and hydrocarbon-substituted siloxy groups, more specifically, methylsilyl groups, dimethylsilyl groups, trimethylsilyl groups, ethylsilyl groups, diethylsilyl groups, triethylsilyl groups, diphenylmethylsilyl groups, triphenylsilyl groups, dimethylphenylsilyl groups, dimethyl-t-butylsilyl groups, dimethyl(pentafluorophenyl)silyl groups, etc. Examples of hydrocarbon-substituted siloxy groups include trimethylsiloxy groups.
The germanium-containing group and the tin-containing group include groups in which the silicon of the above-mentioned silicon-containing group is substituted with germanium or tin.

<R ^e6 >
In formula [A8], R ^e6 is selected from a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms consisting only of primary or secondary carbon, an aliphatic hydrocarbon group having 4 or more carbon atoms, an aryl group-substituted alkyl group, a monocyclic or bicyclic alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a halogen atom. Among these, from the viewpoints of olefin polymerization catalyst activity, of providing a high-molecular-weight olefin polymer, and of hydrogen resistance during polymerization, it is preferable to use a group selected from an aliphatic hydrocarbon group having 4 or more carbon atoms, an aryl-substituted alkyl group, a monocyclic or bicyclic alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and more preferable examples include a branched hydrocarbon group such as a t-butyl group; an aryl-substituted alkyl group such as a benzyl group, a 1-methyl-1-phenylethyl group (cumyl group), a 1-methyl-1,1-diphenylethyl group, or a 1,1,1-triphenylmethyl group (trityl group); and an alicyclic hydrocarbon group having 6 to 15 carbon atoms and an alicyclic or polycyclic structure such as a cyclohexyl group, an adamantyl group, a norbornyl group, or a tetracyclododecyl group which has a hydrocarbon group at the 1-position.
<n1>
In formula [A8], n is a number that satisfies the valence of ^Me .

<X ^e >
In formula [A8], ^Xe represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group. When n is 2 or more, the multiple groups represented by ^Xe may be the same or different, and the multiple groups represented by ^Xe may be bonded to each other to form a ring.
Examples of the halogen atoms and hydrocarbon groups include those exemplified in the above description of R ^e1 to R ^e5 . Of these, halogen atoms and hydrocarbon groups are preferred.

(Transition Metal Complex (9))
The transition metal complex (9) is a compound represented by the following general formula [A9].

<M ^f >
In formula [A9], ^Mf represents a transition metal atom of Groups 4 to 11 of the periodic table, specifically, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, manganese, iron, cobalt, nickel, palladium, etc., and is preferably a metal atom of Groups 4 to 7 and 10 of the periodic table, specifically, titanium, zirconium, hafnium, vanadium, chromium, manganese, nickel, and more preferably titanium and nickel.
In the formula [A9], the dotted line connecting N and ^Mf generally indicates that N is coordinated to ^Mf , but in the present invention, it may or may not be coordinated.
<m2>
In formula [A9], m2 represents an integer of 1 to 4, and is preferably 2.

<Rf ¹ ~Rf ⁵ >
In formula [A9], R ^f1 to R ^f5 may be the same or different and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, , a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring.
Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.
Examples of the hydrocarbon group, the heterocyclic compound residue, the oxygen-containing group, the nitrogen-containing group, the boron-containing group, the sulfur-containing group, the phosphorus-containing group, the silicon-containing group, the germanium-containing group, and the tin-containing group include those represented by the above formula [ A8] are exemplified as R ^f1 to R ^f5 .
A preferred embodiment of R ^f1 is a group exhibiting aromaticity, and more preferably an aryl group represented by the following general formula [A9-1] or a pyrrole which may have a substituent.

In general formula [A9-1], R ^1A to R ^1E may be the same or different, may be bonded to each other to form a ring, and are a hydrogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. Examples of the hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, and tin-containing group include those exemplified as R ^f1 to R ^f5 in formula [A9] above.

<R ^f6 >
In formula [A9], R ^f6 is selected from a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms consisting only of primary or secondary carbon, an aliphatic hydrocarbon group having 5 or more carbon atoms, an aryl group-substituted alkyl group, a monocyclic or bicyclic alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a halogen atom.
R ^f6 represents an aryl group having 6 to 30, preferably 6 to 20, carbon atoms, such as phenyl, benzyl, naphthyl, or anthranyl;
A linear or branched (secondary) alkyl group having 1 to 30, preferably 1 to 20, carbon atoms, such as methyl, ethyl, isopropyl, isobutyl, sec-butyl, or neopentyl;
Preferred are cyclic saturated hydrocarbon groups having 3 to 30, preferably 3 to 20, carbon atoms, such as cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2,6-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and cyclododecyl. Particularly preferred as R ^f6 are aromatic groups such as phenyl, benzyl, and naphthyl, and 3,5-difluorophenyl and 3,5-bistrifluoromethylphenyl in which the hydrogen atoms of these groups are substituted.

<n2>
In formula [A9], n2 is a number satisfying the valence of ^Mf , specifically, 0 to 5, preferably 1 to 4, and more preferably 2.
〈Xf〉 ^​ ​
In formula [A9], ^Xf represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group. When n2 is 2 or more, the multiple groups represented by ^Xf may be the same or different, and the multiple groups represented by X may be bonded to each other to form a ring.
Examples of each group such as a halogen atom and a hydrocarbon group include the same groups as those exemplified in the explanation of R ^f1 to R ^f5 above.
Specific examples of the transition metal complex (9) include the compounds listed in [0079] to [0088] of JP-A-2011-231291.
The transition metal complex is not limited to the above-mentioned transition metal complexes (1) to (9). In addition, for example, transition metal complexes described in [0007] of JP-A-2008-163140, [0030] to [0051] of WO 2010/50256, [0016] of JP-A-2010-150246, [0133] of WO 2013/184579, [0006] of JP-T-2013-534934, [0001] of JP-T-2009-534517, and [0009] to [0017] of JP-T-2001-516776 can be exemplified.

[Organometallic compound (B)]
The organometallic compound (B) containing a Group 13 metal of the periodic table used in the present invention is mainly a compound (B1) which reacts with the transition metal complex (A) to form an ion pair, or an organometallic compound (B2) which mainly contains an aluminum atom. (B2) can be mentioned. These compounds will be explained below.

<Compound (B1) that reacts with transition metal complex (A) to form an ion pair>
In this embodiment, the compound (B1) that reacts with the transition metal complex (A) to form an ion pair is a compound represented by the general formula [B1].

In formula [B1], R ^e+ represents a carbenium cation, and R ^f to R ⁱ each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms. In this embodiment, the carbenium cation represented by R ^e+ is specifically a three-coordinate carbocation having a structure represented by R ^j C ⁺ . Here, the three R ^j may be the same or different from each other, and may have various substituents. In general, examples of the substituents include a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20, and more preferably 1 to 10 carbon atoms; an alicyclic hydrocarbon group having 3 to 30 carbon atoms, preferably 3 to 20, and more preferably 3 to 10 carbon atoms; and an aromatic hydrocarbon group having 6 to 30 carbon atoms, preferably 6 to 20, and more preferably 6 to 10 carbon atoms. Furthermore, at least one hydrogen atom of the various hydrocarbon groups may be substituted with another hydrocarbon group.

Specific examples of the carbenium cation include trisubstituted carbenium cations such as triphenylcarbenium cation, tris(methylphenyl)carbenium cation, and tris(dimethylphenyl)carbenium cation. The triphenylcarbenium cation is preferred from the viewpoints that it exhibits high polymerization activity over a wide range of polymerization temperatures and is easily available industrially.

In general, ionizing ionic compounds that can be used as components of olefin polymerization catalysts include compounds having an anilinium cation in addition to the above-mentioned compounds having a carbenium cation. However, it has been found that it is difficult to completely dissolve an ionizing ionic compound having an anilinium cation in a saturated hydrocarbon solvent when the olefin polymerization catalyst used in this embodiment is composed of a metallocene compound, an ionizing ionic compound, and an aluminum compound.

On the other hand, in the case of ionized ionic compounds having a carbenium cation, as described below, they are relatively reactive with the following compound (B2), and therefore can be dissolved even in saturated hydrocarbon solvents within a specific concentration range.

Among the substituents represented by R ^f to R ⁱ , examples of the hydrocarbon group having 1 to 20 carbon atoms include aromatic hydrocarbon groups having 6 to 20 carbon atoms, and unsubstituted aryl groups and substituted aryl groups are preferred. Examples of the substituent in the aryl group include hydrocarbon groups.

Examples of halogenated hydrocarbon groups having 1 to 20 carbon atoms include halogenated aromatic hydrocarbon groups having 6 to 20 carbon atoms, with halogenated aryl groups being preferred. Examples of substituents on the aryl group include halogenated hydrocarbon groups and halogen atoms.

Specific examples of the hydrocarbon group and halogenated hydrocarbon group include a phenyl group, a tolyl group, a dimethylphenyl group, a trifluoromethylphenyl group, a ditrifluoromethylphenyl group, and a pentafluorophenyl group.

Specific examples of the compound represented by the general formula [B1] include triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(3,5-ditrifluoromethylphenyl)borate, tris(4-methylphenyl)carbenium tetrakis(pentafluorophenyl)borate, tris(3,5-dimethylphenyl)carbenium tetrakis(pentafluorophenyl)borate, and the like.
The component (B1) may be used alone or in combination of two or more kinds.
As the component (B1), triphenylcarbenium tetrakis(pentafluorophenyl)borate is particularly preferred from the viewpoints of reactivity with the following compound (B2), high solubility in saturated hydrocarbon solvents, and industrial availability.

<Compound (B2)>
In this embodiment, the compound (B2) is at least one compound selected from an organoaluminum compound (C-1) and an organoaluminum oxy compound (C-2), and it is preferable to use at least one organoaluminum compound (C-1). In this embodiment, the organoaluminum oxy compound (C-2) refers to a compound having an Al-C bond and a plurality of independent Al-O bonds, and the organoaluminum compound (C-1) refers to a compound having an Al-C bond and no plurality of independent Al-O bonds (having no independent Al-O bonds or one independent Al-O bond). However, the independent Al-O bond means that the Al atom and the O atom are not counted in duplicate, for example, in the case of -Al(R ^k )-O-Al(R ^k )-O-Al-, the number of Al-O bonds is 2, and in the case of R ^k Al(OR ^k ) ₂ , the number of Al-O bonds is 1 (R ^k is, for example, a hydrocarbon group). Therefore, in this embodiment, the organoaluminum compound (C-1) does not include the organoaluminum oxy-compound (C-2).
When the organoaluminum compound (C-1) is selected, one type may be used alone or two or more types may be used in combination. When the organoaluminum oxy compound (C-2) is selected, one type may be used alone or two or more types may be used in combination.

<Organoaluminum Compound (C-1)>
Examples of the organoaluminum compound (C-1) include organoaluminum compounds represented by the general formulas [C2] and [C3], and alkyl complexes of aluminum and metals of Group 1 of the periodic table represented by the general formula [C4].
R ^a _m3 Al (OR ^b ) _n3 X ^g _p2 ...[C2]
In formula [C2], R ^a and R ^b each independently represent a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms, X ^g represents a halogen atom, m3 is a number satisfying 0<m3≦3, n3 is a number satisfying 0≦n3<3, p2 is a number satisfying 0≦p2<3, and m3+n3+p2=3.

Examples of the organoaluminum compound represented by the general formula [C2] include tri-n-alkylaluminum compounds such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, and trioctylaluminum;
Tri-branched alkylaluminums such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, and tri-2-ethylhexylaluminum;
Tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminums such as triphenylaluminum and tritolylaluminum;
alkenylaluminum such as isoprenylaluminum represented by the general formula (i-C ₄ H ₉ ) _x1 Al _y (C ₅ H ₁₀ ) _z (wherein x1, y and z are positive numbers, and z≦2x1); alkylaluminum dialkoxides such as isobutylaluminum dimethoxide and isobutylaluminum diethoxide; dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;
partially alkoxylated alkylaluminums having an average composition represented by the general formula R ^a _2.5 Al(OR ^b ) _0.5 (wherein R ^a and R ^b have the same meanings as R ^a and R ^b in formula [C2]); alkylaluminum aryloxides such as diethylaluminum phenoxide and diethylaluminum (2,6-di-t-butyl-4-methylphenoxide); dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide;
Partially halogenated alkylaluminums, such as alkylaluminum dihalides, such as ethylaluminum dichloride; partially alkoxylated and halogenated alkylaluminums, such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide, and the like.

R ^m _q2 AlH _r1 ...[C3]
In formula [C3], R ^m represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and when there are a plurality of R d s, each R ^m may be the same or different. Examples of the alkyl group include an alkyl group having 1 to 15 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aryl group having 6 to 15 carbon atoms. q2 is 0≦q2≦2, and r1 is 1. The number ≦r1≦3, and q2+r1=3.

Examples of aluminum compounds having an Al-H bond represented by the general formula [C3] include dimethylaluminum hydride, diethylaluminum hydride, diisopropylaluminum hydride, dibutylaluminum hydride, diisobutylaluminum hydride, diisohexylaluminum hydride, diphenylaluminum hydride, dicyclohexylaluminum hydride, phenylaluminum dihydride, and alan.

M ² AlR ^a ₄ ...[C4]
In formula [C4], ^M2 represents Li, Na or K, and each of the multiple R ^a's independently represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.
Examples of the compound represented by the general formula [C4] include LiAl(C ₂ H ₅ ) ₄ and LiAl(C ₇ H ₁₅ ) ₄ .

Compounds similar to the compound represented by formula [C4] can also be used, such as organoaluminum compounds in which two or more aluminum compounds are bonded via nitrogen atoms, such as (C ₂ H ₅ ) ₂ AlN(C ₂ H ₅ )Al(C ₂ H ₅ ) ₂ .

As the organoaluminum compound (C-1), a compound represented by the general formula [C2] is preferred, and among these, a compound represented by m3=3 in the general formula [C2] is preferred from the viewpoint of industrial availability. Furthermore, among these, a compound represented by the general formula [C1] is particularly preferred from the viewpoints of reactivity with component (B1), stability and solubility of the catalyst solution, etc.

AlR ⁿ ₃ ...[C1]

In formula [C1], ^Rn represents a linear or branched alkyl group having 3 to 10 carbon atoms.
Specifically, triisopropylaluminum, tri-normal propylaluminum, triisobutylaluminum, tri-normal butylaluminum, tri-normal hexylaluminum, and tri-normal octylaluminum are preferred, and among these, triisobutylaluminum, tri-normal hexylaluminum, and tri-normal octylaluminum are particularly preferred from the viewpoints of solubility in saturated hydrocarbon solvents and industrial availability.

Organoaluminum oxy compound (C-2)
Examples of the organoaluminum oxy compound (C-2) include conventionally known aluminoxanes such as the compounds represented by the general formula [C5] and the compounds represented by the general formula [C6], methylaluminoxane analogues such as the modified methylaluminoxane represented by the general formula [C7], and boron-containing organoaluminum oxy compounds represented by the general formula [C8].

In formulas [C5] and [C6], R ^p represents a hydrocarbon group having 1 to 10 carbon atoms, preferably a methyl group, n4 represents an integer of 2 or more, preferably 3 or more, more preferably 10 or more, and the upper limit of n4 is not particularly limited, but is usually 30. Multiple R ^p's may be the same or different. An organoaluminum oxy compound in which R ^p is a methyl group is hereinafter also referred to as "methylaluminoxane".

In formula [C7], R ^q represents a hydrocarbon group having 2 to 20 carbon atoms, m4 and n5 each independently represent an integer of 2 or more, and the upper limit of m4 + n5 is not particularly limited, but is usually 40. Multiple R ^q's may be the same or different.

The modified methylaluminoxane represented by formula [C7] is prepared, for example, using trimethylaluminum and an alkylaluminum other than trimethylaluminum (for example, the manufacturing method is disclosed in US Pat. No. 4,960,878 and US Pat. No. 5,041,584). Modified methylaluminoxane prepared using trimethylaluminum and triisobutylaluminum (i.e., R is an isobutyl group) is commercially produced by manufacturers such as Tosoh Finechem under the names MMAO and TMAO (for example, see "Tosoh Research and Technology Report" Vol. 47, p. 55 (2003)).

In addition, in the solution polymerization in the olefin polymer production method of this embodiment, a benzene-insoluble organoaluminum oxy compound exemplified in JP-A-2-78687 can also be used.

In formula [C8], R ^c represents a hydrocarbon group having 1 to 10 carbon atoms. Each of the multiple R ^ds independently represents a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

<Saturated Hydrocarbon Solvent (D)>
The saturated hydrocarbon solvent (D) used to dissolve each of the above components (A) to (B2) is an inert hydrocarbon solvent, and more preferably a saturated hydrocarbon solvent having a boiling point of 20 to 200° C. under normal pressure.
As the saturated hydrocarbon solvent (D), it is preferable to use at least one hydrocarbon solvent selected from aliphatic hydrocarbon solvents and alicyclic hydrocarbon solvents.As the aliphatic hydrocarbon solvent, for example, pentane, hexane, heptane, octane, decane, dodecane, kerosene can be mentioned;As the alicyclic hydrocarbon solvent, for example, cyclopentane, cyclohexane, methylcyclopentane can be mentioned.Among these, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane are more preferable.

In this embodiment, the solvent used to dissolve each of the components (A) to (B2) is preferably the saturated hydrocarbon solvent (D) described above alone, but in addition to the saturated hydrocarbon solvent (D), aromatic hydrocarbons such as benzene, toluene, xylene, etc. and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane, etc. may be contained within a range in which the residual solvent in the obtained polymer, which is the effect of this embodiment, is acceptable and further, the load of the solvent removal step in the olefin polymer production process is acceptable. In the preparation of the olefin polymerization catalyst solution, the amount of each of the aromatic hydrocarbon solvent and the halogenated hydrocarbon solvent to be used is preferably 10% by weight or less, more preferably 5% by weight or less, based on the total amount of the solvent, but as described above, it is particularly preferable not to use an aromatic hydrocarbon solvent or a halogenated hydrocarbon solvent.
The saturated hydrocarbon solvent (D) may be used alone or in combination of two or more kinds.

Preparation of Olefin Polymerization Catalyst Solution
In the process for producing an olefin polymer of this embodiment, the olefin polymerization catalyst solution may be prepared by dissolving each of the above components (A) to (B2) in a saturated hydrocarbon solvent (D).
With regard to the solubility of each of the components (A) to (B2) in the saturated hydrocarbon solvent (D), the components (A) and (B2) are often soluble, whereas the component (B1) is often insoluble.
In general, when components (A) to (B2) are dissolved (suspended) separately in a saturated hydrocarbon solvent (D) and then each is fed into a polymerization reactor, the reaction between components (A) to (B2) in the reactor is very slow because component (B1) is insoluble in the saturated hydrocarbon solvent (D), and active species may not be easily formed.
In this embodiment, a method is preferred in which the components (A) to (B2) are mixed in advance with a saturated hydrocarbon solvent (D) before being fed into a polymerization reactor to prepare an olefin polymerization catalyst solution in which each component has a specific concentration range.

When preparing the above-mentioned olefin polymerization catalyst solution, the component (A) is used in an amount of usually 10 ⁻⁷ to 10 ⁻² mol, preferably 10 ⁻⁶ to 10 ⁻³ mol, per liter of the saturated hydrocarbon solvent (D).
The component (B1) is used in an amount of usually 10 ⁻⁷ to 10 ⁻² mol, preferably 10 ⁻⁶ to 15×10 ⁻³ mol, per liter of the saturated hydrocarbon solvent (D).
Component (B2) is used in such an amount that the amount of aluminum atoms in component (B2) is usually 10 ⁻⁵ to 5 mol, preferably 10 ⁻⁴ to 2 mol, per liter of the saturated hydrocarbon solvent (D).

Furthermore, in this embodiment, in order to completely dissolve the components (A) to (B2) in the saturated hydrocarbon solvent and to carry out olefin polymerization with high activity, it is preferable that the components (A) to (B2) to be mixed in advance with the saturated hydrocarbon solvent satisfy the following requirements (i) to (iv):
(i) the amount of the transition metal complex (A) added to 1 L of the saturated hydrocarbon solvent (D) is 0.02 to 0.6 mmol;
(ii) the molar ratio ((B2)/(A)) of the aluminum atom in the compound (B2) to be added to the saturated hydrocarbon solvent (D) to the transition metal complex (A) is 33 to 5,000;
(iii) the amount of aluminum atoms in the compound (B2) added to 1 L of the saturated hydrocarbon solvent (D) is 3 to 1,000 mmol;
(iv) The molar ratio ((B)/(A)) of the compound (B1) to the transition metal complex (A) added to the saturated hydrocarbon solvent (D) is 1 to 15.
Conditions (i) to (iv) will be explained below.

<Condition (i)>
The amount of the transition metal complex (A) added is 0.02 to 0.6 mmol per 1 liter of the saturated hydrocarbon solvent (D). When the amount added is within this range, the transition metal complex (A) is completely dissolved in the saturated hydrocarbon solvent (D), and olefin polymerization can be performed with high activity, which is preferable. On the other hand, if the amount of the transition metal complex (A) added is less than 0.02 mmol, the olefin polymerization activity may be reduced. If the amount added exceeds 0.6 mmol, the transition metal complex (A) may remain undissolved, or active species resulting from the reaction of the components (A), (B1), and (B2) may precipitate. However, even in this case, the effect of this embodiment can be achieved by using the part in which the transition metal complex (A) is dissolved (supernatant) as the olefin polymerization catalyst solution.

The amount of transition metal complex (A) added is more preferably 0.03 to 0.6 mmol, even more preferably 0.05 to 0.5 mmol, and even more preferably 0.075 to 0.4 mmol.

<Condition (ii)>
The molar ratio ((B2)/(A)) of the aluminum atom in the compound (B2) to be added to the saturated hydrocarbon solvent (D) to the transition metal complex (A) is preferably 33 to 5000. If the molar ratio ((B2)/(A)) is within this range, it is preferable from the viewpoint that the active species is less likely to be deactivated.
The molar ratio ((B2)/(A)) is more preferably 50 to 2,500, even more preferably 100 to 2,000, and even more preferably 150 to 1,000.

<Condition (iii)>
The amount of compound (B2) added is preferably 3 to 1000 mmol of aluminum atoms in compound (B2) per liter of saturated hydrocarbon solvent (D). When the amount added is within this range, an amount sufficient for the activation reaction of transition metal complex (A) is ensured, and the catalytically active species generated by compound (B2) capturing impurities such as H ₂ O that are present in trace amounts in the saturated hydrocarbon solvent (D) and act as a catalyst poison can be stably maintained.
The amount of compound (B2) added is more preferably 5 to 500 mmol, even more preferably 10 to 300 mmol, and even more preferably 50 to 250 mmol.
When both the organoaluminum compound (C-1) and the organoaluminum oxy compound (C-2) are used as the compound (B2), the amount of the compound (B2) to be added is the total amount thereof.

<Condition (iv)>
The molar ratio ((B)/(A)) of the compound (B1) and the transition metal complex (A) added to the saturated hydrocarbon solvent (D) is preferably 1 to 15. As is clear from the above-mentioned reaction mechanism, the component (A) and the component (B1) react at a ratio of 1:1 in terms of the number of moles, and therefore, as long as the molar ratio is 1 or more, it can be used without any problem, particularly from the viewpoint of the polymerization activity of the olefin. On the other hand, there is no particular restriction on the upper limit of the molar ratio, but increasing the ratio too much leads to an increase in costs and may cause the compound (B1) to remain undissolved, so the upper limit is specified for the sake of convenience.
The molar ratio ((B)/(A)) is more preferably 1 to 10, even more preferably 1 to 7, and even more preferably 1.5 to 5.

The amounts of components (A) and (B2) added to the saturated hydrocarbon solvent (D) under conditions (i) and (iii) may be any amount that satisfies the conditions when preparing the olefin polymerization catalyst solution. Therefore, there is no difference in effectiveness even if the solution is diluted after preparation and then fed to the polymerization reactor.

The order in which components (A) to (B2) are added to the saturated hydrocarbon solvent (D) is not particularly limited. Specific examples include a method in which components (A) to (B2) are added simultaneously to the saturated hydrocarbon solvent (D), and a method in which components (A) to (B2) are added to the saturated hydrocarbon solvent (D) in any order. In the above addition method, components (A) to (B2) can be added to the saturated hydrocarbon solvent (D) all at once or in portions.

Among these, the preferred order of addition for preparing the catalyst solution by sequentially adding (A), (B1), and (B2) includes a method of adding components (A) and (B2) to the saturated hydrocarbon solvent (D) and then adding component (B1), and a method of adding components (B1) and (B2) to the saturated hydrocarbon solvent (D) and then adding component (A).

In this case, if components (B1) and (B2) are added to the saturated hydrocarbon solvent (D) and then component (A) is added, it depends on the degree of dissolution of the two previously added components in the saturated hydrocarbon solvent (D), but it is preferable to add component (A) 0 to 60 minutes, preferably 0 to 30 minutes, and more preferably 0 to 15 minutes after starting to mix the two previously added components in the saturated hydrocarbon solvent (D) in terms of the ease of dissolving each component in the saturated hydrocarbon solvent (D), the lifetime of the generated catalytically active species and component (B1), etc.

In addition, when component (B1) is added after components (A) and (B2) have been added to the saturated hydrocarbon solvent (D), there are no particular restrictions, but the time to add component (B1) is preferably 0 to 600 minutes, more preferably 0 to 300 minutes, and even more preferably 0 to 120 minutes after starting to mix the two previously added components into the saturated hydrocarbon solvent (D).

<Carrier (E)>
In the present invention, a carrier (E) may be used as a component of the olefin polymerization catalyst, if necessary. The carrier (E) that may be used in the present invention is an inorganic or organic compound, and is a granular or fine particle solid. Among these, the inorganic compound is preferably a porous oxide, an inorganic chloride, a clay, a clay mineral, or an ion-exchangeable layered compound.

As the porous oxide, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ and the like, or a composite or mixture containing these, such as natural or synthetic zeolite, SiO ₂ -MgO, SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -Cr ₂ O ₃ , SiO ₂ -TiO ₂ -MgO, etc. Among these, those containing SiO ₂ and/or Al ₂ O ₃ as the main component are preferable. Although the properties of such porous oxides vary depending on the type and production method, the carriers preferably used in the present invention have a particle size of preferably 0.5 to 300 μm, more preferably 1.0 to 200 μm, a specific surface area of preferably 50 to 1000 m ² /g, more preferably 100 to 700 m ² /g, and a pore volume of preferably 0.3 to 3.0 cm ³ /g. Such carriers are calcined, if necessary, preferably at 100 to 1000° C., more preferably 150 to 700° C. before use.

Examples of inorganic chlorides that can be used include _MgCl2 , _MgBr2 , _MnCl2 , and _MnBr2 . The inorganic chlorides may be used as they are, or may be used after being pulverized by a ball mill or a vibration mill. In addition, the inorganic chlorides may be dissolved in a solvent such as alcohol, and then precipitated into fine particles using a precipitating agent.

Clay is usually composed of clay minerals as the main component. In addition, ion-exchangeable layered compounds are compounds having a crystal structure in which the constituent faces are stacked in parallel with weak binding force by ionic bonds, etc., and the ions contained therein are exchangeable. Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchangeable layered compounds are not limited to natural products, and artificial synthetic products can also be used. In addition, examples of clays, clay minerals, and ion-exchangeable layered compounds include clays, clay minerals, and ionic crystalline compounds having layered crystal structures such as hexagonal close packing type, antimony type, _CdCl2 type, and _CdI2 type. Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gairome clay, allophane, hisingerite, pyrophyllite, unmo group, montmorillonite group, vermiculite, ryokudeite group, palygorskite, kaolinite, nacrite, dickite, and halloysite. Examples of ion-exchangeable layered compounds include α-Zr(HAsO ₄ ) _{2.H 2} O, α-Zr(HPO ₄ ) ₂ , α-Zr(KPO ₄ ) 2.3H ₂ O, α- _Ti (HPO ₄ ) ₂ , α-Ti(HAsO ₄ ) _{2.H 2} O, α-Sn(HPO ₄ ) 2.H ₂ O, γ-Zr(HPO ₄ ) ₂ , and γ-Ti(HPO ₄ ) _{2 .} and crystalline acid salts of polyvalent metals such as γ-Ti(NH ₄ PO ₄ ) _{2.H 2} O. It is also preferable to subject the clay and clay minerals used in the present invention to a chemical treatment. As the chemical treatment, any of surface treatments for removing impurities adhering to the surface and treatments for affecting the crystal structure of the clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment.

The ion-exchangeable layered compound may be a layered compound in which the space between layers is expanded by utilizing the ion exchangeability and exchanging the exchangeable ions between layers with other large bulky ions. Such bulky ions play a role of supporting the layered structure, and are usually called pillars. In addition, the introduction of another substance (guest compound) between layers of the layered compound in this way is called intercalation. Examples of the guest compound include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , metal alkoxides such as Ti(OR) ₄ , Zr(OR) ₄ , PO(OR) ₃ , and B(OR) ₃ (R is a hydrocarbon group, etc.), and metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , and [Fe ₃ O(OCOCH ₃ ) ₆ ] ⁺ . These compounds may be used alone or in combination of two or more. In addition, when intercalating these compounds, polymers obtained by hydrolysis and polycondensation of metal alkoxides (R is a hydrocarbon group, etc.) such as Si(OR) ₄ , Al(OR) ₃ , and Ge(OR) ₄ , and colloidal inorganic compounds such as SiO ₂ can be coexisted. In addition, examples of pillars include oxides produced by intercalating the above-mentioned metal hydroxide ions between layers and then dehydrating them with heat. Among these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, taeniolite, and synthetic mica.

As the organic compound as the carrier (E), there can be mentioned granular or fine particle solids having a particle size in the range of 0.5 to 300 μm. Specific examples include (co)polymers produced mainly from α-olefins having 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, or (co)polymers produced mainly from vinylcyclohexane and styrene, and their modified products.

<Copolymerization of ethylene and α-olefin using the above olefin polymerization catalyst>
As an example of a polymerization method using the α-olefin obtained by the method of the present invention, a method for producing an ethylene/α-olefin copolymer is introduced here. Homopolymerization or copolymerization of α-olefins can be carried out by a conventional method or in accordance with the following method.
The method for producing the ethylene/α-olefin copolymer is characterized by copolymerizing ethylene with the α-olefin obtained by the method of the present invention in the presence of the above-mentioned olefin polymerization catalyst.

Examples of α-olefins obtained by the method of the present invention include linear or branched α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and vinylcyclohexane. As the α-olefin, linear or branched α-olefins having 3 to 10 carbon atoms are preferred, and propylene, 1-butene, 1-hexene, and 1-octene are more preferred. These α-olefins can be used alone or in combination of two or more.

The polymerization can also be carried out by allowing at least one other monomer selected from a polar group-containing monomer, an aromatic vinyl compound, and a cyclic olefin to coexist in the reaction system. For a total of 100 parts by weight of ethylene and an α-olefin having 3 or more carbon atoms, the other monomer can be used in an amount of, for example, 20 parts by weight or less, preferably 10 parts by weight or less.

Examples of polar group-containing monomers include α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, and maleic anhydride, as well as metal salts such as sodium salts of these acids, α,β-unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, methyl methacrylate, and ethyl methacrylate, vinyl esters such as vinyl acetate and vinyl propionate, and unsaturated glycidyls such as glycidyl acrylate and glycidyl methacrylate.

Examples of aromatic vinyl compounds include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, methoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, p-chlorostyrene, divinylbenzene, α-methylstyrene, and allylbenzene.

Examples of cyclic olefins include cyclic olefins having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, and tetracyclododecene.

The method for producing the ethylene/α-olefin copolymer includes a method of copolymerizing ethylene with an α-olefin having 3 or more carbon atoms in the presence of the olefin polymerization catalyst, and polymerizing the copolymer in such a way that the proportion of ethylene-derived structural units is 50 mol % or more when the total proportion of structural units derived from each monomer in the polymer is taken as 100 mol %.

When ethylene is copolymerized with one olefin selected from α-olefins having 3 to 20 carbon atoms, the molar ratio of ethylene to α-olefin having 3 to 20 carbon atoms is usually ethylene:α-olefin=10:90 to 99.9:0.1, preferably ethylene:α-olefin=30:70 to 99.9:0.1, and more preferably ethylene:α-olefin=50:50 to 99.9:0.1.

The use and order of addition of each component of the olefin polymerization catalyst may be selected arbitrarily, and at least two of the components in the catalyst may be pre-contacted.
The transition metal complex (A) (hereinafter also referred to as "component (A)") is used in an amount of usually 10 ^-9 to 10 ^-1 mol, preferably 10 ^-8 to 10 ^-2 mol, per liter of reaction volume.

The organoaluminum compound (C-1) (hereinafter also referred to as "component (C-1)") is used in an amount such that the molar ratio [(B-1)/M] of component (B-1) to the transition metal atom (M) in component (A) is usually 0.01 to 50,000, preferably 0.05 to 10,000.

The organoaluminum oxy compound (C-2) (hereinafter also referred to as "component (C-2)") is used in an amount such that the molar ratio [(C-2)/M] of the aluminum atoms in component (C-2) to the transition metal atoms (M) in component (A) is usually 10 to 5000, preferably 20 to 2000.

The compound (B1) (hereinafter also referred to as "component (B1)") that reacts with the transition metal complex (A) to form an ion pair is used in an amount such that the molar ratio [(B1)/M] of component (B1) to the transition metal atom (M) in component (A) is usually 1 to 10,000, preferably 1 to 5,000.

The polymerization temperature is preferably high enough to maximize the effects of the present invention, and is usually 100°C to 300°C, with the lower limit being preferably 120°C, more preferably 130°C, and the upper limit being preferably 250°C, more preferably 200°C. In the polymerization temperature range of 100°C or higher, the solution viscosity during polymerization decreases as the temperature increases, making it easier to remove the heat of polymerization, and the resulting ethylene/α-olefin copolymer can have a high molecular weight. However, if the polymerization temperature excessively exceeds 300°C, the resulting polymer may deteriorate, which is not preferable. In addition, from the viewpoint of the properties of the ethylene/α-olefin copolymer preferably produced by the olefin polymerization of the present invention, it is possible to efficiently produce ethylene/α-olefin copolymers suitable for use in many industrial fields, such as films, in the polymerization temperature range of 100°C to 200°C.

The polymerization pressure is usually from normal pressure to 10 MPa gauge pressure (MPa-G), preferably from normal pressure to 8 MPa-G.
The polymerization reaction can be carried out in any of batch, semi-continuous and continuous systems. Furthermore, the polymerization can be carried out continuously in two or more polymerization vessels with different reaction conditions.

The molecular weight of the resulting ethylene/α-olefin copolymer can be adjusted by changing the hydrogen concentration in the polymerization system or the polymerization temperature. It can also be adjusted by the amount of component (B) used. When hydrogen is added, the appropriate amount is about 0.001 to 5000 NL per kg of the ethylene/α-olefin copolymer produced.

The polymerization solvent used in the liquid phase polymerization method is usually an inert hydrocarbon solvent, preferably a saturated hydrocarbon having a boiling point of 50°C to 200°C under normal pressure. Specific examples of the polymerization solvent include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, and alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane, with hexane, heptane, octane, decane, and cyclohexane being particularly preferred. The α-olefin itself, which is the subject of polymerization, can also be used as the polymerization solvent. Aromatic hydrocarbons such as benzene, toluene, and xylene, and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane can also be used as polymerization solvents, but their use is not preferred from the viewpoint of reducing the burden on the environment and minimizing the impact on human health.

The density of the olefin polymer obtained by the olefin polymerization process of the present invention is specified by the ASTM D1505 standard and is usually from 850 to 950 kg/m ³ , preferably from 860 to 950 kg/m ³ .
The melt flow rate MFR (ASTM D-1238, 190° C., 2.16 kg load) of the olefin polymer obtained by the olefin polymerization method of the present invention is usually 0.01 to 200 g/10 min, preferably 0.05 to 100 g/10 min. If the MFR is within the above range, it is preferable in terms of excellent moldability.

The ethylene-derived structural units in the ethylene/α-olefin copolymer obtained by the present invention are usually 99.9 to 50 mol%, preferably 99.9 to 65 mol%, and more preferably 99.7 to 70 mol%, and the α-olefin-derived structural units are 50 mol% to 0.1 mol%, preferably 35 mol% to 0.1 mol%, and more preferably 30 mol% to 0.3 mol%. However, the total of the ethylene-derived structural units and the α-olefin-derived structural units is 100 mol%.

In the ethylene/α-olefin copolymer obtained by the present invention, the amount of vinyl, vinylidene, di-substituted olefin, and tri-substituted olefin double bonds in the molecular chain is preferably less than 0.2, more preferably less than 0.1 per 1000 carbons. The lower limit of each is preferably 0 per 1000 carbons. If the amount of double bonds in the molecular chain is within this range, crosslinking and scission of the polymer molecular chain during heat molding are suppressed, and fluctuations in MFR and scorching during molding and processing are less likely to occur, and deterioration during use under heated conditions can be suppressed, which is preferable.

Example 1
Polymerization of ethylene and 1-butene was carried out using an apparatus (see FIG. 1 ) equipped with a solvent feed line, a raw material gas feed line, a catalyst feed line, and a content withdrawal line in a 1.0 L pressure-resistant reactor equipped with a stirrer and equipped with a temperature-controllable jacket.
In this case, 1-butene was passed through a column packed with 500 g of Zeorum (registered trademark) F-9 manufactured by Tosoh Corporation at a rate of LHSV of 3.0/hour, and then through a column packed with 500 g of alumina (trade name: Selexsorb COS) manufactured by BASF (maintained at a temperature of 25° C.), and then supplied to the polymerization reactor.
The polymerization conditions were as follows:
Polymerization temperature: 115°C
Hexane: 2 L/hour Hafnocene (*1): 0.8 μmol/hour Boron-based cocatalyst (*2): 4.0 μmol/hour Triisobutylaluminum: 500 μmol/hour Ethylene: 300 g/hour 1-butene: 500 mL/hour Hydrogen: 2 L/hour Pressure: 2.5 MPaG
Amount of polymerization: 216 g/hour The obtained polymer had an MFR of 6.9 g/10 min and a density of 871 kg/ ^m3 .
*1 Hafnocene: Diphenylsilylene (η ⁵ cyclopentadienyl) (η ⁵ 3,6-di-t-butylfluorenyl) hafnium dichloride *2 Boron-based cocatalyst: Triphenylcarbenium tetrakis (pentafluorophenyl) borate

Comparative Example 1
Ethylene polymerization was carried out in the same manner as in Example 1, except that the column through which 1-butene was passed was a column packed with 1,000 g of Zeorum® F-9 manufactured by Tosoh Corporation.
The obtained polymer had an MFR of 6.3 g/10 min and a density of 869 kg/m ^{3 ,} which were similar to those of Example 1. However, the polymerization amount was 11 g/hour, and the activity was poor.

Example 2
Propylene was used in place of 1-butene, and the polymerization reaction was carried out in the same manner as in Example 1. The results are given below.
Polymerization temperature: 115°C
Hexane: 2 L/hour Metallocene: 0.8 μmol/hour Boron-based cocatalyst: 4.0 μmol/hour Triisobutylaluminum: 500 μmol/hour Ethylene: 100 g/hour Propylene: 600 mL/hour Hydrogen: 1 L/hour Pressure: 2.5 MPaG
Amount of polymerization: 167 g/hour The obtained polymer had an MFR of 5.6 g/10 min and a density of 863 kg/m ³ .

Comparative Example 2
Ethylene polymerization was carried out in the same manner as in Example 2, except that the column through which propylene was passed was a column packed with 1,000 g of Zeorum (registered trademark) F-9 manufactured by Tosoh Corporation. The polymer obtained had an MFR of 6.7 g/10 min and a density of 863 kg/ ^m3, which were comparable to those of Example 2, but the polymerization amount was 3 g/hour, and the activity was poor.

Claims (7)

A process for producing an α-olefin using an olefin polymerization catalyst containing the following transition metal complex (3), which comprises contacting an α-olefin with a porous zeolite and porous alumina under the following conditions (I) and (II):
(I) The weight ratio of the porous zeolite to the porous alumina is in the range of 0.1 to 10.
(II) An α-olefin is contacted with a porous zeolite, and then the α-olefin is contacted with porous alumina.
The transition metal complex (3) is a compound represented by the following general formula [A3].

In formula [A3], R ^b1 , R ^b2 , R ^b3 , R ^b4 , R ^b5 , R ^b6 , R ^b7 , R ^b8 , R ^b9 , R ^b10 , R ^b11 , R ^b12 , R ^b13 and R ^b14 each independently represent a hydrogen atom, a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, any two of the substituents from R ^b1 to R ^b4 may be bonded to each other to form a ring, any two of the substituents from R ^b5 to R ^b12 may be bonded to each other to form a ring, R ^b13 and R ^b14 may be bonded to each other to form a ring,
Yb is a carbon atom, a silicon atom, a germanium atom or a tin atom ^;
Mb is a Group 4 transition metal ^;
Qj is a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordinating with a lone electron pair, and j is an integer of 1 to 4 . The method for producing α-olefins for polymerization according to claim 1, in which the porous zeolite and the porous alumina are in contact with a hydrocarbon compound selected from saturated hydrocarbon compounds and aryl alkyl compounds. The method for producing α-olefins for polymerization according to claim 2, wherein the boiling point of the hydrocarbon compound is in the range of -60°C to 40°C. The method for producing α-olefins for polymerization according to any one of claims 1 to 3, wherein the conditions for supplying and contacting the α-olefins to the porous zeolite and the porous alumina are a liquid hourly space velocity (LHSV) of 0.1 to 10/hr. The method for producing α-olefins for polymerization according to any one of claims 1 to 4, wherein the contact temperature between the α-olefins, the porous zeolite, and the porous alumina is in the range of -10°C to 50°C. The process according to any one of claims 1 to 5, wherein the α-olefin is a linear or branched olefin having 3 to 10 carbon atoms. The method according to any one of claims 1 to 6, wherein the α-olefin is at least one selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene.

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