JP2021147477A - Production method of olefin polymer - Google Patents

Abstract

To provide a production method of an olefin polymer capable of stably producing an intended polymer, even when a plurality of kinds of polymers is produced, by switching a plurality of kinds of transition metal complex.SOLUTION: There is provided a production method of an olefin polymer using an olefin polymer device comprising: a reactor; and a heat exchanger for performing heat exchange of a gaseous substance generated in the reactor, and the method comprises: a step for producing an olefin polymer P in presence of an olefin polymerization catalyst including (A) a transition metal complex (A) and an organic metal compound (B) including a group 13 metal in a periodic table; a deactivating step for, during execution or after execution of the production step, for removing the transition metal complex (A) existing in a heat exchanger, or deactivating polymerization activity thereof, supplying an organic compound (H) into the heat exchanger, the organic compound H including a hetero atom.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for producing an olefin polymer.

As a catalyst system capable of producing an olefin polymer, a catalyst system in which a metallocene compound which is a transition metal compound such as zirconocene or hafnocent and an organic aluminum oxy compound are combined, or a metallocene compound and N, N-dimethylanilinium tetrakis (penta) Many catalytic systems combining a metallocene compound and a compound forming an ion pair, such as fluorophenyl) borate, have already been reported (see, for example, Patent Documents 1 to 4).

Since the behavior of olefin polymerization of these catalyst compounds may differ depending on their structure, in the case of a multi-product production plant that produces a plurality of types of olefin polymers, the type and brand (production type) of the olefin polymer to be produced may be used. There are cases where a plurality of types of the above transition metal compounds are used properly. In other words, when changing the type or brand of polymer to be produced, the polymerization catalyst used may also be changed.

International Publication No. 01/027124 International Publication No. 2004/029062 Japanese Unexamined Patent Publication No. 2004-175707 International Publication No. 2014/050817

Usually, when switching a brand to be manufactured or the like, a technique for switching to an environment suitable for the brand to be manufactured in the apparatus is known mainly by an oil run process. However, when the inventors switch and use a plurality of types of transition metal complexes such as metallocene compounds to sequentially produce a plurality of types of polymers, a phenomenon may occur in which nonstandard products are produced irregularly. I noticed. It has also been confirmed that such a phenomenon does not occur or is rare in a manufacturing plant using only one kind of the metallocene compound. It has also become clear that this problem cannot be solved by ordinary improvement methods such as extending the oil run time.

In view of the above problems, the present invention provides an olefin polymer capable of stably producing the desired plurality of types of polymers even when a plurality of types of transition metal complexes are switched to produce a plurality of types of polymers. It is an object of the present invention to provide a manufacturing method.

The present inventors have made diligent studies to solve the above problems. As a result, it was discovered that a part of the olefin polymerization catalyst containing the transition metal complex such as a metallocene compound was mainly attached to the heat exchanger in addition to the reactor in the series of production equipment. Usually, the olefin polymerization catalyst moves together with the produced polymer as it proceeds from the reactor to the polymer separation step and the drying step. Therefore, it is considered that a part of the polymerization catalyst that moved together with the polymer adhered to the inner wall surface of the heat exchanger. Further, it has been found that the adhered polymerization catalyst may be relatively strongly adhered to the inner surface of a heat exchanger or the like as the polymer is purified over time, and thus it is difficult to remove it by an oil run or the like. From these results, it is conceivable that at least a part of the polymerization catalyst adhering to the heat exchanger falls off from the heat exchanger irregularly or constantly, and returns to the reactor. Alternatively, when unreacted gas is circulated and used, it is conceivable that the metallocene compound may also be circulated. In this way, when the polymerization catalyst adhering to the heat exchanger is transferred to the reactor by backflow or circulation, the metallocene compound mainly used at that time is different from the above-mentioned backflow or circulating metallocene compound. It was expected that it would end up. In this case, since a polymer derived from both metallocene compounds is produced, it is considered that a nonstandard polymer may be given.

From these findings, it was found that the above-mentioned problems can be solved by adding a step of surely removing or inactivating a polymerization catalyst containing a transition metal complex such as a metallocene compound existing in a heat exchanger to a manufacturing step, and the present invention has been made. Has been completed.

That is, the present invention has the following configurations [1] to [7].
A method for producing an olefin polymer using an olefin polymer apparatus having a reactor and a heat exchanger for exchanging heat of a gaseous substance generated by the reactor.
A production process for producing an olefin polymer (P) in the presence of an olefin polymerization catalyst containing a transition metal complex (A) and an organic metal compound (B) containing a Group 13 metal in the periodic table.
An organic substance containing a heteroatom in the heat exchanger for the purpose of removing the transition metal complex (A) existing inside the heat exchanger or eliminating its polymerization activity during or after the execution of the manufacturing process. Deactivation step to supply compound (H),
A method for producing an olefin polymer, which comprises.
[2] In the deactivation step, during the execution of the manufacturing step, the hetero is continuously supplied to the heat exchanger at a supply amount corresponding to the usage amount of the transition metal complex (A) used in the manufacturing step. The production method according to the above [1], which supplies an organic compound (H) containing an atom.
[3] The production according to the above [1] or [2], wherein the organic compound (H) is a compound having 1 to 5 carbon atoms containing a group 15 element or a group 16 element in the periodic table as a heteroatom. Method.
[4] The deactivation step is described in any one of [1] to [3] above, wherein the organic compound (H) is supplied in the form of gas or mist to the upstream side of the gas flow of the heat exchanger. Manufacturing method.
[5] The production method according to any one of [1] to [4], wherein the deactivating step supplies the organic compound (H) together with an inert solvent that does not contribute to the polymerization reaction.
[6] The production method according to any one of [1] to [5] above, wherein the transition metal complex (A) is a metallocene compound containing zirconium, hafnium or titanium.
[7] The production method according to any one of [1] to [6] above, wherein the transition metal complex (A) is at least one metallocene compound selected from non-crosslinked metallocene compounds and crosslinked metallocene compounds. ..

According to the present invention, there is provided a method for producing an olefin polymer capable of stably producing a desired plurality of types of polymers even when a plurality of types of transition metal complexes are switched to produce a plurality of types of polymers. can do.
That is, according to the present invention, a nonstandard polymer is generated for a long period of time simply by washing the heat exchanger with a heteroatom-containing compound such as alcohol at the stage of switching the production of the polymer. It is possible to stably produce a desired polymer without doing so. This is useful not only from an economic point of view but also from the viewpoint of environmental problems such as energy and resources, and has a great influence on the industry of the present invention.

It is a block diagram of the manufacturing apparatus of the olefin polymer in one Embodiment of this invention.

An embodiment of the present invention is an olefin polymerization apparatus having, for example, as shown in FIG. 1, a reactor (reactor) and a heat exchanger (heat exchanger) for exchanging heat of a gaseous substance generated by the reactor. It is applied to the method for producing an olefin polymer using.

The feature of this embodiment is preferably heat exchange of the manufacturing apparatus used during the production of the olefin polymer (during the execution of the production process) or when the brand of the olefin polymer to be produced is switched (after the execution of the production process). It is in the process of supplying a compound having a hetero atom (organic compound (H)) such as alcohol, ketone, and amine to the vessel and bringing it into contact with the inner wall surface of the heat exchanger. This substantially removes or inactivates the transition metal complex (A) such as the metallocene compound adhering to or possibly adhering to the inside of the heat exchanger from the heat exchanger to increase the olefin polymerization ability. This is a step of preventing the transition metal complex (A) having a transition metal complex (A) from returning to the reactor and exerting a catalytic action. That is, even if the organic compound (H) is supplied to the heat exchanger to wash away the transition metal complex (A) so that it does not return to the reactor, or if the polymerization catalytic activity is deactivated and the transition metal complex (A) is returned to the reactor. Do not affect other polymerization reactions that are taking place at that time.
The organic compound (H) is a component that can be a catalyst poison for the catalyst for olefin polymerization, and is usually a component that should be removed from the system. However, in the present invention, surprisingly, the problem of the present invention can be solved by appropriately using the organic compound (H) in combination.

In the present invention, as the polymerization catalyst of the olefin polymerization reaction, a catalyst in which the transition metal complex (A) and the organic metal compound (B) containing the Group 13 metal of the periodic table are combined is used. The transition metal complex (A) typically includes metallocene compounds such as zirconium, hafnium, and titanosen, which are transition metal compounds containing zirconium, hafnium, or titanium. The organometallic compound (B) is typically represented by an organoaluminum oxy compound (hereinafter, may be referred to as “aluminoxane”), N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, or the like. Examples thereof include compounds that react with metallocene compounds to form ion pairs (hereinafter, also referred to as “ionized ionic compounds”).

Specific examples of the organic compound (H) having a heteroatom include compounds containing Group 15 or Group 16 elements of the periodic table. Specifically, it is a compound such as alcohols, ketones, and amines. Such a compound can cause the polymerization activity of the polymerization catalyst containing the transition metal complex (A) such as the metallocene compound to be lost.

Such a compound is not particularly limited as long as it has a function of inactivating the catalyst. Specifically, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, 1-hexanol, 1-octanol, 2-ethyl-1-hexanol, 1-decanol, 1- Alcohols having 1 to 20 carbon atoms such as hexadecanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, amines such as trimethylamine, triethylamine, tributylamine and diethylamine, and carboxylic acids such as acetic acid and propionic acid. It can be mentioned as a suitable example. Since the polymerization apparatus is generally made of metal, it is preferable to use a neutral compound. Specific examples include alcohols and ketones.

Among these, alcohols and ketones having 1 to 5 carbon atoms are preferable from the viewpoint of high effect and ease of removal from the heat exchanger, and alcohols having 1 to 4 carbon atoms are particularly preferable. Is. Specific examples thereof include known alcohols such as methanol, ethanol, 1-propanol, 2-propanol (also known as isopropyl alcohol), 1-butanol and 2-butanol.

The organic compound (H) can be supplied to the heat exchanger alone, or can be supplied in combination (mixed) with another inert solvent such as a hydrocarbon that does not contribute to the polymerization reaction. Examples of such an inert solvent include aliphatic hydrocarbons used for olefin polymerization described later and aromatic hydrocarbons such as toluene.

When the organic compound (H) and the inert solvent are used in combination, the preferable weight ratio of the amount used is 1/1000 to 1/10, more preferably 1/500 to 1/50, still more preferably 1/400 to 1/400. It is 1/50, particularly preferably 1/300 to 1/80.
Within such a range, the attached transition metal complex can be removed from the heat exchanger or the complex can be substantially inactivated. Further, since such an organic compound (H) may be a catalyst poison, it is preferable to remove it from the system after supplying it to the heat exchanger. , When switching the production type, it can also be done by an oil run or the like.

The temperature of the organic compound (H) supplied to the heat exchanger is not particularly limited. Considering the influence on the polymerization reaction, it is desirable to set the temperature in the same range as the polymerization temperature described later.

It is preferable to continuously supply the organic compound (H) containing a heteroatom to the heat exchanger at a supply amount corresponding to the amount of the transition metal complex (A) used in the manufacturing process.
For example, considering the case where the organic compound (H) that was not involved in the deactivation of the transition metal complex (A) invades the reaction system in the heat exchanger, the organic compound (H) is the reaction. In the system, the heteroatom of the organic compound (H) and the organic metal compound (B) are opposed to the organic metal compound (B) containing the organic aluminum compound described later and the group 13 metal of the periodic table such as the organic aluminum oxy compound. The molar ratio of the compound to the metal atom is preferably 1/5 to 1/1000, more preferably 1/10 to 1/500, and even more preferably 1/10 to 1/20. Within such a range, even if the organic compound (H) invades the reaction system, it is often possible to maintain high polymerization reactivity.

In the present embodiment, the organic compound (H) is preferably in the form of a gas or a mist and is preferably brought into contact with the heat exchanger. Specifically, for example, the organic compound (H) can be supplied in the form of gas or mist to the upstream side of the gas flow flowing into the heat exchanger. However, in that case, it is preferable that the gas flow flowing into the heat exchanger is a downward flow. This is because if the gas flow flowing from the reactor enters from the upper part of the heat exchanger, the supplied liquid organic compound (H) does not flow back into the reactor. However, if the gas flow velocity is sufficiently large, there is no possibility that the organic compound (H) will flow back, so that the gas flow direction of the heat exchanger may be an upward flow.

The timing of supplying the organic compound (H) to the heat exchanger may be during the manufacturing process in which the polymerization reaction is being carried out in the reactor (during the execution of the manufacturing process of one product), or in the manufacturing process in which the polymerization reaction is completed. It may be after the end. However, it must be supplied at least before the manufacturing process of the next product is started. When supplying during the polymerization reaction, it is continuously supplied at a predetermined ratio with respect to the amount of the transition metal complex in the reactor so as to inactivate the transition metal complex accompanying the heat exchanger. It is preferable to do so. Further, it is preferable to supply at least until the polymerization reaction is completed. Moreover, the supply may be intermittent rather than continuous.

The model of the heat exchanger is not limited. It may be a vertical type or a horizontal type. It may be a multi-tube type or a plate type. The gas flow may be a downward flow or an upward flow. However, since the organic compound (H) loses the polymerization activity of the transition metal complex (A), it is preferable to configure the organic compound (H) so that the supplied organic compound (H) does not flow back into the reactor.

In particular, when the organic compound (H) is supplied to the heat exchanger during the manufacturing process of the olefin polymer, an environment in which a gas flow having a sufficient linear velocity is provided so that the organic compound (H) does not flow back into the reactor is created. It is preferable to keep it. Alternatively, it is preferable to set the gas flow as a downward flow and supply the organic compound (H) to the upstream side of the gas flow of the heat exchanger.

The type of reactor connected to the heat exchanger is also not limited. It may be a liquid phase polymerization reactor or a gas phase polymerization reactor. It may be a continuous polymerization reactor or a batch type polymerization reactor. In the case of a liquid phase polymerization reactor, the polymerization catalyst is suspended in the solution. In the case of a gas phase polymerization reactor, a polymerization catalyst is present in the reaction layer. In any case, any device configuration in which the polymerization catalyst (transition metal complex) present in the reactor may accompany the gas phase and reach the heat exchanger is the target of the present embodiment.

The deactivation step of substantially removing or inactivating the transition metal complex such as a metallocene compound from the heat exchanger shall be applied without limitation as long as it is a manufacturing process using the transition metal complex such as a metallocene compound as a polymerization catalyst. Can be done. Hereinafter, as an example, a specific example of a process for producing an olefin polymer using a preferable metallocene compound will be shown.

[Olefin polymerization catalyst solution]
As the olefin polymerization catalyst solution used in the present embodiment, it is preferable to use the transition metal complex (A) and the organic metal compound (B) as a solution of the saturated hydrocarbon solvent (D). If the desired amount of the organometallic compound (B) cannot be dissolved in the hydrocarbon solvent (D), it is preferably used in a slurry state.
Typical examples of the organometallic compound (B) are a specific compound (B1) and a specific aluminum compound (B2) that react with the transition metal complex (A) to form an ion pair.

Hereinafter, the compounds (A), (B), (B1), and (B2) may be referred to as components (A), (B), (B1), and (B2), respectively. The olefin polymerization catalyst solution may contain other additives.

In the present embodiment, the "olefin polymerization catalyst solution" refers to a solution in which the components (A), (B), (B1), and (B2) are dissolved in a saturated hydrocarbon solvent (D). This is preferably a solution in which the components (A), (B), (B1) and (B2) added to the saturated hydrocarbon solvent (D) are completely dissolved, but the components (A) and (B) , (B1) and (B2) may be partially insoluble, and the concept includes the supernatant portion thereof.

The transition metal complex (A) is not particularly limited, and examples thereof include a transition metal complex used in a conventionally known catalyst for olefin polymerization.
Examples of the transition metal complex used in the catalyst for olefin polymerization include the following transition metal complexes (1) to (9).

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

<R ^{1 to} R ⁸ >
In the formula [A1], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently hydrogen atoms, hydrocarbon groups, halogen-containing groups, oxygen-containing groups and nitrogen, respectively. It is selected from a 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. It may be formed.
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, a t-butyl group, an n-pentyl group, a neopentyl group, and an n-hexyl group. , N-octyl group, nonyl group, dodecyl group and 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 anthrasenyl group, a phenanthryl group and a benzyl group. Examples thereof include a phenyl group, a pyrenyl group, an acenaphthyl group, a phenalenyl group, an acetylenyl 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 the formula [A1], Y is a divalent group that binds two ligands, specifically, a divalent group containing a hydrocarbon group having 1 to 20 carbon atoms and a halogen. It is a group selected from a group, a silicon-containing group, a germanium-containing group and a tin-containing group, and is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent silicon-containing group.
Examples of the divalent hydrocarbon group include an alkylene group, a substituted alkylene group and an alkylidene group, and specific examples thereof include a divalent hydrocarbon group.
Alkylene groups such as methylene, ethylene, propylene and butylene;
Isopropyridene, diethylmethylene, dipropylmethylene, diisopropylmethylene, dibutylmethylene, methylethylmethylene, methylbutylmethylene, methyl-t-butylmethylene, dihexylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, ditrill Substituted alkylene groups such as methylene, methylnaphthylmethylene, dinaphthylmethylene, 1-methylethylene, 1,2-dimethylethylene and 1-ethyl-2-methylethylene; and cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexyl Included are cycloalkylidene groups such as silidene, cycloheptylidene, bicyclo [3.3.1] nonylidene, norbornylidene, adamantilidene, tetrahydronaphthylidene and dihydroindanylidene, and alkylidene groups such as ethylidene, propylidene and butylidene. ..

As a divalent silicon-containing group,
Sirylene; as well as methyl silylene, dimethyl silylene, diisopropyl silylene, dibutyl silylene, methyl butyl silylene, methyl-t-butyl silylene, dicyclohexyl silylene, methyl cyclohexyl silylene, methylphenyl silylene, diphenyl silylene, ditril silylene, methylnaphthyl silylene, dinaphthyl Alkylylylene groups such as silylene, cyclodimethylene silylene, cyclotrimethylene silylene, cyclotetramethylene silylene, cyclopentamethylene silylene, cyclohexamethylene silylene and cycloheptamethylene silylene can be mentioned, with particular preference being a dimethylsilylene group and a dibutylsilylene. Examples thereof include a dialkylsilylene group such as a group.

<M>
In the 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 the formula [A1], X is independently 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. It is an atom or group, preferably a halogen atom or a hydrocarbon group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine, and chlorine is particularly preferable.
Specific examples of the transition metal complex (1) include the compounds listed in [0077] of JP2013-224408A.

(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 the 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 independently hydrogen atoms, respectively. Selected from hydrocarbon groups, halogen-containing groups, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups and tin-containing groups, which may be the same or different from each other. Alternatively, two adjacent groups may be connected to each other to form a ring.
Examples of the hydrocarbon group include the hydrocarbon groups listed as ^{R a1 to} R ^a8 in the above-mentioned formula [A1].
R ^{a1 to} R ^a6 and R ^{a11 to} R ^a16 are independently, preferably hydrogen atoms or hydrocarbon groups, and more preferably hydrogen atoms or alkyl groups having 1 to 20 carbon atoms.
<Y>
In the formula [A2], Y is a divalent group that binds two ligands, specifically, a divalent group containing a hydrocarbon group having 1 to 20 carbon atoms and a halogen. It is a group selected from a group, a silicon-containing group, a germanium-containing group and a tin-containing group, and is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent silicon-containing group.
Examples of these groups include divalent groups listed as Y in the above-mentioned formula [A1].
<M ^a >
In the formula [A2], ^Ma is a Group 4 transition metal, preferably Ti, Zr or Hf, more preferably Zr or Hf, and particularly preferably Zr.
<X>
In the formula [A2], X is independently 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. It is an atom or group, preferably a halogen atom or a hydrocarbon group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine, and chlorine is particularly preferable.
Specific examples of the transition metal complex (2) include the compounds listed in [0071] of JP2013-224408A.

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

<R ^b1 to R ^b14 >
Wherein ^{[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} are each independently Is a hydrogen atom, a hydrocarbon group, a hetero atom-containing hydrocarbon group or a silicon-containing group, and any two substituents from R ^{b1 to R b4} are bonded to each other to form a ring. Of 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. May be.

Examples of the hydrocarbon groups in R ^b1 to R ^b14 include one or two or more of linear hydrocarbon groups, branched hydrocarbon groups, cyclic saturated hydrocarbon groups, cyclic unsaturated hydrocarbon groups, and saturated hydrocarbon groups. A group formed by substituting a cyclic unsaturated hydrocarbon group with a cyclic unsaturated hydrocarbon group can be mentioned. The hydrocarbon group usually has 1 to 20, preferably 1 to 15, and more preferably 1 to 10.

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

Examples of the cyclic saturated hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and methylcyclohexyl group; polycyclic groups such as norbornyl group, adamantyl group and methyladamantyl group. Be done.
Examples of the cyclic unsaturated hydrocarbon group include an aryl group such as a phenyl group, a tolyl group, a naphthyl group, a biphenyl group, a phenanthryl group and an anthrasenyl group; a cycloalkenyl group such as a cyclohexenyl group; 5-bicyclo [2.2. 1] Examples thereof include a polycyclic unsaturated alicyclic group such as a hepta-2-enyl group.

Examples of the group formed by substituting one or more hydrogen atoms of the saturated hydrocarbon group with a cyclic unsaturated hydrocarbon group include a benzyl group, a cumyl group, a 1,1-diphenylethyl group and a triphenylmethyl group. Examples thereof include a group in which one or more hydrogen atoms of the alkyl group of the above are substituted with an aryl group.
Examples of the heteroatom-containing hydrocarbon group in R ^b1 to R ^b14 include an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an oxygen atom-containing hydrocarbon group such as a frill group; N-methylamino. Examples include an amino group such as a group, an N, N-dimethylamino group and an N-phenylamino group, a nitrogen atom-containing hydrocarbon group such as a pyryl group; and a sulfur atom-containing hydrocarbon group such as a thienyl group. The heteroatom-containing hydrocarbon group usually has 1 to 20, preferably 2 to 18, and more preferably 2 to 15. However, silicon-containing groups are excluded from heteroatom-containing hydrocarbon groups.
As the silicon-containing groups from R ^b1 in R ^b14, for example, trimethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, diphenylmethylsilyl group, the formula -SiR 3 _(wherein such a triphenylsilyl group, the plurality of R each Independently, it is an alkyl group or a phenyl group having 1 to 15 carbon atoms.)

Of the substituents from R ^b1 to R ^b14 , any two substituents, for example, two adjacent substituents (eg, 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)} are bond to each other to form a ring May be good. The ring formation may be present at two or more positions in the molecule.
In the present specification, examples of the ring (additional ring) formed by bonding two substituents to each other include an alicyclic ring, an aromatic ring, and a heterocycle. Specific examples thereof include a cyclohexane ring; a benzene ring; a hydrogenated benzene ring; a cyclopentene ring; a heterocycle such as a furan ring and a thiophene ring, and a hydrogenated heterocycle corresponding thereto, preferably a cyclohexane ring; a benzene ring and hydrogen. It is a benzene ring. Further, such a ring structure may further have a substituent such as an alkyl group on the ring.

R ^b5 , R ^b8 , R ^b9 and R ^b12 are preferably hydrogen atoms.
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, and 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 hetero atom-containing hydrocarbon group or a silicon-containing group, and more preferably an aryl group or a substituted aryl group (an aryl group having a hetero atom-containing hydrocarbon group or a silicon-containing group). ).

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

< ^Mb , Q, j>
In the formula [A3], M ^b is a Group 4 transition metal, preferably Ti, Zr or Hf, and more preferably Zr or Hf.
Q is a neutral ligand that can be coordinated with a halogen atom, a hydrocarbon group, an anion ligand or a lone electron pair, and when j is an integer of 2 or more, Q is selected in 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 , preferably an alkyl group such as a linear alkyl group or a branched alkyl group.
Examples of the anion ligand in Q include an alkoxy group such as methoxy and tert-butoxy; an aryloxy group such as phenoxy; a carboxylate group such as acetate and benzoate; a sulfonate group such as mesylate and tosylate; dimethylamide and diisopropylamide. , Methylanilide, diphenylamide and other amide groups.
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; tetrahydrofuran, diethyl ether, dioxane, 1,2-. Examples include ethers such as dimethoxyethane.
It is preferable that at least one 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 in the same or different combinations.

Specific examples of the transition metal complex (3) include the compounds listed on pages 29 to 43 of International Publication No. 2004/87775, and the compounds listed on pages 9 to 37 of International Publication No. 2006/25540. , The compounds listed in [0117] of International Publication No. 2015/122414, and the compounds listed in [0143] of International Publication No. 2015/122415.

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

<R ^c1 to R ^c16 >
In formula [A4], R ^c1 , R ^c2 , R ^c3 , R ^c4 , R ^c5 , R ^c6 , R ^c7 , R ^c8 , R ^c9 , R ^c10 , R ^c11 , R ^c12 , R ^c13 , R ^c14 , R ^c15. And R ^c16 are independently hydrogen atoms, hydrocarbon groups, heteroatom-containing hydrocarbon groups or silicon-containing groups, and any two substituents from R ^{c1 to R c16} are bonded to each other. It may form a ring.
Hydrocarbon radicals from R ^c1 in ^{R c16,} the hetero atom-containing hydrocarbon group and a silicon-containing group, hydrocarbon groups exemplified as ^R b1 ^{to R b14} in the above-mentioned formula [A3], heteroatom-containing hydrocarbon group and a silicon Examples include containing groups.

Of the substituents from R ^c1 to R ^c16 , two adjacent substituents (eg, 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, and Rc ⁶ and Rc ⁷ may be bonded to each other to form a ring. It may be formed, 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, and R ^c3 and R ^{c5 may be formed.} May combine with each other to form a ring. The ring formation may be present at two or more positions in the molecule.

In the present specification, examples of the ring (additional ring) formed by bonding two substituents to each other include an alicyclic ring, an aromatic ring, and a heterocycle. Specific examples thereof include a cyclohexane ring; a benzene ring; a hydrogenated benzene ring; a cyclopentene ring; a heterocycle such as a furan ring and a thiophene ring, and a hydrogenated heterocycle corresponding thereto, preferably a cyclohexane ring; a benzene ring and hydrogen. It is a benzene ring. Further, such a ring structure may further have a substituent such as an alkyl group on the ring.

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

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, which are more preferable. Is a substituent in which the carbon having a free atomic value such as tert-butyl group, tert-pentyl group, 1-methylcyclohexyl group, 1-adamantyl group is a tertiary carbon, and particularly preferably 1-adamantyl group, tert-. It is a butyl group.
R ^c4 is one of the preferable forms when the transition metal complex (4) is represented by the following general formula [A4'], which is a hydrogen atom.

In this case, the transition metal complex (4) is a mirror image isomer of the transition metal complex represented by the general formula [A4'], for example, the general formula [A4''], as long as the gist of the present invention is not deviated. Includes transition metal complexes represented by.

In notation formula [A4 '] and [A4''], it is assumed that M ^c Q _j portion to the paper before, the bridge portion is present in the depth of the page surface. ^{That is, in these transition metal complexes, a hydrogen atom (R c4} ) facing the central metal side exists at the α-position of the cyclopentadiene ring (based on the carbon atom substituted at the crosslinked site).
On the other hand, in the general formula [A4] described above, whether M ^c Q _j moiety and bridges are present in the paper before, either present in the depth of the page surface is not specified. That is, the transition metal compound (A4) represented by the general formula [A4] includes a transition metal compound having a specific structure and an enantiomer thereof.

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, with R ^c4 and R ^c5 being hydrogen atoms or hydrocarbons. more preferably a group, more preferably R ⁵ is a linear alkyl group, alkyl groups such as branched alkyl group, a cycloalkyl group or cycloalkenyl group, is an alkyl group having 1 to 10 carbon atoms Is particularly preferred. Further, from the viewpoint of synthesis, ^{it is one of the preferable forms that both R c4} and R ^c5 are alkyl groups, and an alkyl group having 1 to 10 carbon atoms is particularly preferable. Similarly, from the viewpoint of synthesis, it is also preferable that ^{R c6} and R ^{c7 are hydrogen atoms.} It is more preferable that R ^c5 and R ^c7 are bonded to each other to form a ring, and it is particularly preferable that 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 has a structure obtained from a known fluorene derivative. R ^c9 , R ^c12 , R ^c13 and R ^c16 are preferably hydrogen atoms.
R ^c10 , R ^c11 , R ^c14 and R ^c15 are preferably hydrogen atoms, hydrocarbon groups, oxygen atom-containing hydrocarbon groups or nitrogen atom-containing hydrocarbon groups, more preferably hydrocarbon groups, and even more preferably. It is a hydrocarbon group having 1 to 20 carbon atoms, for example, 2,7-di-tert-butylfluorenyl group, 3,6-di-tert-butylfluorenyl group, 2,7-diphenyl-3, Examples thereof include a 6-di-tert-butylfluorenyl group, and a 2,7-di-tert-butylfluorenyl group is particularly preferable.

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 group, dibenzofluorenyl group, octahydrodibenzofluorenyl group, 1,1,4,4,7,7,10,10-octamethyl-2. , 3,4,7,8,9,10,12-octahydro-1H-dibenzo [b, h] fluorenyl group, 1,1,3,3,6,6,8,8-octamethyl-2,3 6,7,8,10-Hexahydro-1H-dicyclopenta [b, h] fluorenyl group, 1', 1', 3', 6', 8', 8'-hexamethyl-1'H, 8'H-dicyclopenta [B, h] Fluolenyl groups are mentioned, and particularly preferably 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-. 1H-dibenzo [b, h] fluorenyl group can be mentioned.

< ^Mc , Q, j>
In the 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 neutral ligand that can be coordinated with a halogen atom, a hydrocarbon group, an anion ligand or a lone electron pair.
The halogen atom, hydrocarbon group, anionic ligand and lone electron pair in Q can be coordinated with the halogen atom, hydrocarbon group, anionic ligand and lone pair of neutral ligands in the above formula [A3]. Examples thereof include neutral ligands that can be coordinated with an electron pair.
j is an integer of 1 to 4, preferably 2. When j is an integer of 2 or more, Q may be selected in the same or different combinations.

Specific examples of the transition metal complex (4) are listed in the compounds listed on pages 11 to 15 of International Publication No. 2006/68308, and [0075]-[0086] of International Publication No. 2014/50816. Examples thereof include the compounds listed in [0072]-[0084] of JP-A-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] described in Japanese Patent Application Laid-Open No. 2000-516228.

(Wherein, M ^A is 1 3-13 of the Periodic Table of the Elements, a metal from the lanthanide or actinide, it + 2, located in the +3 or +4 formal oxidation state, and 5 substituents, namely in _{^{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 It is π-bonded to one cyclopentadienyl (Cp) group, which is a cyclic delocalized π-binding ligand group having (is), and T is a Cp ring when k is 1 or 2. and a heteroatom which is covalently bonded to ^{R B,} further when k is 0, T is F, Cl, Br or I; when k is 1, T is O or S, or N or P There, and R ^B has a double bond to T; when k is 2, T is N or P, further R ^B is, independently at each occurrence, is hydrogen, or hydrocarbyl, Hydrocarbylsilyl, halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilylhydrocarbyl, hydrocarbylamino, di (hydrocarbyl) amino, hydrocarbyloxy, a group having 1-80 non-hydrogen atoms, each R ^B optionally has 1-20 non-hydrogen atoms independently in each case hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di (hydrocarbylsilyl) amino, hydrocarbylamino, di (hydrocarbyl) amino, di (hydrocarbyl) Phosphino, hydrocarbyl sulfide, hydrocarbyl, halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl or hydrocarbylsilyl-substituted with one or more groups that are non-interfering groups with 1-20 non-hydrogen atoms. ^{Each of RA} , ^RC and ^RD may be hydrogen or hydrocarbyl, halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl, hydrocarbylsilylhydrocarbyl 1 ^A group having -80 non-hydrogen atoms, each of RA, ^RC and R ^D optionally independently having 1-20 non-hydrogen atoms in each of the hydrocarbyloxy, hy. Drocarbylsiloxy, hydrocarbylsilylamino, di (hydrocarbylsilyl) amino, hydrocarbylamino, di (hydrocarbyl) amino, di (hydrocarbyl) phosphino, hydrocarbylsulfide, hydrocarbyl, halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, or a hydrocarbylsilyl or hydrocarbylsilyl hydrocarbyl, or 1-20 amino may be substituted by one or more groups which are non-interfering groups bearing a non-hydrogen atoms; or optionally, R ^{a, R B,} R ^{Two or more of C} and R ^D covalently bond with 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 fused rings or rings. The ring system is unsubstituted or in each case independently having 1-20 non-hydrogen atoms, hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di (hydrocarbylsilyl) amino, hydrocarbylamino, di (hydrocarbyl). ) Amino, di (hydrocarbyl) phosphino, hydrocarbyl sulfide, hydrocarbyl, halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl, or a non-interfering group with 1-20 non-hydrogen atoms Substituted by one or more groups;
Z ^A is a divalent group bonded to both Cp and M ^A through the coupling sigma, Z ^A is a Group 14 members of the Periodic Table of the or element is boron, and further nitrogen, Consists of phosphorus, sulfur or oxygen;
X ^A is an anionic or dianionic ligand group having up to 60 atoms, excluding the group of ligands that are cyclic delocalized π-bonded ligand groups;
X A ^'is an Lewis base coordination bond compound neutral with in each case independently 20 or fewer atoms;
p is 0, 1 or 2, and 2 less than formal oxidation state of ^{M A} when ^{X A} is an anionic ligand; when ^{X A} is a dianionic ligand, p is 1; 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 Japanese Patent Application Laid-Open No. 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) periodic table group 4 metal and aluminum compound corresponding to the following general formula [A6] described in JP-A-2002-522551.

(In the equation, L'is a π-bonded group,
M ^B is a periodic table Group 4 metal,
J is nitrogen or phosphorus,
Z ^B is a divalent bridging bond and
R'is an inert monovalent ligand,
r is 1 or 2
X ^B is a Lewis basic ligand group capable of independently forming a μ-bridge binding ligand group in each case, two X ^B groups may optionally bind together, and A'is each. In the case of independently, it is an aluminum-containing Lewis acid compound having up to 50 atoms excluding hydrogen, and the compound forms an adduct with a metal complex by a μ-bridge bond group, and optionally two A'groups. May bind together to form 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-A-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 formulas [A7-1], [A7-2] or [A7-3] described in JP-A-2003-501433.

(Wherein, M D is a metal selected from one of 3-13 aromatic lanthanide or actinide of the periodic table;
Z D is a divalent group having boron, or a member of Group 14 of the Periodic Table of the Elements, and having nitrogen, phosphorus, sulfur or oxygen;
X D is an anionic ligand group having 60 or less of atoms without inclusion of hydrogen, optionally two X groups form a divalent anionic ligand group together;
X D 'is a neutral Lewis base ligands having up to 20 atoms in each case independently;
p1 is a number of 0 to 5, 2 less than formal oxidation state of M D;
q1 is 0, 1 or 2;
E is silicon or carbon;
RA1 is hydrogen or RB1 independently in each case;
Or R B1 is BR C1 2, or a hydrocarbyl, hydrocarbylsilyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, di (hydrocarbyl) amino-substituted hydrocarbyl, BR C1 2 - substituted hydrocarbyl, hydrocarbylsilyl hydrocarbyl, di (hydrocarbyl) amino, hydrocarbadiyl amino, or a hydrocarbyloxy group, each R B1 has 1 to 18 atoms without inclusion of hydrogen, and optionally the two R B1 groups one or more fused rings covalently bonded May be formed;
RC1 is independently hydrocarbyl, halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, dihydrocarbylamino-substituted hydrocarbyl, hydrocarbaziylamino-substituted hydrocarbyl, hydrocarbylsilyl, hydrocarbylsilylhydrocarbyl, or R D ;
R D1 each independently has 1 to 20 atoms of dihydrocarbylamino or hydrocarbyloxy groups without the inclusion of hydrogen, and optionally two R D1 groups on a single boron together. It forms a boron-bound hydrocarbaziylamino-, hydrocarbaziyloxy-, hydrocarbaziyldiamino-, or hydrocarbaziyloxy-group with both valences;
However the R A1 in the case of at least one BR C1 2, BR C1 2 - substituted hydrocarbyl group, and with them are selected from the derivatives combined, at least one R C1 is R D1;
R F is independently hydrogen each case, or a silyl, hydrocarbyl, a hydrocarbyloxy and group selected from combinations thereof, said R F is has 30 or fewer carbon or silicon atoms; and x is 1 to 8 There or optionally (R F 2 E) x is -T'Z D '- or - (T'Z D') 2 - a, where at T 'is boron or aluminum in each case independently , And Z D' in each case independently

Is;
R ^d1 is each independently hydrogen, hydrocarbyl group, trihydrocarbylsilyl group, or trihydrocarbylsilylhydrocarbyl group, the R ^d1 group having 20 or less atoms without carbon inclusion, and two of these. The R ^d1 groups may optionally be 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 [0030] of Japanese Patent Application Laid-Open 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].

< ^Me >
Wherein [A8], M ^e is the periodic table 4,5 transition metal atom, preferably a Group 4 transition metal atoms. Specifically, it is titanium, zirconium, hafnium, vanadium, niobium, tantalum, etc., more preferably titanium, zirconium, hafnium, and particularly preferably titanium or zirconium.
Dotted line connecting the N and M ^e in equation [A8] is typically indicate that N is coordinated to M ^e, but may not be also be coordinated in the present invention.
<M1>
In the formula [A8], m1 represents an integer of 1 to 4, preferably an integer of 2 to 4, and more preferably 2.

<R ^{e1 to} R ^e5 >
In the formula [A8], R ^{e1 to} R ^e5 may be the same or different from each other, and may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, and a boron-containing group. , Sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group, and two or more of these may be linked to each other to form a ring.
Examples of the halogen atom 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-mentioned formula [A3], and in particular, the hydrocarbon groups.
1 to 30 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group, n-hexyl group, 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, and an anthrasenyl group;
These aryl groups are provided with a halogen atom, an alkyl group or an alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20, and a substituent such as an aryl group or an aryloxy group having 6 to 30 carbon atoms, preferably 6 to 20. Substituted aryl groups substituted with 1 to 5 are preferable.

^{Re 1} is a linear or branched hydrocarbon group having 1 to 20 carbon atoms and 3 to 20 carbon atoms from the viewpoint of olefin polymerization catalytic activity and giving a high molecular weight olefin polymer. A group selected from an alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable.

Heterocyclic compound residues include nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine, oxygen-containing compounds such as furan and pyran, sulfur-containing compounds such as thiophene, and heterocyclic compounds thereof. Examples of the compound residue include an alkyl group having 1 to 30 carbon atoms, preferably 1 to 20, and a group further substituted with a substituent such as an alkoxy group.
Examples of the oxygen-containing group include an alcohol 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 acid anhydride group.
Examples of the nitrogen-containing group include an amino group, an imino group, an amide group, an imide 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. Examples include those that have become ammonium salts.
Examples of the boron-containing group include a bolangyl group, a bolantriyl 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 thiosian acid ester group, an isothian acid ester group, a sulfone ester group, a sulfonamide group and a thiocarboxyl group. Examples thereof include a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group and a sulfenyl group.
Examples of the phosphorus-containing group include a phosphide group, a phosphoryl group, a thiophosphoryl group, a phosphato group and the like.
Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, and more specifically, a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, and a diethylsilyl group. , Triethylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-t-butylsilyl group, dimethyl (pentafluorophenyl) silyl group and the like. Examples of the hydrocarbon-substituted siloxy group include a trimethylsiloxy group.
Examples of the germanium-containing group and the tin-containing group include a group in which the silicon of the silicon-containing group is replaced with germanium or tin.

<R ^e6 >
In the formula [A8], ^Re6 is a hydrocarbon group having 1 to 4 carbon atoms consisting of only hydrogen atoms and primary or secondary carbons, an aliphatic hydrocarbon group having 4 or more carbon atoms, an aryl group substituted alkyl group, and a simple substance. It is selected from cyclic or bicyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups and halogen atoms. Among these, from the viewpoint of olefin polymerization catalytic activity, from the viewpoint of providing a high molecular weight olefin polymer, and from the viewpoint of hydrogen resistance at the time of polymerization, an aliphatic hydrocarbon group having 4 or more carbon atoms, an aryl group-substituted alkyl group, and the like. It is preferably a group selected from monocyclic or bicyclic alicyclic hydrocarbon groups and aromatic hydrocarbon groups, more preferably branched hydrocarbon groups such as t-butyl groups; benzyl group, 1-. Aryl-substituted alkyl groups such as methyl-1-phenylethyl group (cumyl group), 1-methyl-1,1-diphenylethyl group, 1,1,1-triphenylmethyl group (trityl group); hydrocarbons at the 1-position Examples thereof include an alicyclic group having 6 to 15 carbon atoms such as a cyclohexyl group having a group, an adamantyl group, a norbornyl group, and a tetracyclododecyl group, or an alicyclic group hydrocarbon group having a compound ring structure.
<N1>
In the formula [A8], n is a number satisfying a valence of ^{M e.}

<X ^e >
In the formula [A8], X ^e is 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, and a heterocycle. Formula A compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, the ^{plurality of groups represented by X e} may be the same or different from each other, and in X ^e . The plurality of groups shown 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 ^{above explanations of Re 1 to} Re 5. Of these, a halogen atom or a hydrocarbon group is preferable.

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

<M ^f >
In the formula [A9], M ^f represents a transition metal atom of Group 4 to 11 of the periodic table, specifically titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, manganese, iron, cobalt, nickel, palladium. Such as, preferably a metal atom of groups 4 to 7, 10; specifically, titanium, zirconium, hafnium, vanadium, chromium, manganese, nickel, and more preferably titanium, nickel.
^{The dotted line connecting N and M f} in the formula [A9] generally indicates that N is ^{coordinated to M f} , but in the present invention, it may or may not be coordinated.
<M2>
In the formula [A9], m2 represents an integer of 1 to 4, and is preferably 2.

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

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

<R ^f6 >
In the formula [A9], R ^f6 is a hydrocarbon group having 1 to 4 carbon atoms consisting of only hydrogen atoms and primary or secondary carbons, an aliphatic hydrocarbon group having 5 or more carbon atoms, an aryl group substituted alkyl group, and a simple substance. It is selected from cyclic or bicyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups and halogen atoms.
R ^f6 is an aryl group having 6 to 30, preferably 6 to 20 carbon atoms such as phenyl, benzyl, naphthyl, and anthranil;
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, neopentyl;
Cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2,6-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, etc. have 3 to 30 carbon atoms. , Preferably 3 to 20 cyclic saturated hydrocarbon groups, and R ^f6 is an aromatic group such as phenyl, benzyl, naphthyl, and 3,5-difluorophenyl, 3,5 in which these hydrogen atoms are substituted. -Bistrifluoromethylphenyl and the like are particularly preferred.

<N2>
In the formula [A9], n2 is a ^{number satisfying the valence of Mf} , specifically 0 to 5, preferably 1 to 4, and more preferably 2.
<X ^f >
In the formula [A9], X ^f is 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, and a heterocycle. Formula Indicates a compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n2 is 2 or more, the ^{plurality of groups represented by X f} may be the same or different from each other, and are represented by X. The plurality of groups 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 ^{above description of R f 1 to} R ^{f 5.}
Specific examples of the transition metal complex (9) include the compounds listed in [0079] to [0088] of JP2011-231291.
The transition metal complex is not limited to the transition metal complexes (1) to (9) described above, and other than these, for example, Japanese Patent Application Laid-Open No. 2008-163140 [0007] and International Publication No. 2010/50256. [0030] to [0051], Japanese Patent Application Laid-Open No. 2010-150246 [0016], International Publication No. 2013/184579 [0133], Japanese Patent Application Laid-Open No. 2013-534934 [0006], Japanese Patent Application Laid-Open No. 2009-534517. [0001], and the transition metal complexes described in [0009] to [0017] of JP-A-2001-516767 can be exemplified.

[Organometallic compound (B)]
Examples of the organometallic compound (B) used in the present invention include a compound (B1) that mainly reacts with a transition metal complex (A) to form an ion pair and an organometallic compound (B2) that mainly contains an aluminum atom. .. Hereinafter, these compounds will be described.
<Compound (B1) that reacts with the transition metal complex (A) to form an ion pair>
In the present 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].

Wherein [B1], ^{R e +} represents a carbenium ^cation, R f to R ⁱ each independently a halogenated hydrocarbon group or a hydrocarbon group having 1 to 20 carbon atoms having 1 to 20 carbon atoms. In the present embodiment, the carbenium cation represented by Re ⁺ is specifically a tricoordinated carbon cation having a structure represented by ^{R j} C ^+. Here, the R ^j may be different each even are three identical, it is possible to take various substituents, in general, from 1 to 30 carbon atoms, preferably 1 to 20, further Preferred 1 to 10 linear or branched aliphatic hydrocarbon groups; 3 to 30, preferably 3 to 20, more preferably 3 to 10 alicyclic hydrocarbon groups; 6 carbon atoms. -30, preferably 6-20, more preferably 6-10 aromatic hydrocarbon groups. Further, in the above-mentioned various hydrocarbon groups, at least one hydrogen atom may be substituted with another hydrocarbon group.

Specific examples of the carbocation cation include triphenylcarbenium cations, tri-substituted carbocation cations such as triphenyl (methylphenyl) carbocation cation, and tris (dimethylphenyl) carbocation cation, which are high even at a wide range of polymerization temperatures. A triphenylcarbenium cation is preferable from the viewpoint of exhibiting polymerization activity and being easily available industrially.

In general, examples of the ionized ionic compound that can be used as a component of the catalyst for olefin polymerization include compounds having an anilinium cation in addition to the compound having a carbenium cation. However, the ionized ionic compound having an anilinium cation is completely contained in a saturated hydrocarbon solvent in the case of a composition composed of a metallocene compound, an ionized ionic compound and an aluminum compound contained in the olefin polymerization catalyst used in the present embodiment. It was found to be difficult to dissolve in.

On the other hand, in the case of an ionized ionic compound having a carbenium cation, as described later, it is relatively rich in reactivity with the following compound (B2), so that it is a saturated hydrocarbon solvent within a specific concentration range. However, it became possible to dissolve it.

Wherein the substituents represented by R ^f to R ^i, the hydrocarbon group having 1 to 20 carbon atoms, for example, include an aromatic hydrocarbon group having 6 to 20 carbon atoms, an unsubstituted aryl group And substituted aryl groups are preferred. Examples of the substituent in the aryl group include a hydrocarbon group.

Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include a halogenated aromatic hydrocarbon group having 6 to 20 carbon atoms, and an aryl halide group is preferable. Examples of the substituent in the aryl group include a halogenated hydrocarbon group and a halogen atom.

Specific embodiments of the hydrocarbon group and the halogenated hydrocarbon group include, for example, 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, and 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.
The component (B1) includes triphenylcarbenium tetrakis (pentafluorophenyl) from the viewpoints of reactivity with the following compound (B2), high solubility in a saturated hydrocarbon solvent, and industrial availability. ) Volate is particularly preferred.

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

<< Organoaluminium compound (C-1) >>
Examples of the organoaluminum compound (C-1) include an organoaluminum compound represented by the general formula [C2] and [C3], and a complex of a metal of Group 1 of the periodic table represented by the general formula [C4] and aluminum. Alkylated products can be mentioned.
^{_{R a m3 Al (OR b)}} n3 X g p2 ··· [C2]
In the formula [C2], ^Ra and R ^b independently represent hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X ^g represents a halogen atom, and m3 is 0 <m3 ≦ 3, n3 is a number of 0 ≦ n3 <3, p2 is a number of 0 ≦ p2 <3, and m3 + n3 + p2 = 3.

Examples of the organoaluminum compound represented by the general formula [C2] include tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, trin-butylaluminum, trihexylaluminum, and trioctylaluminum;
Tri-branched alkylaluminum such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri2-methylbutylaluminum, tri3-methylhexylaluminum, tri2-ethylhexylaluminum;
Tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; triaryl aluminum such as triphenyl aluminum and tritryl aluminum;
Isoprenyl aluminum represented by the general formula (i-C ₄ H ₉ ) _x1 Al _y (C ₅ H ₁₀ ) _z (in the formula, x1, y and z are positive numbers and z≤2x1). Alkenyl aluminum such as; alkylaluminum dialkoxides such as isobutylaluminum dimethoxydo, isobutylaluminum diethoxydo; dialkylaluminum alkoxides such as dimethylaluminum methoxyd, diethylaluminum ethoxide, dibutylaluminum butoxide; ethylaluminum sesquiethoxydo, butylaluminum sesqui Alkylaluminum sesquialkoxides such as butoxide;
(Wherein, ^{R a} and ^{R b} are. Synonymous with ^{R a} and ^{R b} in the formula [C2]) formula ^{_{R a 2.5 Al (OR b)}} 0.5 having an average composition represented by Partially alkoxylated alkylaluminum; alkylaluminum aryloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide); dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum Dialkylaluminum halides such as chloride, diethylaluminum bromide, diisobutylaluminum chloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibramide;
Partially halogenated alkylaluminum such as alkylaluminum dihalide such as ethylaluminum dichloride; partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxychloride, butylaluminum butokicyclolide, ethylaluminum ethoxybromid Can be mentioned.

R ^m _q2 AlH _r1 ... [C3]
In the 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 Rd, the R ^m may be the same or different. Examples of the hydrocarbon 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 a number of 0 ≦ q2 ≦ 2, r1 is a number of 1 ≦ r1 ≦ 3, and q2 + r1 = 3.

Examples of the aluminum compound having an Al—H bond represented by the general formula [C3] include dimethylaluminum hydride, diethylaluminum hydride, diisopropylaluminum hydride, dibutylaluminum hydride, diisobutylaluminum hydride, diisohexyl aluminum hydride, and diphenylaluminum. Examples thereof include hydride, dicyclohexylaluminum hydride, phenylaluminum dihydride, and allan.

M ² AlR ^a ₄ ... [C4]
Wherein [C4], ^{M 2} represents a Li, Na or K, plural ^{R a} 1 to 15 carbon atoms are each independently preferably a 1-4 hydrocarbon group.
Examples of the compound represented by the general formula [C4] include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

Further, a compound similar to the compound represented by the general formula [C4] can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Examples of such a compound include (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 preferable, and among them, from the viewpoint of industrial availability, it is represented by m3 = 3 in the general formula [C2]. Compounds are preferred. Further, among them, the compound represented by the general formula [C1] is particularly preferable from the viewpoint of reactivity with the component (B1), stability of the catalyst solution, solubility and the like.

AlR ⁿ ₃ ... [C1]

In the formula [C1], R ⁿ represents a linear or branched alkyl group having 3 to 10 carbon atoms.
Specifically, triisopropylaluminum, trinormalpropylaluminum, triisobutylaluminum, trinormalbutylaluminum, trinormalhexylaluminum, and trinormaloctylaluminum are preferable, and among these, solubility in a saturated hydrocarbon solvent and industrial From the viewpoint of availability, triisobutylaluminum, trinormalhexylaluminum, and trinormaloctylaluminum are particularly preferable.

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

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

In the 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. .. A plurality of R ^qs may be the same or different from each other.

Methylaluminoxane is an organoaluminum oxy compound that has been widely used in the polyolefin industry because of its availability and high polymerization activity. Further, a methylaluminoxane analog having excellent solubility in saturated hydrocarbons (eg, modified methylaluminoxane represented by the formula [C7]) has also been developed.

The modified methylaluminoxane represented by the formula [C7] is prepared using, for example, trimethylaluminum and alkylaluminum other than trimethylaluminum (for example, the production method is disclosed in US4960878, US5041584, etc.). Modified methylaluminoxane prepared with trimethylaluminum and triisobutylaluminum (ie, R ^q is an isobutyl group) from manufacturers such as Tosoh Finechem is commercially produced under the names MMAO and TMAO. (For example, see "Tosoh Research and Technology Report", Vol. 47, 55 (2003)).

In the solution polymerization by the method for producing an olefin polymer of the present embodiment, a benzene-insoluble organoaluminum oxy compound exemplified in JP-A-2-78687 can also be used.

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

<Saturated hydrocarbon solvent (D)>
The saturated hydrocarbon solvent (D) used for dissolving each of the constituents (A) to (B2) is an inert hydrocarbon solvent, more preferably saturated hydrocarbon having a boiling point of 20 to 200 ° C. under normal pressure. It is a hydrogen solvent.

As the saturated hydrocarbon solvent (D), it is preferable to use at least one hydrocarbon solvent selected from an aliphatic hydrocarbon solvent and an alicyclic hydrocarbon solvent. Examples of the aliphatic hydrocarbon solvent include pentane, hexane, heptane, octane, decane, dodecane, and kerosene; examples of the alicyclic hydrocarbon solvent include cyclopentane, cyclohexane, and methylcyclopentane. Among these, aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane are more preferable.

In the present embodiment, the above-mentioned saturated hydrocarbon solvent (D) is preferably used alone as the solvent used for dissolving each of the constituent components (A) to (B2) of the present embodiment. In addition to the saturated hydrocarbon solvent (D), benzene, toluene, etc. It can contain aromatic hydrocarbons such as xylene and halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane. In the preparation of the olefin polymerization catalyst solution, the amounts of the aromatic hydrocarbon solvent and the halogenated hydrocarbon solvent used are preferably 10% by mass or less, more preferably 5% by mass or less, based on the total amount of the solvent. As described above, it is particularly preferable not to use an aromatic hydrocarbon solvent and a halogenated hydrocarbon solvent.
The saturated hydrocarbon solvent (D) may be used alone or in combination of two or more.

<Preparation of olefin polymerization catalyst solution>
In the method for producing an olefin polymer of the present embodiment, the olefin polymerization catalyst solution preferably dissolves each of the above components (A) to (B2) in a saturated hydrocarbon solvent (D).
As the solubility of each component (A) to (B2) in the saturated hydrocarbon solvent (D), the components (A) and (B2) are often soluble, and the component (B1) is insoluble. Often.
Generally, when each of the components (A) to (B2) is separately dissolved (suspended) in a saturated hydrocarbon solvent (D) and then fed into a polymerization reactor, the component (B1) is saturated. Since it is insoluble in the hydrocarbon solvent (D), the reaction between the components (A) to (B2) in the reactor is very slow, and it may be difficult to form an active species.
In the present embodiment, before the components (A) to (B2) are fed into the polymerization reactor, the olefin polymerization catalyst is mixed with the saturated hydrocarbon solvent (D) in advance so that each component has a specific concentration range. The method of preparing the solution may be preferred.

When preparing the olefin polymerization catalyst solution as described above, the component (A) is usually ^10-7 to ^10-2 mol, preferably ^10-6 to ^10-3 mol, per 1 L of the saturated hydrocarbon solvent (D). It is used in such an amount.
The component (B1) is usually used in an amount of ^10-7 to ^10-2 mol, preferably ^10-6 to 15 × 10 ^-3 mol, per 1 L of the saturated hydrocarbon solvent (D).
The component (B2) is used in an amount such that the aluminum atom in the component (B2) is usually ^{10-5 to 5} mol, preferably ^{10-4 to 2 mol, per 1 L of the saturated hydrocarbon solvent (D).}

Further, in the present embodiment, in order to completely dissolve the components (A) to (B2) in the saturated hydrocarbon solvent and further carry out the polymerization of the olefin with high activity, the components (A) to be mixed in advance with the saturated hydrocarbon solvent (in order to carry out the polymerization of the olefin with high activity). It is preferable that A) to (B2) satisfy the following requirements (i) to (iv).
(I) 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 to the transition metal complex (A) in the compound (B2) added to the saturated hydrocarbon solvent (D) is 33 to 5000.
(Iii) The aluminum atom in the compound (B2) added to 1 L of the saturated hydrocarbon solvent (D) is 3 to 1000 mmol.
(Iv) The molar ratio ((B) / (A)) of the compound (B1) to be added to the saturated hydrocarbon solvent (D) and the transition metal complex (A) is 1 to 15.
Hereinafter, the conditions (i) to (iv) will be described.

<Condition (i)>
The amount of the transition metal complex (A) added is preferably 0.02 to 0.6 mmol per liter of the saturated hydrocarbon solvent (D). When the addition amount is within the above range, the transition metal complex (A) is completely dissolved in the saturated hydrocarbon solvent (D), and olefin polymerization can be carried out 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 polymerization activity of the olefin may decrease. Further, if the addition amount exceeds 0.6 mmol, the transition metal complex (A) may remain undissolved, or the active species in which the components (A), (B1) and (B2) have reacted may precipitate. .. However, even in this case, if the portion (supernatant portion) in which the transition metal complex (A) is dissolved is used as the olefin polymerization catalyst solution, the effect of the present embodiment can be exhibited.
The amount of the transition metal complex (A) added is more preferably 0.03 to 0.6 mmol, still 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 to the transition metal complex (A) in the compound (B2) added to the saturated hydrocarbon solvent (D) is preferably 33 to 5000. When the molar ratio ((B2) / (A)) is within the above range, it is preferable from the viewpoint that the active species is less likely to be inactivated.
The molar ratio ((B2) / (A)) is more preferably 50 to 2500, even more preferably 100 to 2000, and even more preferably 150 to 1000.

<Condition (iii)>
The amount of the compound (B2) added is such that the number of aluminum atoms in the compound (B2) is preferably 3 to 1000 mmol per liter of the saturated hydrocarbon solvent (D). When the addition amount is within the above range, an amount that can be used for the activation reaction of the transition metal complex (A) is secured, and a catalyst such as _{H 2 O present in a trace amount in the saturated hydrocarbon solvent (D) is secured.} By supplementing the toxic impurities with the compound (B2), it becomes possible to stably maintain the catalytically active species produced.
The amount of compound (B2) added is more preferably 5 to 500 mmol, still more preferably 10 to 300 mmol, and even more preferably 50 to 250 mmol.
The amount of the compound (B2) added is the total amount when both the (C-1) organoaluminum compound and the (C-2) organoaluminum oxy compound are used as the compound (B2).

<Condition (iv)>
The molar ratio ((B) / (A)) of the compound (B1) to the transition metal complex (A) added to the saturated hydrocarbon solvent (D) is preferably 1 to 15. As is clear from the reaction mechanism described above, since the reaction of the component (A) and the component (B1) is 1: 1 in terms of the number of moles, if the molar ratio is 1 or more, especially from the viewpoint of the polymerization activity of the olefin. Can be used without problems. On the other hand, the upper limit of the molar ratio is not particularly limited, but if the ratio is increased too much, it leads to an increase in cost and there is a possibility that undissolved residue of the compound (B1) may occur. Therefore, the upper limit is set for 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 the components (A) and (B2) added to the saturated hydrocarbon solvent (D) under the conditions (i) and (iii) may satisfy the conditions at the time of preparing the olefin polymerization catalyst solution. Therefore, there is no difference in effect even if it is diluted after preparation and sent to the polymerization reactor.

The order of addition of the components (A) to (B2) to the saturated hydrocarbon solvent (D) is not particularly limited. Specifically, a method of simultaneously adding the components (A) to (B2) to the saturated hydrocarbon solvent (D), or adding the components (A) to (B2) to the saturated hydrocarbon solvent (D) in an arbitrary order. There is a way to do it. In the above addition method, either a method of collectively adding the components (A) to (B2) to the saturated hydrocarbon solvent (D) or a method of adding the components (B2) in a divided manner can be adopted.

Of these, (A), (B1), and (B2) are sequentially added to prepare the catalyst solution, and the preferred order of addition is to add the components (A) and (B2) to the saturated hydrocarbon solvent (D). Examples thereof include a method of adding the component (B1) after the addition, and a method of adding the component (B1) and (B2) to the saturated hydrocarbon solvent (D) and then adding the component (A).

At this time, when the components (B1) and (B2) are added to the saturated hydrocarbon solvent (D) and then the component (A) is added later, the two components added earlier are added to the saturated hydrocarbon solvent (D). Although it depends on the degree of dissolution of the above, it is preferably 0 to 60 minutes, more preferably 0 to 30 minutes, and even more preferably after the start of mixing the two components added earlier with the saturated hydrocarbon solvent (D). It is preferably after 0 to 15 minutes from the viewpoint of ease of dissolution of each component in the saturated hydrocarbon solvent (D), the life of the produced catalytically active species and the component (B1), and the like.

Further, when the component (A) and (B2) are added to the saturated hydrocarbon solvent (D) and then the component (B1) is added later, there is no particular limitation, but the saturated hydrocarbon of the two components added earlier is not particularly limited. It is preferably 0 to 600 minutes, more preferably 0 to 300 minutes, and even more preferably 0 to 120 minutes after the start of mixing with the solvent (D).

[Method for producing olefin polymer]
The method for producing an olefin polymer of the present embodiment includes a step of feeding the above-mentioned olefin polymerization catalyst solution into a polymerization reactor and solution-polymerizing the olefin in the polymerization reactor. "Solution polymerization" is a general term for a method of performing polymerization in a state where the polymer is dissolved in a reaction solvent.
Generally, in solution polymerization, as a method of feeding the olefin polymerization catalyst component into the polymerization reactor, for example, when the above-mentioned components (A) to (B2) are used, [m1] the above-mentioned component (A) to A method of directly feeding the mixed solution obtained by mixing (B2) with a hydrocarbon solvent into a polymerization reactor as it is, [m2] Hydrocarbon solvent of each component (A) to (B2) above. Examples thereof include a method in which solutions (or suspensions) are individually prepared and individually fed into a polymerization reactor.

When the hydrocarbon solvent is an aromatic hydrocarbon solvent, each of the components (A) to (B2) is easily dissolved in the solvent, so that there is little problem in the polymerization reaction of the olefin.
However, when the above-mentioned hydrocarbon solvent is a saturated hydrocarbon solvent (D), the catalyst often does not become a completely uniform solution in the methods [m1] and [m2], and the insoluble matter is sent to the polymerization reactor together with the solution. If it is added, (a) the insoluble matter may precipitate at the catalytic feed line and the line may be blocked, or (b) the feed amount may not be constant and the polymerization activity may not be stable. c) Insoluble matter may remain in the product polymer and cause poor transparency (fish eye). Furthermore, the active sites in the reaction field are non-uniform as in the case where the ionized ionic compound is used as it is in a solvent in a turbid state without being dissolved, so that a polymer other than the target polymer is produced during polymerization. As a result, the productivity can be significantly reduced. To give a specific example, in the case of continuously producing an ethylene / butene copolymer composed of ethylene and butene, if the polymerization is carried out while continuously supplying the catalyst, ethylene and butene into the polymerization vessel, the operating time will be increased. As the length increases, a polymer having a higher ethylene content than the product is precipitated in the polymer, and the precipitated polymer adheres to the polymer wall and the stirring blade, so that long-term continuous operation cannot be performed.

From this, when the methods of [m1] and [m2] are adopted, it is preferable that the components (A) to (B2) are in a uniform solution state, and therefore, the olefin polymerization catalyst solution in the present embodiment is used. It is particularly preferable to adopt the conditions specified in the preparation method.

If insoluble components are present in the components (A) to (B2), [m3] the above components (A) to (B2) are mixed together with the saturated hydrocarbon solvent (D). A method of feeding the supernatant obtained by removing the insoluble matter from the liquid to the polymerization reactor, [m4] Saturated hydrocarbon solvent (D) solution (or suspension) of each of the above components (A) to (B2). There is also a method of feeding the supernatant liquid obtained by removing the insoluble matter from the mixed liquid obtained by mixing the liquids) to the polymerization reactor.

Further, when the olefin polymerization catalyst solution is fed into the polymerization reactor, the olefin polymerization catalyst solution prepared by the above method can be fed into the polymerization reactor as it is, but the physical properties of the desired olefin polymer can be obtained. Therefore, the olefin polymerization catalyst solution can be appropriately diluted and used.

The polymerization temperature in solution polymerization is usually 20 to 300 ° C, preferably 30 to 250 ° C, and more preferably 50 to 200 ° C. The polymerization pressure is usually under normal pressure to 10 MPa gauge pressure, preferably normal pressure to 8 MPa gauge pressure. The polymerization reaction can be carried out by any of a batch type, a semi-continuous type and a continuous type. Further, it is also possible to carry out the polymerization in two or more stages having different reaction conditions.

When solution polymerization of olefins is carried out using the above-mentioned catalyst solution for olefin polymerization, the concentrations of the components (A) to (B2) in the polymerization reactor are set to the respective concentrations in the olefin polymerization catalyst solution adjusted by the above-mentioned method. Although it depends, it is generally used in the following range.

Component (A) per liter of the reaction volume, usually ¹⁰ -10 ^{to 10 -1} mol, used in an amount such preferably ¹⁰ -9 ^{to 10 -2} mol.

The molar ratio [(B) / M] of the component (B1) to the transition metal atom (M) in the component (A) is usually 1 to 50, preferably 1 to 20, particularly preferably. It is used in an amount such that it becomes 1 to 10.

The molar ratio [Al / M] of the aluminum atom (Al) in the component (B2) to the transition metal atom (M) in the component (A) of the component (B2) is usually 10 to 5,000, preferably 10 to 5,000. It is used in an amount such that it is 20 to 2,000.

At the time of solution polymerization, in addition to the component (B2) used for preparing the olefin polymerization catalyst solution, an organoaluminum compound (C-1) (eg, triisobutylaluminum, triethylaluminum) is separately added into the polymerization reactor. be able to. The reaction solvent may contain a trace amount of impurities such as H2O that are catalytic poisons. By adding a considerable amount of the organoaluminum compound (C-1), the catalyst poison can be excluded, and the deactivation of the catalyst can be further prevented.

The concentration of the organoaluminum compound (C-1) to be added separately is usually 0.001 to 2 mmol / L, preferably 0.005 to 1.5 mmol / L, more preferably 0 in the reaction solvent in solution polymerization. It is about 0.01 to 1 mmol / L.

Examples of the olefin applicable to the method for producing the olefin polymer of the present embodiment include ethylene and α-olefins having 3 to 20 carbon atoms (eg, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, etc. 4-Methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene), cyclic olefins with 3 to 20 carbon atoms (eg, cyclopentene) , Cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro Naphthalene), styrene, vinylcyclohexane, diene and the like.
One type of olefin may be used alone, or two or more types may be used in combination.

The reaction solvent used in the solution polymerization is preferably an inert hydrocarbon solvent, as in the case of the saturated hydrocarbon solvent (D) described above, and more preferably a saturated hydrocarbon solvent having a boiling point of 20 to 200 ° C. under normal pressure. be.

As the reaction solvent, it is preferable to use at least one hydrocarbon solvent selected from an aliphatic hydrocarbon solvent and an alicyclic hydrocarbon solvent. Hydrocarbons include, for example, pentane, hexane, heptane, octane, decane, dodecane, kerosene; alicyclic hydrocarbons include, for example, cyclopentane, cyclohexane, methylcyclopentane. Among these, aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane are more preferable.
If an aromatic hydrocarbon solvent or a halogenated hydrocarbon solvent is present in the system as the reaction solvent, these solvents may remain inside the obtained olefin polymer, which is not preferable from the viewpoint of environmental load and the like. Therefore, the amounts of each of the aromatic hydrocarbon solvent and the halogenated hydrocarbon solvent used are preferably 10% by mass or less, more preferably 5% by mass or less, based on the total amount of the reaction solvent; the aromatic hydrocarbon solvent and the halogen. It is particularly preferable not to use a hydrocarbon solvent.
The reaction solvent may be used alone or in combination of two or more.

The molecular weight of the olefin polymer obtained in the present embodiment can be adjusted by changing the hydrogen concentration and the polymerization temperature in the polymerization reactor. It can also be adjusted according to the amount of the component (B1) and the component (B2) used. When hydrogen is added, the amount thereof is appropriately about 0.001 to 5,000 NL per 1 kg of the olefin polymer produced.

After producing the olefin polymer by the above method, the organic compound (H) containing a hetero atom is supplied to the heat exchanger to inactivate the polymerization catalyst. Then, by producing another type of olefin polymer using another type of polymerization catalyst, a desired polymer can be stably produced.
Since such a production method can suppress the formation of unnecessary polymers, it is useful not only from an economic point of view but also from the viewpoint of environmental problems such as energy and resources, and has an impact on the industry of the present invention. Is big.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.

<Example 1>
A pressure reactor with an internal volume of 100 L with a jacket that can control the temperature, a compressor that can circulate unreacted gas, a line with a heat exchanger and a valve (sometimes called a circulation line), and a solvent. Using an apparatus (see FIG. 1) equipped with a (n-hexane) feed line, a raw material gas (ethylene) feed line, a 1-butene feed line, a catalyst feed line, and a content (product) extraction line. Continuous polymerization of ethylene and 1-butene was carried out. Here, the ethanol feed line was installed near the upstream side of the heat exchanger.
The conditions in the steady state were as shown in Table 1, and the opening degree of the valve of the circulation line was adjusted to circulate the unreacted gas (ethylene, 1-butene) so as to be in the steady state. The target polymer is an amorphous ethylene-butene polymer.
In the above polymerization reaction, first, dimethylmethylene (η ⁵ cycloventadienyl) (η ⁵ octamethyloctahydrodibenzofluorenyl) zirconium dichloride was used as the transition metal complex, and the operation was carried out for 7 days under the conditions shown in Table 1. ..
After the above continuous polymerization was completed, the reaction solution was taken out of the system, and oil run (washing by hexane circulation) was carried out for 8 hours according to a conventional method. After completion of the oil run ^{, continuous polymerization was carried out using diphenylsilylene (η 5} cycloventadienyl) (η ⁵ 3,6-di t-butyl fluorenyl) hafnium dichloride.
When the ethylene / butene copolymers produced under both conditions were analyzed by a DSC apparatus, no heat of fusion (ΔHm) derived from crystals, which was considered to be based on the ethylene chain, was observed.
(Dimethylmethylene (eta ⁵ cyclo preventor dienyl) (eta ⁵ octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenylsilylene (eta ⁵ cyclo preventor dienyl) (eta ⁵ 3,6-di t- Buchirufuruore It is known that ethylene has a property of reacting more easily than hafnium dichloride.

Comparative Example 1
Continuous polymerization was carried out in the same manner as in Example 1 except that ethanol was not supplied. (See Table 2 for conditions)
Ethylene in the latter half of the DSC measurement of the ethylene / butene copolymer obtained by continuous polymerization using ^{diphenylsilylene (η 5} cycloventadienyl) (η ^{5 3,6-di t-butylfluorenyl) hafnium dichloride.} The heat of fusion (ΔHm) derived from the crystals, which is thought to be based on the chain, was observed. This is due to the polymerization reaction of ethylene and 1-butene by ^{dimethylmethylene (η 5} cycloventadienyl) (η ⁵ octamethyloctahydrodibenzofluorenyl) zirconium dichloride slightly retained in a heat exchanger or the like, and the ethylene unit. It is considered that this is because the ethylene / butene copolymer having a high content was purified.

Claims (7)

A method for producing an olefin polymer using an olefin polymer apparatus having a reactor and a heat exchanger for exchanging heat of a gaseous substance generated by the reactor.
A production process for producing an olefin polymer (P) in the presence of an olefin polymerization catalyst containing a transition metal complex (A) and an organic metal compound (B) containing a Group 13 metal in the periodic table.
An organic substance containing a heteroatom in the heat exchanger for the purpose of removing the transition metal complex (A) existing inside the heat exchanger or eliminating its polymerization activity during or after the execution of the manufacturing process. The deactivation step of supplying the compound (H) and
A method for producing an olefin polymer, which comprises. In the deactivation step, during the execution of the manufacturing step, the heat exchanger continuously contains the heteroatom in a supply amount corresponding to the amount of the transition metal complex (A) used in the manufacturing step. The production method according to claim 1, wherein the organic compound (H) is supplied. The production method according to claim 1 or 2, wherein the organic compound (H) is a compound having 1 to 5 carbon atoms containing a group 15 element or a group 16 element in the periodic table as a hetero atom. The production method according to any one of claims 1 to 3, wherein the deactivation step supplies the organic compound (H) in the form of gas or mist to the upstream side of the gas flow of the heat exchanger. The production method according to any one of claims 1 to 4, wherein the deactivating step supplies the organic compound (H) together with an inert solvent that does not contribute to the polymerization reaction. The production method according to any one of claims 1 to 5, wherein the transition metal complex (A) is a metallocene compound containing zirconium, hafnium or titanium. The production method according to any one of claims 1 to 6, wherein the transition metal complex (A) is at least one metallocene compound selected from non-crosslinked metallocene compounds and crosslinked metallocene compounds.

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