JP2022078934A - Method for producing cyclic olefin-based copolymer, and cyclic olefin-based copolymer - Google Patents

Abstract

To provide a method for efficiently producing a cyclic olefin-based copolymer reduced in an aluminum content of 100 ppm or less.SOLUTION: A method for producing a cyclic olefin-based copolymer includes a polymerization step of copolymerizing α-olefin (X') having 2 to 20 carbon atoms, cyclic olefin (Y') having no aromatic ring, and cyclic olefin (Z') having an aromatic ring, in the presence of a catalyst for olefin polymerization containing a transition metal compound (A) and a compound (B), and a catalyst removal step of removing the catalyst for olefin polymerization, in which the cyclic olefin-based copolymer obtained by the production method has a structural unit (X) derived from the α-olefin (X'), a structural unit (Y) derived from the cyclic olefin (Y') and a structural unit (Z) derived from the cyclic olefin (Z'), an aluminum content of the cyclic olefin-based copolymer is 100 ppm or less, the transition metal compound (A) contains one or two or more selected from the group consisting of a transition metal compound (A-1), a transition metal compound (A-2) and a transition metal compound (A-3), and the compound (B) contains one or two or more selected from the group consisting of an organometal compound (B-1), an organic aluminum oxy compound (B-2), and a compound (B-3) forming an ion pair by reacting with the metal compound (A).SELECTED DRAWING: None

Description

The present invention relates to a method for producing a cyclic olefin-based copolymer and a cyclic olefin-based copolymer. More specifically, the present invention relates to a method for producing a cyclic olefin-based copolymer in which metal residues derived from a polymerization catalyst component are reduced.

Cyclic olefin polymers are used in optical lenses such as image pickup lenses, Fθ lenses, and pickup lenses. Cyclic olefin-based polymers used in molded products such as optical lenses are required to have characteristics such as high transparency, excellent dimensional stability, and excellent heat resistance.

Examples of the technique relating to such a cyclic olefin polymer include those described in Patent Documents 1 and 2.

Japanese Unexamined Patent Publication No. 10-287713 Japanese Unexamined Patent Publication No. 2010-235719

Polymerization of cyclic olefins is generally carried out by a solution polymerization method. Among them, the solution polymerization method using a polymerization catalyst is one of the polymerization methods preferably used for producing a cyclic olefin-based copolymer because the reaction controllability is good and a polymer having high uniformity can be obtained. It is one. However, while solution polymerization has various advantages, when the polymerization catalyst component is dissolved in the polymerization reaction solution, there is a problem that the metal component derived from the polymerization catalyst component tends to remain in the obtained polymer. is doing.

Further, in order to activate the polymerization catalyst, a co-catalyst typified by an organic aluminum compound may be used in combination, but in that case, the amount of the co-catalyst such as the organic aluminum compound used is larger than that of the polymerization catalyst. However, there is a problem that the content of the aluminum component in the cyclic olefin-based polymer becomes extremely large. Such metal component residues such as aluminum adversely affect the color tone and physical properties during molding, and therefore need to be sufficiently removed.

In the polymerization of a cyclic olefin-based polymer using a polymerization catalyst, in order to deactivate the polymerization catalyst after the completion of the polymerization reaction and further remove the deactivated polymerization catalyst, an alkaline aqueous solution such as sodium hydroxide and a polymerization reaction solution are generally used. Is liquid-liquid mixed, and the metal component is extracted into an alkaline aqueous layer. At this time, the liquid viscosity of the polymerization solution increases, the metal component residue derived from the catalyst is difficult to be extracted into the alkaline aqueous layer, and the removal of the metal component residue is hindered.

In this regard, some cyclic olefin-based polymers such as copolymers obtained by polymerizing norbornene and ethylene may solidify due to an increase in the liquid viscosity of the polymer solution after a certain period of time has passed after the preparation of the polymer solution. Is known (Japanese Patent Laid-Open No. 2013-064114 [0007] paragraph, etc.). Therefore, in the production of cyclic olefin-based polymers, there has been a problem of inhibition of removal of metal component residues due to an increase in the liquid viscosity of the polymerization solution.

To solve the above problems, a method of diluting a polymerization reaction solution with a solvent to lower the liquid viscosity of the polymerization reaction solution and promoting the removal of metal component residues is disclosed (Patent No. 5735367 [Claim 1]). etc). However, this method has a problem in terms of production efficiency because the amount of the polymerization solution that must be treated in the subsequent steps (catalyst removal step and polymer separation step) increases.

An object of the present invention is to provide a method for efficiently producing a cyclic olefin-based copolymer having an aluminum content reduced to 100 ppm or less.

The present inventors have diligently studied to solve the above problems. As a result, by carrying out the polymerization in the presence of the olefin polymerization catalyst containing the transition metal compound (A) and the compound (B), the metal content derived from the polymerization catalyst component contained in the cyclic olefin-based copolymer We have found that the residue can be reduced, and have completed the present invention.

That is, according to the present invention, the following method for producing a cyclic olefin-based copolymer is provided.

上記式（Ｉ）において、
Ｍ^１は、周期律表４族の遷移金属原子を示し、
Ｒ^０は、アルキレン基、アルキリデン基、アリレン基およびシリレン基からなる群、ならびにそれらの置換体からなる群より選択される基を示し、
Ｒ^１およびＲ^２は、それぞれ独立に、シクロアルカジエニル基またはそれらの置換体を示し、
Ｒ^３およびＲ^４は、それぞれ独立に、水素原子、ハロゲン原子、炭化水素基、ハロゲン含有基、酸素含有基、硫黄含有基、窒素含有基、リン含有基、ケイ素含有基、ホウ素含有基およびアルミニウム含有基からなる群、ならびにそれらの置換体からなる群より選択される原子または基を示す。

上記式（ＩＩ）において、
Ｍ^２は、周期律表４族の遷移金属原子を示し、
ｎ^１は、１～３の整数を示し、
Ｌは、それぞれ独立に、周期律表１５族の原子が配位原子となる１価のアニオン性配位子を示し、
Ｘ^１は、それぞれ独立に、水素原子、ハロゲン原子、炭化水素基、ハロゲン含有基、酸素含有基、硫黄含有基、窒素含有基、リン含有基、ケイ素含有基、ホウ素含有基およびアルミニウム含有基からなる群、ならびにそれらの置換体からなる群より選択される基または原子を示し、
Ｒ^５～Ｒ^９は、それぞれ独立に、水素原子、ハロゲン原子、炭化水素基、ハロゲン含有基、酸素含有基、硫黄含有基、窒素含有基、リン含有基、ケイ素含有基、ホウ素含有基およびアルミニウム含有基からなる群、ならびにそれらの置換体からなる群より選択される基または原子を示し、Ｒ^５～Ｒ^９のうち任意の２つまたは３つが縮合し環を形成していてもよく、形成される環は共役二重結合を含む芳香族性を有するものでもよい。

上記式（ＩＩＩ）において、
Ｍ^３は、周期律表４族の遷移金属原子を示し、
ｎ^２は、１～４の整数を示し、
Ｘ^２は、それぞれ独立に、水素原子、ハロゲン原子、炭化水素基、ハロゲン含有基、酸素含有基、硫黄含有基、窒素含有基、リン含有基、ケイ素含有基、ホウ素含有基およびアルミニウム含有基からなる群より選択される原子または基を示し、
Ｒ^１０～Ｒ^１７は、それぞれ独立に、水素原子、ハロゲン原子、炭化水素基、ハロゲン含有基、酸素含有基、硫黄含有基、窒素含有基、リン含有基、ケイ素含有基、ホウ素含有基およびアルミニウム含有基からなる群、ならびにそれらの置換体からなる群より選択される原子または基を示し、Ｒ^１０～Ｒ^１７のうち隣接するもの同士は互いに結合して環を形成していてもよく、形成される環は共役二重結合を含む芳香族性を有するものでもよい。
［２］
［１］に記載の環状オレフィン系共重合体の製造方法であって、
上記式（Ｉ）において、
Ｒ^１およびＲ^２は、それぞれ独立に、シクロペンタジエニル基、メチルシクロペンタジエニル基、エチルシクロペンタジエニル基、ジメチルシクロペンタジエニル基、インデニル基、テトラヒドロインデニル基およびフルオレニル基からなる群、ならびにそれらの置換体からなる群より選択される基を示す、環状オレフィン系共重合体の製造方法。
［３］
［１］に記載の環状オレフィン系共重合体の製造方法であって、
上記式（ＩＩ）において、
Ｌは、下記の式（ＩＶ）で表される１価のアニオン性配位子である、環状オレフィン系共重合体の製造方法。

上記式（ＩＶ）において、
Ｙは、周期律表１５族の原子を示し、
Ｚは、周期律表１４族、１５族または１６族から選ばれる一種類の原子を示し、
ｎ^３は、１～３の整数を示し、
Ｒ^１８は、それぞれ独立に、水素原子、ハロゲン原子、炭化水素基、ハロゲン含有基、酸素含有基、硫黄含有基、窒素含有基、リン含有基、ケイ素含有基、ホウ素含有基およびアルミニウム含有基からなる群、ならびにそれらの置換体からなる群より選択される基または原子を示し、各々が互いに結合して環を形成していてもよく、形成される環は共役二重結合を含む芳香族性を有するものでもよく、形成される環がシクロペンタジエニル基と結合していてもよい。
［４］
［１］に記載の環状オレフィン系共重合体の製造方法であって、
上記式（ＩＩＩ）において、
Ｒ^１０～Ｒ^１４およびＲ^１７は、それぞれ独立に、水素原子、ハロゲン原子、炭化水素基、ハロゲン含有基およびケイ素含有基からなる群、ならびにそれらの置換体からなる群より選択される原子または基を示し、Ｒ^１０～Ｒ^１４のうち隣接するもの同士は互いに結合して環を形成していてもよく、形成される環は共役二重結合を含む芳香族性を有するものでもよい。
Ｒ^１５およびＲ^１６は、それぞれ独立に、水素原子、ハロゲン原子、炭化水素基およびハロゲン含有基からなる群、ならびにそれらの置換体からなる群より選択される原子または基を示す、環状オレフィン系共重合体の製造方法。 [1]
In the presence of an olefin polymerization catalyst containing the transition metal compound (A) and the compound (B), an α-olefin (X') having 2 to 20 carbon atoms and a cyclic olefin having no aromatic ring (Y). ´) and a polymerization step of copolymerizing a cyclic olefin (Z ′) having an aromatic ring;
With the catalyst removal step of removing the catalyst for olefin polymerization;
Is a method for producing a cyclic olefin-based copolymer comprising the above.
The cyclic olefin-based copolymer obtained by the production method has a structural unit (X) derived from the α-olefin (X'), a structural unit (Y) derived from the cyclic olefin (Y'), and the cyclic olefin. It has a structural unit (Z) derived from (Z') and has.
The aluminum content of the cyclic olefin-based copolymer is 100 ppm or less, and the content is 100 ppm or less.
The transition metal compound (A) is
The transition metal compound (A-1) represented by the following formula (I),
Contains one or more selected from the group consisting of the transition metal compound (A-2) represented by the following formula (II) and the transition metal compound (A-3) represented by the following formula (III). death,
The above compound (B) is
Organometallic compound (B-1),
Cyclic containing one or more selected from the group consisting of the organic aluminum oxy compound (B-2) and the compound (B-3) that reacts with the transition metal compound (A) to form an ion pair. A method for producing an olefin-based copolymer.

In the above formula (I)
M ¹ represents a transition metal atom of Group 4 of the Periodic Table.
^R0 indicates a group selected from the group consisting of an alkylene group, an alkylidene group, an arylene group and a silylene group, and a group consisting of their substitutions.
R ¹ and R ² each independently represent a cycloalkazienyl group or a substitution thereof.
R ³ and R ⁴ are independently hydrogen atom, halogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, silicon-containing group, boron-containing group and aluminum. An atom or group selected from the group consisting of containing groups and the group consisting of their substituents is shown.

In the above formula (II)
M ² represents a transition metal atom of Group 4 of the periodic table.
n ¹ represents an integer of 1 to 3 and represents
L independently represents a monovalent anionic ligand in which an atom of Group 15 of the periodic table is a coordination atom.
X ¹ is independently composed of hydrogen atom, halogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, silicon-containing group, boron-containing group and aluminum-containing group. Group, as well as groups or atoms selected from the group consisting of their substitutions,
R ⁵ to R ⁹ are independently hydrogen atom, halogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, silicon-containing group, boron-containing group and aluminum. It represents a group or atom selected from the group consisting of containing groups and the group consisting of their substituents, and any two or ^three of R5 to ^R9 may be fused to form a ring. The ring to be formed may have aromaticity including a conjugated double bond.

In the above formula (III)
M ³ represents a transition metal atom of Group 4 of the Periodic Table.
n ² represents an integer from 1 to 4 and represents
X ² is independently composed of hydrogen atom, halogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, silicon-containing group, boron-containing group and aluminum-containing group. Indicates an atom or group selected from the group
R ¹⁰ to R ¹⁷ are independently hydrogen atom, halogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, silicon-containing group, boron-containing group and aluminum. Indicates an atom or group selected from the group consisting of containing groups and the group consisting of their substituents, and adjacent ones of R ¹⁰ to R ¹⁷ may be bonded to each other to form a ring. The ring to be formed may have aromaticity including a conjugated double bond.
[2]
The method for producing a cyclic olefin-based copolymer according to [1].
In the above formula (I)
R ¹ and R ² are independently composed of a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, a dimethylcyclopentadienyl group, an indenyl group, a tetrahydroindenyl group and a fluorenyl group, respectively. A method for producing a cyclic olefin-based copolymer, which comprises a group selected from the group and a group consisting of a substituent thereof.
[3]
The method for producing a cyclic olefin-based copolymer according to [1].
In the above formula (II)
L is a method for producing a cyclic olefin-based copolymer, which is a monovalent anionic ligand represented by the following formula (IV).

In the above formula (IV)
Y indicates an atom of Group 15 of the periodic table.
Z represents one kind of atom selected from Group 14, Group 15, or Group 16 of the Periodic Table.
n ³ represents an integer of 1 to 3 and represents
R ¹⁸ is independently composed of hydrogen atom, halogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, silicon-containing group, boron-containing group and aluminum-containing group. Group, as well as groups or atoms selected from the group consisting of their substituents, each of which may be bonded to each other to form a ring, the ring of which is aromatic, including conjugated double bonds. The ring formed may be bonded to a cyclopentadienyl group.
[4]
The method for producing a cyclic olefin-based copolymer according to [1].
In the above formula (III)
R ¹⁰ to R ¹⁴ and R ¹⁷ are independently selected atoms or groups from the group consisting of hydrogen atom, halogen atom, hydrocarbon group, halogen-containing group and silicon-containing group, and the group consisting of their substitutions. , And R ¹⁰ to R ¹⁴ adjacent to each other may be bonded to each other to form a ring, and the formed ring may have aromaticity including a conjugated double bond.
R ¹⁵ and R ¹⁶ each independently represent an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a halogen-containing group, and a group consisting of their substitutions. Method for producing a polymer.

Further, according to the present invention, the cyclic olefin-based copolymers shown below are provided.

上記式（Ｖ）において、
ｎ^１０１は０または１を示し、
ｍ^１０１は０または正の整数を示し、
ｑ^１０１は０または１を示し、
Ｒ^１０１～Ｒ^１１８ならびにＲ^ａおよびＲ^ｂは、それぞれ独立に、水素原子、ハロゲン原子またはハロゲン原子で置換されていてもよい炭化水素基を示し、Ｒ^１１５～Ｒ^１１８は互いに結合して単環または多環を形成していてもよく、かつ、該単環または多環は二重結合を有していてもよく、またＲ^１１５とＲ^１１６とで、またはＲ^１１７とＲ^１１８とでアルキリデン基を形成していてもよい。ただし、芳香環を含まない。
［９］
［５］～［８］のいずれか一つに記載の環状オレフィン系共重合体であって、
上記構成単位（Ｚ）が、下記の式（ＶＩ）で示される化合物、下記の式（ＶＩＩ）で示される化合物、および下記の式（ＶＩＩＩ）で示される化合物からなる群から選択される一種または二種以上の化合物由来の構成単位を含む、環状オレフィン系共重合体。

上記式（ＶＩ）において、
ｎ^２０１およびｑ^２０１は、それぞれ独立に、０、１または２であり、
Ｒ^２０１～Ｒ^２１７は、それぞれ独立に、水素原子、フッ素原子を除くハロゲン原子、またはフッ素原子を除くハロゲン原子で置換されていてもよい炭素原子数１～２０の炭化水素基であり、
Ｒ^２１０～Ｒ^２１７のうち一つは結合手であり、
ｑ^２０１＝０のとき、Ｒ^２１０とＲ^２１１、Ｒ^２１１とＲ^２１２、Ｒ^２１２とＲ^２１３、Ｒ^２１３とＲ^２１４、Ｒ^２１４とＲ^２１５、Ｒ^２１５とＲ^２１０は互いに結合して単環または多環を形成していてもよく、
ｑ^２０１＝１または２のとき、Ｒ^２１０とＲ^２１１、Ｒ^２１１とＲ^２１７、Ｒ^２１７とＲ^２１７、Ｒ^２１７とＲ^２１２、Ｒ^２１２とＲ^２１３、Ｒ^２１３とＲ^２１４、Ｒ^２１４とＲ^２１５、Ｒ^２１５とＲ^２１６、Ｒ^２１６とＲ^２１６、Ｒ^２１６とＲ^２１０は互いに結合して単環または多環を形成していてもよく、
上記単環または上記多環が二重結合を有していてもよく、
上記単環または上記多環が芳香族環であってもよい。

上記式（ＶＩＩ）において、
ｎ^２０２およびｍ^２０１は、それぞれ独立に、０、１または２であり、
ｑ^２０２は、１、２または３であり、
Ｒ^２１８～Ｒ^２３１は、それぞれ独立に、水素原子、フッ素原子を除くハロゲン原子、またはフッ素原子を除くハロゲン原子で置換されていてもよい炭素原子数１～２０の炭化水素基であり、
ｑ^２０２＝１のとき、Ｒ^２２８とＲ^２２９、Ｒ^２２９とＲ^２３０、Ｒ^２３０とＲ^２３１は互いに結合して単環または多環を形成していてもよく、
ｑ^２０２＝２または３のとき、Ｒ^２２８とＲ^２２８、Ｒ^２２８とＲ^２２９、Ｒ^２２９とＲ^２３０、Ｒ^２３０とＲ^２３１、Ｒ^２３１とＲ^２３１は互いに結合して単環または多環を形成していてもよく、
上記単環または上記多環が二重結合を有していてもよく、
上記単環または上記多環が芳香族環であってもよい。

上記式（ＶＩＩＩ）において、
ｑ^２０３は１、２または３であり、
Ｒ^２３２～Ｒ^２３９は、それぞれ独立に、水素原子、フッ素原子を除くハロゲン原子、またはフッ素原子を除くハロゲン原子で置換されていてもよい炭素原子数１～２０の炭化水素基であり、
ｑ^２０３＝１のとき、Ｒ^２３６とＲ^２３７、Ｒ^２３７とＲ^２３８、Ｒ^２３８とＲ^２３９は互いに結合して単環または多環を形成していてもよく、
ｑ^２０３＝２または３のとき、Ｒ^２３６とＲ^２３６、Ｒ^２３６とＲ^２３７、Ｒ^２３７とＲ^２３８、Ｒ^２３８とＲ^２３９、Ｒ^２３９とＲ^２３９は互いに結合して単環または多環を形成していてもよく、
上記単環または上記多環が二重結合を有していてもよく、
上記単環または上記多環が芳香族環であってもよい。
［１０］
［５］～［９］のいずれか一項に記載の環状オレフィン系共重合体であって、
示差走査熱量計（ＤＳＣ）で測定される、当該環状オレフィン系共重合体のガラス転移温度（Ｔｇ）が１２０℃以上１８０℃以下である、環状オレフィン系共重合体。 [5]
A structural unit (X) derived from an α-olefin (X') having 2 to 20 carbon atoms, a structural unit (Y) derived from a cyclic olefin (Y') having no aromatic ring, and a cyclic olefin having an aromatic ring. A cyclic olefin-based copolymer having a structural unit (Z) derived from (Z').
The cyclic olefin-based copolymer has an aluminum content of 100 ppm or less.
[6]
The cyclic olefin-based copolymer according to [5].
When the total content of the structural unit (X), the structural unit (Y) and the structural unit (Z) in the cyclic olefin-based copolymer is 100 mol%, the cyclic olefin-based copolymer is contained. A cyclic olefin-based copolymer having a content of the structural unit (X) of 10 mol% or more and 80 mol% or less.
[7]
The cyclic olefin-based copolymer according to [5] or [6].
When the total content of the structural unit (Y) and the structural unit (Z) in the cyclic olefin-based copolymer is 100 mol%, the structural unit (Z) in the cyclic olefin-based copolymer A cyclic olefin-based copolymer having a content of 5 mol% or more and 95 mol% or less.
[8]
The cyclic olefin-based copolymer according to any one of [5] to [7].
A cyclic olefin-based copolymer in which the structural unit (Y) contains a structural unit derived from a compound represented by the following formula (V).

In the above formula (V)
n ¹⁰¹ indicates 0 or 1 and represents
m ¹⁰¹ indicates 0 or a positive integer,
q ¹⁰¹ indicates 0 or 1 and represents
R ¹⁰¹ to R ¹¹⁸ and R ^a and R ^b each independently represent a hydrocarbon group which may be substituted with a hydrogen atom, a halogen atom or a halogen atom, and R ¹¹⁵ to R ¹¹⁸ are bonded to each other to form a single ring. Alternatively, a polycycle may be formed, and the monocyclic or polycycle may have a double bond, and an alkylidene group may be formed between R ¹¹⁵ and R ¹¹⁶ , or between R ¹¹⁷ and R ¹¹⁸ . May be formed. However, it does not contain an aromatic ring.
[9]
The cyclic olefin-based copolymer according to any one of [5] to [8].
The structural unit (Z) is one selected from the group consisting of a compound represented by the following formula (VI), a compound represented by the following formula (VII), and a compound represented by the following formula (VIII). A cyclic olefin-based copolymer containing a structural unit derived from two or more compounds.

In the above formula (VI)
n ²⁰¹ and q ²⁰¹ are independently 0, 1 or 2, respectively.
R ²⁰¹ to R ²¹⁷ are hydrocarbon groups having 1 to 20 carbon atoms which may be independently substituted with a hydrogen atom, a halogen atom excluding a fluorine atom, or a halogen atom excluding a fluorine atom.
One of R ²¹⁰ to R ²¹⁷ is a bond,
When q ²⁰¹ = 0, R ²¹⁰ and R ²¹¹ , R ²¹¹ and R ²¹² , R ²¹² and R ²¹³ , R ²¹³ and R ²¹⁴ , R ²¹⁴ and R ²¹⁵ , R ²¹⁵ and R ²¹⁰ are monocyclic or are coupled to each other. It may form a polycycle,
When q ²⁰¹ = 1 or 2, R ²¹⁰ and R ²¹¹ , R ²¹¹ and R ²¹⁷ , R ²¹⁷ and R ²¹⁷ , R ²¹⁷ and R ²¹² , R ²¹² and R ²¹³ , R ²¹³ and R ²¹⁴ , R ²¹⁴ and R ^215. , R ²¹⁵ and R ²¹⁶ , R ²¹⁶ and R ²¹⁶ , R ²¹⁶ and R ²¹⁰ may be coupled to each other to form a monocyclic or polycyclic.
The monocyclic or polycyclic may have a double bond,
The monocyclic ring or the polycyclic ring may be an aromatic ring.

In the above formula (VII)
n ²⁰² and m ²⁰¹ are independently 0, 1 or 2, respectively.
q ²⁰² is 1, 2 or 3 and
R ²¹⁸ to R ²³¹ are hydrocarbon groups having 1 to 20 carbon atoms which may be independently substituted with a hydrogen atom, a halogen atom excluding a fluorine atom, or a halogen atom excluding a fluorine atom.
When q ²⁰² = 1, R ²²⁸ and R ²²⁹ , R ²²⁹ and R ²³⁰ , and R ²³⁰ and R ²³¹ may be bonded to each other to form a monocyclic or polycyclic ring.
When q ²⁰² = 2 or 3, R ²²⁸ and R ²²⁸ , R ²²⁸ and R ²²⁹ , R ²²⁹ and R ²³⁰ , R ²³⁰ and R ²³¹ and R ²³¹ and R ²³¹ combine with each other to form a monocyclic or polycyclic. You may be
The monocyclic or polycyclic may have a double bond,
The monocyclic ring or the polycyclic ring may be an aromatic ring.

In the above formula (VIII)
q ²⁰³ is 1, 2 or 3,
^R232 to ^R239 are hydrocarbon groups having 1 to 20 carbon atoms which may be independently substituted with a hydrogen atom, a halogen atom excluding a fluorine atom, or a halogen atom excluding a fluorine atom.
When q ²⁰³ = 1, R ²³⁶ and R ²³⁷ , R ²³⁷ and R ²³⁸ , and R ²³⁸ and R ²³⁹ may be bonded to each other to form a monocyclic or polycyclic ring.
When q ²⁰³ = 2 or 3, R ²³⁶ and R ²³⁶ , R ²³⁶ and R ²³⁷ , R ²³⁷ and R ²³⁸ , R ²³⁸ and R ²³⁹ , and R ²³⁹ and R ²³⁹ combine with each other to form a monocyclic or polycyclic. May be
The monocyclic or polycyclic may have a double bond,
The monocyclic ring or the polycyclic ring may be an aromatic ring.
[10]
The cyclic olefin-based copolymer according to any one of [5] to [9].
A cyclic olefin-based copolymer having a glass transition temperature (Tg) of 120 ° C. or higher and 180 ° C. or lower as measured by a differential scanning calorimeter (DSC).

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for efficiently producing a cyclic olefin-based copolymer having an aluminum content reduced to 100 ppm or less.

Hereinafter, the present invention will be described based on the embodiments. In this embodiment, "A to B" indicating a numerical range represent A or more and B or less unless otherwise specified.

[Method for producing cyclic olefin copolymer]
Hereinafter, the method for producing the cyclic olefin-based copolymer of the present invention will be described in detail.

The method for producing a cyclic olefin-based copolymer of the present embodiment is an α-olefin having 2 to 20 carbon atoms in the presence of a catalyst for olefin polymerization containing the transition metal compound (A) and the compound (B). It comprises a polymerization step of copolymerizing X'), a cyclic olefin (Y') having no aromatic ring, and a cyclic olefin (Z') having an aromatic ring.
By carrying out the polymerization in the presence of a catalyst for olefin polymerization containing the transition metal compound (A) and the compound (B), it is possible to provide a method for producing a cyclic olefin-based copolymer in which the aluminum content is reduced to 100 ppm or less. ..

<Transition metal compound (A)>
The transition metal compound (A) is
The transition metal compound (A-1) represented by the following formula (I),
Contains one or more selected from the group consisting of the transition metal compound (A-2) represented by the following formula (II) and the transition metal compound (A-3) represented by the following formula (III). do.

(Transition metal compound (A-1))
The transition metal compound (A-1) is represented by the following formula (I).

In the above formula (I)
M ¹ represents a transition metal atom of Group 4 of the Periodic Table.
Examples of M ¹ include a titanium atom, a zirconium atom, a hafnium atom, and the like.

M ¹ is preferably a titanium atom or a zirconium atom, and more preferably a zirconium atom.

^R0 represents a group selected from the group consisting of an alkylene group, an alkylidene group, an arylene group and a silylene group, and a group consisting of their substitutions.

Examples of the alkylene group indicated by ^R0 include a methylene group, an ethylene group, a propylene group, a butylene group and a diphenylmethylene group.
Examples of the alkylidene group indicated by ^R0 include an isopropylidene group and a cyclohexylidene group.
Examples of the arylene group indicated by R ⁰ include a phenylene group and the like.

Examples of the substituent of the alkylene group, the alkylidene group, the arylene group or the silylene group indicated by ^R0 include a dimethylmethylene group, a diphenylphenylene group and a dimethylsilylene group.

^R0 is preferably an alkylene group or a substituent of an alkylene group, more preferably a methylene group or a substituent of a methylene group, and further preferably a dimethylmethylene group or a diphenylphenylene group.

^R0 preferably has 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms.

R ¹ and R ² each independently represent a cycloalkazienyl group or a substitute thereof.

R ¹ and R ² are independently composed of a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, a dimethylcyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, and a fluorenyl group, respectively. It is preferably a group selected from the group and the group consisting of their substitutions.
It is more preferable that R ¹ and R ² are each independently a cyclopentadienyl group or a fluorenyl group, or a substitute thereof.

It is preferable that R ¹ and R ² have 1 to 20 carbon atoms independently of each other.

R ³ and R ⁴ are independently hydrogen atom, halogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, silicon-containing group, boron-containing group and aluminum. An atom or group selected from the group consisting of containing groups and the group consisting of their substituents is shown.

Examples of the halogen atom indicated by R ³ and R ⁴ include a fluorine atom, a chlorine atom and a bromine atom.

The hydrocarbon groups indicated by R ³ and R ⁴ include
Alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, hexyl group, octyl group, 2-ethylhexyl group or decyl group;
Cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cyclooctyl group, norbonyl group, bicyclononyl group or tricyclodecane group;
Aryl groups such as phenyl group, tolyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group or anthrasenyl group;
Aralkyl groups such as benzyl group or phenylethyl group;
1,3-Butadienyl group, isoprenyl (2-methyl-1,3-butadienyl) group, piperylenyl (1,3-pentadienyl) group, 2,4-hexadienyl group, 1,4-diphenyl-1,3-pentadienyl group Or a diene divalent derivative group such as a cyclopentadienyl group;
Etc. can be exemplified.

The halogen-containing groups indicated by R ³ and R ⁴ include
Halogen-containing hydrocarbon groups such as trifluoromethyl, pentafluoroethyl, 1,1,1,3,3,3-hexafluoro-2-propyl or nonafluoro-t-butyl;
Halogen-containing aryl groups such as pentafluorophenyl and pentachlorophenyl;
Etc. can be exemplified.

The oxygen-containing groups indicated by R ³ and R ⁴ include
An alcoholic group such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group or a t-butoxy group;
Allyloxy groups such as phenoxy group, 2,6-dimethylphenoxy group or 2,4,6-trimethylphenoxy group;
Ester groups such as acetyloxy group, benzoyloxy group, methoxycarbonyl group, phenoxycarbonyl group or p-chlorophenoxycarbonyl group;
Ether group;
Acrylic groups such as formyl groups, acetyl groups, benzoyl groups, p-chlorobenzoyl groups or p-methoxybenzoyl groups;
Carboxyl group;
Carbonate group;
Hydroxy group;
Peroxy group;
Carboxylic acid anhydride group;
Frill group;
Etc. can be exemplified.

The sulfur-containing groups indicated by R ³ and R ⁴ include
Mercapto group;
Thioester groups such as acetylthio group, benzoylthio group, methylthiocarbonyl group or phenylthiocarbonyl group;
Dithioester group; Alkylthio group such as methylthio group or ethylthio group;
Arylthio groups such as phenylthio groups, methylphenylthio groups or naphthylthio groups;
Thioacyl group;
Thioether group;
Thiocyanate group;
Isothiocyanate group;
Sulfonate ester groups such as methyl sulfonate group, ethyl sulfonate group or phenyl sulfonate group;
Sulfonamide groups such as phenylsulfonamide groups, N-methylsulfonamide groups or N-methyl-p-toluenesulfonamide groups;
Thiocarboxyl group;
Dithiocarboxyl group;
Sulfonic group;
Sulfonyl group;
Sulfinyl group;
Sulfenyl group;
Etc. can be exemplified.

The nitrogen-containing groups indicated by R ³ and R ⁴ include
Amino group;
Alkylamino groups such as dimethylamino groups or ethylmethylamino groups;
Arylamino groups such as diphenylamino groups;
Imine group;
Alkylimino groups such as methylimino groups, ethylimino groups, propylimino or butylimino groups;
Arylimino groups such as phenylimino groups;
Amide group;
Alkylamide groups such as acetamide groups or N-methylacetamide groups;
Arylamide groups such as N-methylbenzamide groups;
Imide group;
Alkylimide groups such as acetimide groups;
Arylimide groups such as benzimide groups;
Pyrrolidine group;
Hydrazino group;
Hydrazono group;
Nitro group;
Nitroso group;
Cyano group;
Isocyano group;
Cyanic acid ester group;
Amidino group;
Diazo group;
Examples thereof include those in which the amino group is an ammonium salt.
As a substitution product of the nitrogen-containing group shown by R ³ and R ⁴ ,
Examples thereof include a silylamide group and a phosphinamide group.

The phosphorus-containing groups indicated by R ³ and R ⁴ include
Phosfido group;
Phosphoryl group;
Thiophosphoyl group;
Phosphate groups and the like can be exemplified.

The silicon-containing groups indicated by R ³ and R ⁴ include
Alkylsilyl group such as methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group or dimethyl-t-butylsilyl group;
Etc. can be exemplified.

The boron-containing groups indicated by R ³ and R ⁴ include
Bolangyle group;
Volunteer group;
Diboranil group;
Etc. can be exemplified.
As a substitution product of the boron-containing group shown by R ³ and R ⁴ ,
Alkyl group substituted boron represented by (Et) _2B- , (iPr) _2B- , (iBu) _2B- , (Et) _3B , (iPr) _3B or (iBu) _3B , etc.;
It is represented by (C ₆ H ₅ ) ₂ B-, (C ₆ H ₅ ) ₃ B, (C ₆ F ₅ ) ₃ B or (3,5- (CF ₃ ) ₂ C ₆ H ₃ ) ₃ B, etc. Aryl group substituted boron;
Boron halide represented by BCl _2- or BCl ₃ or the like;
Alkyl group-substituted boron halides represented by (Et) BCl-, (iBu) BCl- or (C ₆ H ₅ ) ₂ BCl and the like;
Etc. can be exemplified.
Here, Et represents an ethyl group, iPr represents an isopropyl group, and iBu represents an isobutyl group.

As a substitution product of the aluminum-containing group shown by R ³ and R ⁴ ,
Alkyl group substituted aluminum represented by (Et) ₂ Al-, (iPr) ₂ Al-, (iBu) ₂ Al-, (Et) ₃ Al, (iPr) ₃ Al or (iBu) ₃ Al, etc.;
(C ₆ H ₅ ) ₂ Aryl group-substituted aluminum represented by Al- or the like;
AlCl _2- , or aluminum halide represented by AlCl ₃ or the like;
Alkyl-substituted aluminum halides represented by (Et) AlCl-, (iBu) AlCl-, etc.;
Here, Et represents an ethyl group, iPr represents an isopropyl group, and iBu represents an isobutyl group.

From the group consisting of hydrocarbon groups, halogen ^- containing groups, oxygen ^- containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups, aluminum-containing groups, and their substituents. When the group is selected from the group, it is preferable that the number of carbon atoms of R ³ and R ⁴ is 1 to 20 independently of each other.

It is preferable that R ³ and R ⁴ are independently halogen atoms or hydrocarbon groups, respectively.

When R ³ and R ⁴ are halogen atoms, it is more preferable that R ³ and R ⁴ are independent chlorine atoms, respectively.

When R ³ and R ⁴ are hydrocarbon groups, it is more preferable that R ³ and R ⁴ are independently alkyl groups, and even more preferably methyl groups.

(Transition metal compound (A-2))
The transition metal compound (A-2) is represented by the following formula (II).

In the above formula (II)
M ² represents a transition metal of Group 4 of the periodic table.
Examples of M ² include a titanium atom, a zirconium atom, a hafnium atom, and the like.

M ² is preferably a titanium atom or a zirconium atom, and more preferably a titanium atom.

n ¹ represents an integer of 1 to 3. n ¹ is selected so that the entire transition metal compound (A-2) represented by the formula (II) is electrically neutral, depending on the valence of M ² and the type of X ¹ .
n ¹ is preferably 2.

L independently represents a monovalent anionic ligand in which an atom of Group 15 of the periodic table is a coordinating atom.

L is preferably a monovalent anionic ligand represented by the formula (IV).

In the above formula (IV)
Y represents a group 15 atom of the periodic table. Examples of Y include a nitrogen atom, a phosphorus atom, an arsenic atom, and the like.

Y is preferably a nitrogen atom.

Z represents one kind of atom selected from Group 14, Group 15, or Group 16 of the Periodic Table. Examples of Z include carbon atoms or silicon atoms of Group 14; nitrogen atoms, phosphorus atoms or arsenic atoms of Group 15; oxygen atoms or sulfur atoms of Group 16; and the like.

Z is preferably a carbon atom or a nitrogen atom, and more preferably a carbon atom.

n ³ represents an integer of 1 to 3. n ³ is selected so that the entire monovalent anionic ligand represented by formula ⁽ IV) is electrically neutral, depending on the valence of Z and the type of R18.

n ² is preferably 1 or 2, more preferably 2.

R ¹⁸ is independently composed of hydrogen atom, halogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, silicon-containing group, boron-containing group and aluminum-containing group. Group, as well as groups or atoms selected from the group consisting of their substituents, each of which may be bonded to each other to form a ring, the ring of which is aromatic, including conjugated double bonds. The ring formed may be bonded to a cyclopentadienyl group.

As the halogen ^atom , hydrocarbon group, halogen-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, silicon-containing group, boron-containing group and aluminum-containing group represented by R18, and their substitutions. , R ³ and R ⁴ , halogen atoms, hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups and aluminum-containing groups, and their An example can be exemplified as a substituent.

Examples of the structure in which R ¹⁸ are bonded to each other to form a ring and the formed ring is bonded to a cyclopentadienyl group include the following.

R ¹⁸ is a group consisting of a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group and an aluminum-containing group, and a group consisting of their substituents. When it is a more selected group, the number of carbon atoms of R ¹⁹ is preferably 1 to 20 independently, and more preferably 1 to 10.

Each of R ¹⁸ independently has a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an amide group, an aryl group, an aralkyl group, a silyl group, an alkylamide group, an alkylsilyl group, an arylamide group, a silylamide group and a phosphinoamide group. , And groups of phosphido groups, and preferably atoms or groups selected from the group of substituents thereof.
More preferably, it is an alkyl group, a cycloalkyl group or an aryl group, or a substitute thereof.
It is more preferably a t-butyl group, a tricyclodecane group or a phenyl group, or a substitute thereof.
It is even more preferable that it is a t-butyl group.

X ¹ is independently composed of hydrogen atom, halogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, silicon-containing group, boron-containing group and aluminum-containing group. Indicates a group or atom selected from the group consisting of the group and the group consisting of their substitutions.

As the halogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, silicon-containing group, boron-containing group and aluminum-containing group represented by X ¹ , and their substitutions. , R ³ and R ⁴ , halogen atoms, hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups and aluminum-containing groups, and their An example can be exemplified as a substituent.

A group consisting of ^a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group and an aluminum-containing group, and a group consisting of their substituents. When it is a more selected group, the number of carbon atoms of X ¹ is preferably 1 to 20 independently, and more preferably 1 to 10.

X ¹ is preferably a halogen atom, more preferably a chlorine atom.

R ⁵ to R ⁹ are independently hydrogen atom, halogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, silicon-containing group, boron-containing group and aluminum. It represents a group or atom selected from the group consisting of containing groups and the group consisting of their substituents, and any two or ^three of R5 to ^R9 may be fused to form a ring. The ring to be formed may have aromaticity including a conjugated double bond.

Halogen atoms, hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups and aluminum-containing groups represented by R ⁵ to R ⁹ , and their substitutions. As the body, the halogen atom, the hydrocarbon group, the halogen-containing group, the oxygen-containing group, the sulfur-containing group, the nitrogen-containing group, the phosphorus-containing group, the silicon-containing group, the boron-containing group and the aluminum-containing group represented by R ³ and R ⁴ , In addition, those exemplified as their substitutions can be exemplified.

A group ^consisting of a hydrocarbon group, a halogen ^- containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group and an aluminum-containing group, and their substituents. When the group is selected from the group consisting of, the number of carbon atoms of R ⁵ to R ⁹ is preferably 1 to 20 independently, and more preferably 1 to 10.

R ⁵ to R ⁹ are preferably hydrogen atoms.

(Transition metal compound (A-3))
The transition metal compound (A-3) is represented by the following formula (III).

In the above formula (III)
M ³ indicates a transition metal of Group 4 of the periodic table.
Examples of M ³ include a titanium atom, a zirconium atom, and a hafnium atom.

M ³ is preferably a titanium atom or a zirconium atom, and more preferably a titanium atom.

n ² represents an integer of 1 to 4.
n ² is selected so that the entire transition metal compound (A-3) represented by the formula (III) is electrically neutral, depending on the valence of M ³ and the type of X ² .

n ² is preferably 2.

X ² is an independent group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a silicon-containing group and a boron-containing group, and their substituents. Indicates an atom or group selected from the group consisting of.

As the halogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, silicon-containing group, boron-containing group and aluminum-containing group represented by X ² , and their substitutions. , R ³ and R ⁴ , halogen atoms, hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups and aluminum-containing groups, and their An example can be exemplified as a substituent.

A group consisting of a hydrocarbon group, a halogen ^- containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group and an aluminum-containing group, and a group consisting of their substituents. When it is a more selected group, the number of carbon atoms of X ² is preferably 1 to 20 independently, and more preferably 1 to 10.

X ² is preferably a halogen atom, more preferably a chlorine atom.

R ¹⁰ to R ¹⁷ are independently a group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a silicon-containing group and a boron-containing group, and they. Indicates an atom or group selected from the group consisting of substituents of R10 to ^R14 , and adjacent ones of R10 to ^R14 may be bonded to each other to form a ring, and the formed ring is a conjugated double bond. It may have aromaticity including.

Halogen atoms, hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups and aluminum-containing groups represented by R ¹⁰ to R ¹⁷ , and their substitutions. As the body, the halogen atom, the hydrocarbon group, the halogen-containing group, the oxygen-containing group, the sulfur-containing group, the nitrogen-containing group, the phosphorus-containing group, the silicon-containing group, the boron-containing group and the aluminum indicated by R ³ and R ⁴ are contained. Examples can be given as examples of groups and their substitutions.

R ¹⁰ to R ¹⁷ consist of a group consisting of a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group and an aluminum-containing group, and their substitutions. When the group is selected from the group, the number of carbon atoms of R ¹⁰ to R ¹⁷ is preferably 1 to 20 independently, and more preferably 1 to 10.

As a specific example of the combination of R ¹⁰ to R ¹⁷ , R ¹⁰ to R ¹⁴ and R ¹⁷ are independently composed of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group and a silicon-containing group, and a group thereof. It is an atom or group selected from the group consisting of the substituents of, and ^R15 and ^R16 are independently the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a halogen-containing group, and their substitutions. It is preferably an atom or group selected from the group consisting of.
Adjacent ones of R ¹⁰ to R ¹⁴ may be bonded to each other to form a ring, and the formed ring may have aromaticity including a conjugated double bond.

As a specific example of the combination of R ¹⁰ to R ¹⁷ , R ¹⁰ to R ¹⁴ and R ¹⁷ are independently hydrogen atoms or hydrocarbon groups, and R ¹⁵ and R ¹⁶ are independent hydrogen atoms, respectively. Alternatively, it is more preferably a hydrocarbon group or a halogen-containing hydrocarbon group.

As a specific example of the combination of R ¹⁰ to R ¹⁷ , R ¹⁰ to R ¹⁴ and R ¹⁷ are each independently a hydrogen atom or a cyclic hydrocarbon group to which an alkyl group or two or more substituents are bonded, and It is more preferred that R ¹⁵ and R ¹⁶ are independently hydrogen atoms or hydrocarbon groups or halogen-containing alkyl groups, respectively.

As a specific example of the combination of R ¹⁰ to R ¹⁷ , R ¹⁰ to R ¹⁴ and R ¹⁷ are independently hydrogen atoms or t-butyl groups, and R ¹⁵ and R ¹⁶ are independently hydrogen. It is even more preferred to be an atomic or isopropyl group.

As a specific example of the combination of R ¹⁰ to R ¹⁷ , R ¹⁰ to R ¹⁴ are cyclic hydrocarbon groups to which a hydrogen atom, a branched alkyl group or two or more substituents are independently bonded, respectively, and R ¹⁵ and R ¹⁶ are independently hydrogen, cyclic hydrocarbon group, branched alkyl group or halogen-containing alkyl group, and R ¹⁷ is hydrogen atom, branched alkyl group or halogen-containing alkyl group, respectively. Is preferable.

<Compound (B)>
Compound (B) is
Organometallic compound (B-1),
Reacts with the organic aluminum oxy compound (B-2), the transition metal compound represented by the above formula (I), the transition metal compound represented by the above formula (II), or the transition metal compound represented by the above formula (III). It contains one or more selected from the group consisting of the compound (B-3) forming an ion pair.

(Organometallic compound (B-1))
Examples of the organometallic compound (B-1) (hereinafter, also referred to as “component (B-1)”) include an organoaluminum compound (B-1a) represented by the general formula (B-1a) and a general formula (B-1a). A complex alkyl compound (B-1b) of a Group 1 metal represented by B-1b) and aluminum, and a dialkyl compound (B-) of a Group 2 or Group 12 metal represented by the general formula (B-1c). Included are group 1, 2 and group 12 and 13 organometallic compounds such as 1c).

(B-1a): Ram Al ( _ORb ) _n H _p X _q
In the formula (B-1a), Ra and Rb are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X is a halogen atom, m is 0 <m ≦ 3, and n is. 0 ≦ n <3, p is 0 ≦ p <3, q is a number satisfying 0 ≦ q <3, and m + n + p + q = 3. Examples of the organoaluminum compound (B-1a) include trialkylaluminum such as trimethylaluminum, triethylaluminum and triisobutylaluminum, dialkylaluminum hydride such as diisobutylaluminum hydride, and tricycloalkylaluminum.

(B-1b): M2AlRa ₄
In the formula (B-1b), M2 is Li, Na or K, and Ra is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Examples of the complex alkyl compound (B-1b) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

(B-1c): RaRbM3
In the formula (B-1c), Ra and Rb are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M3 is Mg, Zn or Cd. Examples of the compound (B-1c) include dimethylmagnesium, diethylmagnesium, din-butylmagnesium, ethyl n-butylmagnesium, diphenylmagnesium, dimethylzinc, diethylzinc, din-butylzinc and diphenylzinc.

Among the organometallic compounds (B-1), the organoaluminum compound (B-1a) is preferable.

(Organoaluminium oxy compound (B-2))
As the organoaluminum oxy compound (B-2) (hereinafter, also referred to as “component (B-2)”), conventionally known aluminoxane can be used as it is.
Specifically, the compounds represented by the following general formula [B2-1] and / or the following general formula [B2-2], benzene insoluble described in JP-A-2-78687 and JP-A-2-167305. Examples thereof include organoaluminum oxy compounds of the above, and aluminoxane having two or more kinds of alkyl groups described in JP-A-3-103407.
In the formula, R is a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 2 or more.

Further, examples of the organoaluminum oxy compound (B-2) include modified methylaluminoxane as represented by the following general formula [B2-3].
In the formula, R represents a hydrocarbon group having 1 to 10 carbon atoms, and m and n each independently represent an integer of 2 or more.

This modified methylaluminoxane is prepared using trimethylaluminum and alkylaluminum other than trimethylaluminum. Such compounds are commonly referred to as MMAO. Such MMAOs can be prepared by the methods set forth in US Pat. No. 4,960,878 and US Pat. No. 5,451,584.

Further, as the organoaluminum oxy compound (B-2), an organoaluminum oxy compound containing boron represented by the following general formula [B2-4] can also be mentioned.
In the formula, R ^c represents a hydrocarbon group having 1 to 10 carbon atoms. R ^d may be the same or different from each other and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

As the organoaluminum oxy compound (B-2), methylaluminoxane, which is easily available for commercial products, and MMAO prepared using trimethylaluminum and triisobutylaluminum are preferable. Of these, MMAO having improved solubility in various solvents and storage stability is particularly preferable.

(Compound (B-3) that reacts with the transition metal compound (A) to form an ion pair)

The compound (B-3) that reacts with the transition metal compound (A) to form an ion pair (hereinafter, also referred to as “ionic compound (B-3)” or “component (B-3)”) is particularly characterized. Kaihei 1-501950, JP1-52036, JP 3-179005, JP 3-179006, JP 3-207703, JP 3-207704, USP5321106, etc. Examples thereof include the Lewis acid, the ionic compound, the borane compound and the carbolan compound described in the above. Further, heteropoly compounds and isopoly compounds can also be mentioned. However, the above-mentioned (B-2) organoaluminum oxy compound is not included.

The ionic compound (B-3) preferably includes a boron compound represented by the following general formula [B3-1].
In the formula, Examples of Re ⁺ include H ⁺ , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyllienyl cation, ferrosenium cation having a transition metal, and the like. R ^f to ^Ri may be the same or different from each other, and are substituents selected from hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups. Yes, preferably a substituted aryl group.

Examples of the boron compound represented by the general formula [B3-1] are described in triphenylcarbenium tetrakis (pentafluorophenyl) borate, and [0133] to [0144] of International Publication No. 2015/122414. Can be mentioned.

The method for producing a cyclic olefin-based copolymer of the present embodiment includes a catalyst removing step of removing a catalyst for olefin polymerization.

A cyclic olefin copolymer is formed on the organic phase side by mixing the polymerization reaction solution obtained in the polymerization step with an alkaline aqueous solution such as an aqueous sodium hydroxide solution, and then allowing the mixture to stand until the liquid-liquid interface is separated. , The catalyst is extracted on the alkaline aqueous layer side, respectively, and the olefin copolymer and the catalyst are separated.

The aluminum content of the cyclic olefin-based copolymer obtained by the method for producing the cyclic olefin-based copolymer of the present embodiment is as small as 100 ppm or less.
The mechanism by which the aluminum content of the cyclic olefin-based copolymer can be reduced by the production method of the present embodiment is not clear, but by using a catalyst for olefin polymerization containing the transition metal compound (A) and the compound (B). , The liquid viscosity of the polymerization reaction solution can be reduced, or the precipitation of the polymer in the polymerization solution can be suppressed, the catalyst can be easily extracted to the alkaline aqueous layer side, and the catalyst-derived aluminum can be obtained from the cyclic olefin copolymer. It is thought that this is because it is removed efficiently.

The upper limit of the aluminum content of the cyclic olefin-based copolymer obtained by the method for producing the cyclic olefin-based copolymer of the present embodiment is preferably 70 ppm or less, more preferably 50 ppm or less.
Further, the lower limit of the aluminum content of the cyclic olefin-based copolymer obtained by the method for producing the cyclic olefin-based copolymer of the present embodiment is not particularly limited, but is usually 0.0001 ppm or more.

The method for producing a cyclic olefin-based copolymer of the present embodiment may include other steps such as a precipitation step of precipitating the obtained polymer.

[Cyclic olefin copolymer]
The cyclic olefin-based copolymer of the present embodiment has a constitutional unit (X) derived from an α-olefin (X') having 2 to 20 carbon atoms and a constitution derived from a cyclic olefin (Y') having no aromatic ring. A cyclic olefin-based copolymer having a unit (Y) and a structural unit (Z) derived from a cyclic olefin (Z') having an aromatic ring.
The aluminum content of the cyclic olefin-based copolymer is 100 ppm or less.

The structural unit (X) according to the present embodiment may be linear or branched, and may be ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, Linear α-olefins with 2 to 20 carbon atoms such as 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; 3-methyl-1-butene, 3-methyl-1-pentene, 3- Ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, Examples thereof include branched α-olefins having 4 to 20 carbon atoms such as 3-ethyl-1-hexene. Among these, a linear α-olefin having 2 to 4 carbon atoms is preferable, and ethylene is particularly preferable. Such linear or branched α-olefins can be used alone or in combination of two or more.

The cyclic olefin-based copolymer of the present embodiment has a total content of the structural unit (X), the structural unit (Y) and the structural unit (Z) in the cyclic olefin-based copolymer as 100 mol%. The content of the structural unit (X) in the cyclic olefin-based copolymer is preferably 10 mol% or more and 80 mol% or less, more preferably 30 mol% or more and 75 mol% or less, and further preferably 40 mol% or more and 70 mol. % Or less.
When the content of the structural unit (X) is at least the above lower limit value, the heat resistance and dimensional stability of the molded product obtained from the cyclic olefin-based copolymer of the present embodiment can be improved. Further, when the content of the structural unit (X) is not more than the upper limit value, the transparency of the obtained molded product can be improved.
In the present embodiment, the content of the structural unit (X) can be measured by, for example, ¹ H-NMR or ¹³ C-NMR.

The structural unit (Y) according to the present embodiment is a composition derived from a compound represented by the following formula (V) from the viewpoint of further improving the refractive index of the molded product obtained from the cyclic olefin-based copolymer of the present embodiment. It is preferable to include a unit.

In the above formula (V)
n ¹⁰¹ indicates 0 or 1 and represents
m ¹⁰¹ indicates 0 or a positive integer,
q ¹⁰¹ indicates 0 or 1 and represents
R ¹⁰¹ to R ¹¹⁸ and R ^a and R ^b each independently represent a hydrocarbon group which may be substituted with a hydrogen atom, a halogen atom or a halogen atom, and R ¹¹⁵ to R ¹¹⁸ are bonded to each other to form a single ring. Alternatively, a polycycle may be formed, and the monocyclic or polycycle may have a double bond, and an alkylidene group may be formed between R ¹¹⁵ and R ¹¹⁶ , or between R ¹¹⁷ and R ¹¹⁸ . May be formed. However, it does not contain an aromatic ring.

Among these, the structural unit (Y) according to the present embodiment is a structural unit derived from bicyclo [2.2.1] -2-heptene, tetracyclo [4.4.0.12,5.17,10]. -At least one constituent unit selected from the constituent units derived from -3-dodecene and the constituent units derived from hexacyclo [6,6,1,13,6,110,13,02,7,09,14] heptadecene-4. Is preferably contained, and is selected from the constituent units derived from bicyclo [2.2.1] -2-heptene and the constituent units derived from tetracyclo [4.4.0.12,5.17,10] -3-dodecene. It is more preferable to contain at least one structural unit, and it is particularly preferable to include a structural unit derived from tetracyclo [4.4.0.12,5.17,10] -3-dodecene.

The structural unit (Y) according to the present embodiment is selected from the group consisting of the compound represented by the following formula (VI), the compound represented by the following formula (VII), and the compound represented by the following formula (VIII). It is preferable to contain a structural unit derived from one or more compounds to be used.

In the above formula (VI)
n ²⁰¹ and q ²⁰¹ are independently 0, 1 or 2, respectively.
R ²⁰¹ to R ²¹⁷ are hydrocarbon groups having 1 to 20 carbon atoms which may be independently substituted with a hydrogen atom, a halogen atom excluding a fluorine atom, or a halogen atom excluding a fluorine atom.
One of R ²¹⁰ to R ²¹⁷ is a bond,
When q ²⁰¹ = 0, R ²¹⁰ and R ²¹¹ , R ²¹¹ and R ²¹² , R ²¹² and R ²¹³ , R ²¹³ and R ²¹⁴ , R ²¹⁴ and R ²¹⁵ , R ²¹⁵ and R ²¹⁰ are monocyclic or are coupled to each other. It may form a polycycle,
When q ²⁰¹ = 1 or 2, R ²¹⁰ and R ²¹¹ , R ²¹¹ and R ²¹⁷ , R ²¹⁷ and R ²¹⁷ , R ²¹⁷ and R ²¹² , R ²¹² and R ²¹³ , R ²¹³ and R ²¹⁴ , R ²¹⁴ and R ^215. , R ²¹⁵ and R ²¹⁶ , R ²¹⁶ and R ²¹⁶ , R ²¹⁶ and R ²¹⁰ may be coupled to each other to form a monocyclic or polycyclic.
The monocyclic or polycyclic may have a double bond,
The monocyclic ring or the polycyclic ring may be an aromatic ring.

In the above formula (VII)
n ²⁰² and m ²⁰¹ are independently 0, 1 or 2, respectively.
q ²⁰² is 1, 2 or 3 and
R ²¹⁸ to R ²³¹ are hydrocarbon groups having 1 to 20 carbon atoms which may be independently substituted with a hydrogen atom, a halogen atom excluding a fluorine atom, or a halogen atom excluding a fluorine atom.
When q ²⁰² = 1, R ²²⁸ and R ²²⁹ , R ²²⁹ and R ²³⁰ , and R ²³⁰ and R ²³¹ may be bonded to each other to form a monocyclic or polycyclic ring.
When q ²⁰² = 2 or 3, R ²²⁸ and R ²²⁸ , R ²²⁸ and R ²²⁹ , R ²²⁹ and R ²³⁰ , R ²³⁰ and R ²³¹ and R ²³¹ and R ²³¹ combine with each other to form a monocyclic or polycyclic. You may be
The monocyclic or polycyclic may have a double bond,
The monocyclic ring or the polycyclic ring may be an aromatic ring.

In the above formula (VIII)
q ²⁰³ is 1, 2 or 3,
^R232 to ^R239 are hydrocarbon groups having 1 to 20 carbon atoms which may be independently substituted with a hydrogen atom, a halogen atom excluding a fluorine atom, or a halogen atom excluding a fluorine atom.
When q ²⁰³ = 1, R ²³⁶ and R ²³⁷ , R ²³⁷ and R ²³⁸ , and R ²³⁸ and R ²³⁹ may be bonded to each other to form a monocyclic or polycyclic ring.
When q ²⁰³ = 2 or 3, R ²³⁶ and R ²³⁶ , R ²³⁶ and R ²³⁷ , R ²³⁷ and R ²³⁸ , R ²³⁸ and R ²³⁹ , and R ²³⁹ and R ²³⁹ combine with each other to form a monocyclic or polycyclic. May be
The monocyclic or polycyclic may have a double bond,
The monocyclic ring or the polycyclic ring may be an aromatic ring.

The hydrocarbon groups having 1 to 20 carbon atoms in the structural unit (Z) of the present embodiment are independently, for example, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and a cycloalkyl group having 3 to 15 carbon atoms. Examples include aromatic hydrocarbon groups. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group, and the cycloalkyl group includes cyclohexyl. Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a trill group, a naphthyl group, a benzyl group and a phenylethyl group, or an aralkyl group. These hydrocarbon groups may be substituted with halogen atoms other than fluorine atoms.

Among these, as the cyclic olefin having an aromatic ring according to the present embodiment, one having one aromatic ring is preferable, and for example, at least one selected from benzonorbornadiene, indenenorbornene and methylphenylnorbornene is preferable. ..

Examples of the cyclic olefin having an aromatic ring according to the present embodiment include a compound represented by the following formula (VI'), a compound represented by the following formula (VII'), and the following formula (VIII'). The compounds shown may also be mentioned. The cyclic olefins having these aromatic rings may be used alone or in combination of two or more.

In the above formula (VI'), the above formula (VII'), and the above formula (VIII'), m ³⁰¹ , n ³⁰¹ and n ³⁰² are 0, 1 or 2, and R ³⁰¹ to R ³³⁶ are independently hydrogen. A hydrocarbon group having 1 to 20 carbon atoms which may be substituted with an atom, a halogen atom excluding a fluorine atom, or a halogen atom excluding a fluorine atom, R ³¹⁰ and R ³¹¹ and R ³¹¹ and R ³¹² , R ^312. And R ³¹³ , R ³¹³ and R ³¹⁴ , R ³²⁵ and R ³²⁶ , R ³²⁶ and R ³²⁷ , R ³²⁷ and R ³²⁸ , R ³³³ and R ³³⁴ , R ³³⁴ and R ³³⁵ , R ³³⁵ and R ³³⁶ combined with each other. A single ring may be formed, and the single ring may have a double bond.

Further, in the above formula (VI'), the above formula (VII'), and the above formula (VIII'), m ³⁰¹ is preferably 0 or 1, more preferably 1. n ³⁰¹ and n ³⁰² are preferably 0 or 1, more preferably 0. R ³⁰¹ to R ³³⁶ are preferably hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms, and more preferably hydrogen atoms.

Further, the hydrocarbon groups having 1 to 20 carbon atoms in the above formula (VI'), the above formula (VII'), and the above formula (VIII') are independently, for example, alkyl groups having 1 to 20 carbon atoms. , Cycloalkyl groups having 3 to 15 carbon atoms, aromatic hydrocarbon groups and the like. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group, and the cycloalkyl group includes cyclohexyl. Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a trill group, a naphthyl group, a benzyl group and a phenylethyl group, or an aralkyl group. These hydrocarbon groups may be substituted with halogen atoms other than fluorine atoms.

Among these, as the cyclic olefin having an aromatic ring according to the present embodiment, one having one aromatic ring is preferable, and for example, at least one selected from benzonorbornadiene, indenenorbornene and methylphenylnorbornene is preferable. ..

The cyclic olefin copolymer of the present embodiment is contained in the cyclic olefin copolymer when the total content of the structural unit (Y) and the structural unit (Z) in the cyclic olefin copolymer is 100 mol%. The content of the structural unit (Z) is preferably 5 mol% or more and 95 mol% or less, more preferably 10 mol% or more and 90 mol% or less, still more preferably 20 mol% or more and 80 mol% or less, still more preferably 30. It is mol% or more and 79 mol% or less, and even more preferably 40 mol% or more and 78 mol% or less.
When the content of the structural unit (Z) is at least the above lower limit value, the Abbe number can be further reduced while maintaining a high refractive index in the molded product obtained from the cyclic olefin copolymer according to the present embodiment. can. Further, when the content of the structural unit (Z) is not more than the upper limit value, the balance between the refractive index and the Abbe number of the molded product obtained from the cyclic olefin copolymer according to the present embodiment is to be improved. Can be done.
In the present embodiment, the content of the structural unit (Y) and the structural unit (Z) can be measured by, for example, ¹ H-NMR or ¹³ C-NMR.

The copolymerization type of the cyclic olefin-based copolymer according to the present embodiment is not particularly limited, and examples thereof include random copolymers and block copolymers. It is a random copolymer from the viewpoint of being able to obtain a molded product having excellent optical properties such as transparency, Abbe number, refractive index and double refractive index of the molded product obtained from the cyclic olefin copolymer of the present embodiment. Is preferable.

The glass transition temperature (Tg) of the cyclic olefin-based copolymer according to the present embodiment, which is measured by a differential scanning calorimeter (DSC), is the transparency of the molded product obtained from the cyclic olefin copolymer of the present embodiment. From the viewpoint of further improving heat resistance while maintaining good haze, number of polymers, double refraction, refractive index, etc., it is preferably 120 ° C. or higher and 180 ° C. or lower, more preferably 130 ° C. or higher and 170 ° C. or lower, and further preferably. It is 140 ° C. or higher and 160 ° C. or lower.

The ultimate viscosity [η] (in 135 ° C. decalin) of the cyclic olefin-based copolymer according to the present embodiment is, for example, 0.05 to 5.0 dl / g, preferably 0.2 to 4.0 dl / g. Yes, more preferably 0.3 to 2.0 dl / g, and particularly preferably 0.4 to 1.0 dl / g.

The aluminum content of the cyclic olefin-based copolymer according to the present embodiment is 100 ppm or less, preferably 70 ppm or less, and more preferably 50 ppm or less.

The use of the cyclic olefin-based copolymer according to the present embodiment is not particularly limited, and can be used for films, sheets, lenses, containers and the like.
The aluminum content of the cyclic olefin-based copolymer according to the present embodiment is as small as 100 ppm or less, and the adverse effects on the color tone and physical properties when molding the cyclic olefin-based copolymer are suppressed. It can be suitably used for applications that require transparency, such as containers for aluminum.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted.
Further, the present invention is not limited to the above-described embodiment, and modifications, improvements, and the like to the extent that the object of the present invention can be achieved are included in the present invention.

Hereinafter, embodiments of the present invention will be specifically described based on examples, but the embodiments of the present invention are not limited to these examples.

[Example 1]
After passing nitrogen as an inert gas at a flow rate of 100 Nl / hr for 30 minutes in a glass reaction vessel having a volume of 2000 ml equipped with a stirrer, the reagent of (i-1) below is supplied in the following amount and at 600 rpm. The solvent temperature was raised to 50 ° C. while stirring the polymerization solvent.

(I-1)
Cyclohexane / hexane (3/1) mixed solvent: 845 ml
Cyclohexane / hexane (3/1) mixed solution of triisobutylaluminum (hereinafter referred to as TiBAL) (concentration 97.6 g / L): 88 ml
Tetracyclododecene (hereinafter referred to as TD): 30 ml
Benzodiorbornadiene (hereinafter referred to as BNBD): 37 ml

After the temperature of the solvent reaches a predetermined temperature, the flowing gas is switched from nitrogen to ethylene / hydrogen, ethylene is circulated at a flow rate of 150 Nl / hr, and hydrogen is circulated at a flow rate of 5.0 Nl / hr (flow rate ratio 30/1). The reagent of (ii-1) was continuously supplied at the following supply rate, and the polymerization solution was polymerized while being drained as needed so as to keep the liquid level constant.

(Ii-1)
Cyclohexane / hexane (3/1) mixed solvent: 1280 ml / hr
TiBAL cyclohexane / hexane (3/1) mixed solution (concentration 97.6 g / L): 176 ml / hr
Cyclohexane / hexane (3/1) mixed solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate (hereinafter referred to as borate (1)) (concentration 18.4 g / L): 173 ml / hr
Toluene solution (concentration 3.04 g / L) of isopropyridene cyclopentadienyl-9-fluorenyl zirconium dimethyl (hereinafter referred to as transition metal compound (1)): 111 ml / hr.
TD: 134 ml / hr
BNBD: 126 ml / hr

The transition metal compound (1) corresponds to the transition metal compound (A-1).

After 1 hour and 30 minutes have passed from the start of charging the reagent of (ii-1), the solution in the reaction vessel is collected over 30 minutes, and the collected solution is brought into contact with 6.9 g of methanol to form a cyclic olefin system. A copolymer solution was obtained.

500 mL of the obtained cyclic olefin-based copolymer solution was placed in a glass container equipped with a stirrer. The same volume of sodium hydroxide aqueous solution (1.0% by mass) was charged and stirred, and after waiting for the liquid-liquid interface to separate, the aqueous layer portion was drained. The same operation was carried out with ion-exchanged water to obtain a catalyst-removed solution.

270 g of cyclohexane was charged and diluted with respect to 50 g of the obtained catalyst-removed solution. Then, a diluted catalyst-removed solution was gradually added to 1700 mL of agitated acetone to precipitate a cyclic olefin-based copolymer. The precipitated cyclic olefin-based copolymer was recovered by suction filtration and dried in a vacuum dryer at 130 ° C. for 10 hours to obtain 4.75 g of the cyclic olefin-based copolymer.

[Example 2]
A cyclic olefin-based copolymer solution was obtained in the same manner as in Example 1 except for the following points.
-The point where the reagent of the above (i-1) was replaced with the reagent of the following (i-2) -The point where the reagent of the above (ii-1) was replaced with the reagent of the following (ii-2) -The point of the following ( The point where the solution in the reaction vessel was collected over 1 hour after 3 hours had passed from the start of charging the reagent of ii-2) ・ The point where the solution collected from the reaction vessel was brought into contact with 13.8 g of methanol.

(I-2)
Cyclohexane / hexane (3/1) mixed solvent: 771 ml
Cyclohexane / hexane (3/1) mixed solution of TiBAL (concentration 97.6 g / L): 176 ml
TD: 23 ml
BNBD: 31 ml

(Ii-2)
Cyclohexane / hexane (3/1) mixed solvent: 544 ml / hr
TiBAL cyclohexane / hexane (3/1) mixed solution (concentration 97.6 g / L): 176 ml / hr
Borate (1) cyclohexane / hexane (3/1) mixed solution (concentration 8.2 g / L): 79 ml / hr
Toluene solution of transition metal compound (1) (concentration 1.93 g / L): 72 ml / hr
TD: 67 ml / hr
BNBD: 63 ml / hr

From 500 mL of the obtained cyclic olefin-based copolymer solution, a catalyst-removed solution was obtained in the same manner as in Example 1.

393 g of cyclohexane was charged and diluted with respect to 50 g of the obtained catalyst-removed solution. Then, a diluted catalyst-removed solution was gradually added to 2350 mL of agitated acetone to precipitate a cyclic olefin-based copolymer. The precipitated cyclic olefin-based copolymer was recovered by suction filtration and dried in a vacuum dryer at 130 ° C. for 10 hours to obtain 6.65 g of the cyclic olefin-based copolymer.

[Example 3]
A cyclic olefin-based copolymer solution was obtained in the same manner as in Example 1 except for the following points.
-The point where the reagent of the above (i-1) was replaced with the reagent of the following (i-3) -The point where the reagent of the above (ii-1) was replaced with the reagent of the following (ii-3)

(I-3)
Cyclohexane / hexane (3/1) mixed solvent: 842 ml
Cyclohexane / hexane (3/1) mixed solution of TiBAL (concentration 97.6 g / L): 88 ml
TD: 43 ml
BNBD: 28 ml

(Ii-3)
Cyclohexane / hexane (3/1) mixed solvent: 1275 ml / hr
TiBAL cyclohexane / hexane (3/1) mixed solution (concentration 97.6 g / L): 176 ml / hr
Borate (1) cyclohexane / hexane (3/1) mixed solution (concentration 20.3 g / L): 157 ml / hr
Toluene solution of transition metal compound (1) (concentration 2.94 g / L): 115 ml / hr
TD: 184 ml / hr
BNBD: 93 ml / hr

From 500 mL of the obtained cyclic olefin-based copolymer solution, a catalyst-removed solution was obtained in the same manner as in Example 1.

328 g of cyclohexane was charged and diluted with respect to 50 g of the obtained catalyst-removed solution. Then, a diluted catalyst-removed solution was gradually added to 2000 mL of agitated acetone to precipitate a cyclic olefin-based copolymer. The precipitated cyclic olefin-based copolymer was recovered by suction filtration and dried in a vacuum dryer at 130 ° C. for 10 hours to obtain 5.67 g of the cyclic olefin-based copolymer.

[Example 4]
A cyclic olefin-based copolymer solution was obtained in the same manner as in Example 1 except for the following points.
-The point where the reagent of the above (i-1) was replaced with the reagent of the following (i-4) -The point where the reagent of the above (ii-1) was replaced with the reagent of the following (ii-4)

(I-4)
Cyclohexane / hexane (3/1) mixed solvent: 850 ml
Cyclohexane / hexane (3/1) mixed solution of TiBAL (concentration 97.6 g / L): 88 ml
Tetracyclododecene (hereinafter referred to as TD): 27 ml
Benzodiorbornadiene (hereinafter referred to as BNBD): 36 ml

(Ii-4)
Cyclohexane / hexane (3/1) mixed solvent: 1511 ml / hr
TiBAL cyclohexane / hexane (3/1) mixed solution (concentration 97.6 g / L): 176 ml / hr
Borate (1) cyclohexane / hexane (3/1) mixed solution (concentration 20.3 g / L): 74 ml / hr
Toluene solution of transition metal compound (1) (concentration 2.94 g / L): 40 ml / hr
TD: 98 ml / hr
BNBD: 101 ml / hr

From 500 mL of the obtained cyclic olefin-based copolymer solution, a catalyst-removed solution was obtained in the same manner as in Example 1.

164 g of cyclohexane was charged and diluted with respect to 50 g of the obtained catalyst-removed solution. Then, the cyclic olefin-based copolymer was precipitated by gradually adding the diluted catalyst-removed solution to 1250 mL of the agitated aceto. The precipitated cyclic olefin-based copolymer was recovered by suction filtration and dried in a vacuum dryer at 130 ° C. for 10 hours to obtain 3.21 g of the cyclic olefin-based copolymer.

[Example 5]
A cyclic olefin-based copolymer solution was obtained in the same manner as in Example 1 except for the following points.
-The above reagent (i-1) was replaced with the following reagent (i-5).-Ethylene was circulated at a flow rate of 156 Nl / hr and hydrogen at a flow rate of 1.44 l / hr (flow rate ratio 108/1). Point-The point where the reagent of (ii-1) above was replaced with the reagent of (ii-5) below-The point where the solution collected from the reaction vessel was brought into contact with 0.7 g of methanol.

(I-5)
Cyclohexane / hexane (3/1) mixed solvent: 907 ml
Cyclohexane / hexane (3/1) mixed solution of TiBAL (concentration 97.6 g / L): 9 ml
TD: 28 ml
BNBD: 56 ml

(Ii-5)
Cyclohexane / hexane (3/1) mixed solvent: 1564 ml / hr
TiBAL cyclohexane / hexane (3/1) mixed solution (concentration 97.6 g / L): 18 ml / hr
Borate (1) cyclohexane / hexane (3/1) mixed solution (concentration 18.4 g / L): 90 ml / hr
Toluene solution (concentration 2.51 g / L) of diphenylmethylene cyclopentadienyl-9-fluorenyl zirconium dichloride (hereinafter referred to as transition metal compound (2)): 99 ml / hr.
TD: 88 ml / hr
BNBD: 142 ml / hr

The transition metal compound (2) corresponds to the transition metal compound (A-1).

From 500 mL of the obtained cyclic olefin-based copolymer solution, a catalyst-removed solution was obtained in the same manner as in Example 1.

To 50 g of the obtained catalyst-removed solution, 123 g of cyclohexane was charged and diluted. Then, a diluted catalyst-removed solution was gradually added to 920 mL of agitated acetone to precipitate a cyclic olefin-based copolymer. The precipitated cyclic olefin-based copolymer was recovered by suction filtration and dried in a vacuum dryer at 130 ° C. for 10 hours to obtain 2.60 g of the cyclic olefin-based copolymer.

[Example 6]
A cyclic olefin-based copolymer solution was obtained in the same manner as in Example 1 except for the following points.
-The point where the reagent of the above (i-1) was replaced with the reagent of the following (i-6) -The point where the reagent of the above (ii-1) was replaced with the reagent of the following (ii-6) -From the reaction vessel The point where the collected solution was brought into contact with 1.4 g of methanol.

(I-6)
Cyclohexane / hexane (3/1) mixed solvent: 884 ml
Cyclohexane / hexane (3/1) mixed solution of TiBAL (concentration 97.6 g / L): 18 ml
TD: 56 ml
BNBD: 42 ml

(Ii-6)
Cyclohexane / hexane (3/1) mixed solvent: 1494 ml / hr
Cyclohexane / hexane (3/1) mixed solution of TiBAL (concentration 97.6 g / L): 37 ml / hr
Borate (1) cyclohexane / hexane (3/1) solution solution (concentration 32.2 g / L): 103 ml / hr
Toluene solution (concentration 4.66 g / L) of isopropyridenecyclopentadienyl-3,6-di-t-butyl-9-fluorenyl zirconium dichloride (hereinafter referred to as transition metal compound (3)): 105 ml / hr
TD: 148 ml / hr
BNBD: 112 ml / hr

The transition metal compound (3) corresponds to the transition metal compound (A-1).

From 500 mL of the obtained cyclic olefin-based copolymer solution, a catalyst-removed solution was obtained in the same manner as in Example 1.

133 g of cyclohexane was charged and diluted with respect to 50 g of the obtained catalyst-removed solution. Then, a diluted catalyst-removed solution was gradually added to 970 mL of agitated acetone to precipitate a cyclic olefin-based copolymer. The precipitated cyclic olefin-based copolymer was recovered by suction filtration and dried in a vacuum dryer at 130 ° C. for 10 hours to obtain 2.75 g of the cyclic olefin-based copolymer.

[Example 7]
A cyclic olefin-based copolymer solution was obtained in the same manner as in Example 1 except for the following points.
-The above reagent (i-1) was replaced with the following reagent (i-7).-Ethylene was circulated at a flow rate of 156 Nl / hr and hydrogen at a flow rate of 0.96 Nl / hr (flow ratio 163/1). Point-The point where the reagent of (ii-1) above was replaced with the reagent of (ii-7) below-The point where the solution collected from the reaction vessel was brought into contact with 0.6 g of methanol.

(I-7)
Cyclohexane / hexane (3/1) mixed solvent: 942 ml
Cyclohexane / hexane (3/1) mixed solution of TiBAL (concentration 97.6 g / L): 7 ml
TD: 21 ml
BNBD: 31 ml

(Ii-7)
Cyclohexane / hexane (3/1) mixed solvent: 1631 ml / hr
TiBAL cyclohexane / hexane (3/1) mixed solution (concentration 97.6 g / L): 14 ml / hr
Borate (1) cyclohexane / hexane (3/1) solution solution (concentration 18.4 g / L): 55 ml / hr
Toluene solution (concentration 1.53 g / L) of diphenylmethylenecyclopentadienylindenyl zirconium zirconium dichloride (hereinafter referred to as transition metal compound (4)): 91 ml / hr.
TD: 102 ml / hr
BNBD: 107 ml / hr

The transition metal compound (4) corresponds to the transition metal compound (A-1).

From 500 mL of the obtained cyclic olefin-based copolymer solution, a catalyst-removed solution was obtained in the same manner as in Example 1.

239 g of cyclohexane was charged and diluted with respect to 50 g of the obtained catalyst-removed solution. Then, a diluted catalyst-removed solution was gradually added to 1550 mL of agitated acetone to precipitate a cyclic olefin-based copolymer. The precipitated cyclic olefin-based copolymer was recovered by suction filtration and dried in a vacuum dryer at 130 ° C. for 10 hours to obtain 4.34 g of the cyclic olefin-based copolymer.

[Example 8]
A cyclic olefin-based copolymer solution was obtained in the same manner as in Example 1 except for the following points.
-The above reagent (i-1) was replaced with the following reagent (i-8).-Ethylene was circulated at a flow rate of 156 Nl / hr and hydrogen at a flow rate of 1.44 Nl / hr (flow ratio 108/1). Point-The point where the reagent of (ii-1) above was replaced with the reagent of (ii-8) below-The point where the solution collected from the reaction vessel was brought into contact with 0.7 g of methanol.

(I-8)
Cyclohexane / hexane (3/1) mixed solvent: 964 ml
Cyclohexane / hexane (3/1) mixed solution of TiBAL (concentration 97.6 g / L): 9 ml
TD: 10 ml
BNBD: 17 ml

(Ii-8)
Cyclohexane / hexane (3/1) mixed solvent: 1651 ml / hr
Cyclohexane / hexane (3/1) mixed solution of TiBAL (concentration 97.6 g / L): 17 ml / hr
Borate (1) cyclohexane / hexane (3/1) solution solution (concentration 18.6 g / L): 84 ml / hr
Toluene solution (concentration 1.58 g / L) of bis-t-butylketimidcyclopentadienyl titanium dichloride (hereinafter referred to as transition metal compound (5)): 87 ml / hr.
TD: 86 ml / hr
BNBD: 75 ml / hr

The transition metal compound (5) corresponds to the transition metal compound (A-2).

From 500 mL of the obtained cyclic olefin-based copolymer solution, a catalyst-removed solution was obtained in the same manner as in Example 1.

257 g of cyclohexane was charged and diluted with respect to 50 g of the obtained catalyst-removed solution. Then, a diluted catalyst-removed solution was gradually added to 1650 mL of agitated acetone to precipitate a cyclic olefin-based copolymer. The precipitated cyclic olefin-based copolymer was recovered by suction filtration and dried in a vacuum dryer at 130 ° C. for 10 hours to obtain 4.61 g of the cyclic olefin-based copolymer.

[Example 9]
A cyclic olefin-based copolymer solution was obtained in the same manner as in Example 1 except for the following points.
-The above reagent (i-1) was replaced with the following reagent (i-8).-Eethylene was circulated at a flow rate of 156 Nl / hr and hydrogen at a flow rate of 0.24 Nl / hr (flow ratio 650/1). Point-The point where the reagent of (ii-1) above was replaced with the reagent of (ii-8) below-The point where the solution collected from the reaction vessel was brought into contact with 0.6 g of methanol.

(I-9)
Cyclohexane / hexane (3/1) mixed solvent: 655 ml
Cyclohexane / hexane (3/1) mixed solution of TiBAL (concentration 97.6 g / L): 7 ml
TD: 5 ml
BNBD: 23 ml

(Ii-9)
Cyclohexane / hexane (3/1) mixed solvent: 1329 ml / hr
TiBAL cyclohexane / hexane (3/1) mixed solution (concentration 97.6 g / L): 14 ml / hr
Borate (1) cyclohexane / hexane (3/1) solution solution (concentration 16.1 g / L): 223 ml / hr
Toluene solution (concentration 1.83 g / L) of 3,5-bismethylethyl-1-pyrazolate-t-butylcyclopentadienyl titanium dichloride (hereinafter referred to as transition metal compound (6)): 278 ml / hr.
TD: 68 ml / hr
BNBD: 88 ml / hr

The transition metal compound (6) corresponds to the transition metal compound (A-3).

From 500 mL of the obtained cyclic olefin-based copolymer solution, a catalyst-removed solution was obtained in the same manner as in Example 1.

To 50 g of the obtained catalyst-removed solution, 210 g of cyclohexane was charged and diluted. Then, a diluted catalyst-removed solution was gradually added to 1370 mL of agitated acetone to precipitate a cyclic olefin-based copolymer. The precipitated cyclic olefin-based copolymer was recovered by suction filtration and dried in a vacuum dryer at 130 ° C. for 10 hours to obtain 3.90 g of the cyclic olefin-based copolymer.

[Comparative Example 1]
A cyclic olefin-based copolymer solution was obtained in the same manner as in Example 1 except for the following points.
-The above reagent (i-1) was replaced with the following reagent (i-1').-Ethylene was circulated at a flow rate of 150 Nl / hr and hydrogen at a flow rate of 3.2 Nl / hr (flow rate ratio 47/1). -Points where the reagent of (ii-1) above was replaced with the reagent of (ii-1') below-Points where the solution collected from the reaction vessel was brought into contact with 2.0 g of methanol.

(I-1')
Cyclohexane / hexane (3/1) mixed solvent: 932 ml
Toluene solution of methylaluminoxane (concentration 6.5% by mass as the content of organoaluminum oxy compound): 6 ml
TD: 20 ml
BNBD: 24 ml

(Ii-1')
Cyclohexane / hexane (3/1) mixed solvent: 1865 ml / hr
Toluene solution of methylaluminoxane (concentration 6.5% by mass as the content of organoaluminum oxy compound): 12 ml / hr
TD: 40 ml / hr
BNBD: 47 ml / hr
Toluene solution (concentration 1.78 g / L) of bis- [N- (3-phenylsalicylidene) -4-t-butylanilinate] titanium dichloride (hereinafter referred to as transition metal compound (7)): 36 ml / hr

From 500 mL of the obtained cyclic olefin-based copolymer solution, a catalyst-removed solution was obtained in the same manner as in Example 1.

To 50 g of the obtained catalyst-removed solution, 83 g of cyclohexane was charged and diluted. Then, a diluted catalyst-removed solution was gradually added to 700 mL of agitated acetone to precipitate a cyclic olefin-based copolymer. The precipitated cyclic olefin-based copolymer was recovered by suction filtration and dried in a vacuum dryer at 130 ° C. for 10 hours to obtain 2.00 g of the cyclic olefin-based copolymer.

[Comparative Example 2]
A cyclic olefin-based copolymer solution was obtained in the same manner as in Example 1 except for the following points.
-The above reagent (i-1) was replaced with the following reagent (i-2').-Ethylene was circulated at a flow rate of 150 Nl / hr and hydrogen at a flow rate of 3.2 Nl / hr (flow rate ratio 47/1). -Points where the reagent of (ii-1) above was replaced with the reagent of (ii-2') below-Points where the solution collected from the reaction vessel was brought into contact with 2.0 g of methanol.

(I-2')
Cyclohexane / hexane (3/1) mixed solvent: 930 ml
Toluene solution of methylaluminoxane (concentration 6.5% by mass as the content of organoaluminum oxy compound): 6 ml
TD: 21 ml
BNBD: 28 ml

(Ii-2')
Cyclohexane / hexane (3/1) mixed solvent: 1860 ml / hr
Toluene solution of methylaluminoxane (concentration 6.5% by mass as the content of organoaluminum oxy compound): 12 ml / hr
TD: 43 ml / hr
BNBD: 55 ml / hr
Toluene solution of transition metal compound (7) (concentration 2.14 g / L): 30 ml / hr

From 500 mL of the obtained cyclic olefin-based copolymer solution, a catalyst-removed solution was obtained in the same manner as in Example 1.

To 50 g of the obtained catalyst-removed solution, 103 g of cyclohexane was charged and diluted. Then, a diluted catalyst-removed solution was gradually added to 800 mL of agitated acetone to precipitate a cyclic olefin-based copolymer. The precipitated cyclic olefin-based copolymer was recovered by suction filtration and dried in a vacuum dryer at 130 ° C. for 10 hours to obtain 2.30 g of the cyclic olefin-based copolymer.

[Comparative Example 3]
A cyclic olefin-based copolymer solution was obtained in the same manner as in Example 1 except for the following points.
-The point where the reagent of the above (i-1) was replaced with the reagent of the following (i-3')-The point where the reagent of the above (ii-1) was replaced with the reagent of the following (ii-3')-Reaction The point where the solution collected from the container was brought into contact with 2.1 g of methanol.

(I-3')
Cyclohexane / hexane (3/1) mixed solvent: 900 ml
Toluene solution of methylaluminoxane (concentration 6.5% by mass as the content of organoaluminum oxy compound): 8 ml,
TD: 6 ml,
BNBD: 14 ml

(Ii-3')
Cyclohexane / hexane (3/1) mixed solvent: 1838 ml / hr
Toluene solution of methylaluminoxane (concentration 6.5% by mass as the content of organoaluminum oxy compound): 13 ml / hr
TD: 49 ml / hr
BNBD: 65 ml / hr
Toluene solution of transition metal compound (7) (concentration 1.93 g / L): 35 ml / hr

From 500 mL of the obtained cyclic olefin-based copolymer solution, a catalyst-removed solution was obtained in the same manner as in Example 1.

To 50 g of the obtained catalyst-removed solution, 33 g of cyclohexane was charged and diluted. Then, a diluted catalyst-removed solution was gradually added to 450 mL of agitated acetone to precipitate a cyclic olefin-based copolymer. The precipitated cyclic olefin-based copolymer was recovered by suction filtration and dried in a vacuum dryer at 130 ° C. for 10 hours to obtain 1.25 g of the cyclic olefin-based copolymer.

[Comparative Example 4]
A cyclic olefin-based copolymer solution was obtained in the same manner as in Comparative Example 3.

From 500 mL of the obtained cyclic olefin-based copolymer solution, a catalyst-removed solution was obtained in the same manner as in Example 1.

A cyclic olefin-based copolymer was precipitated by gradually adding the catalyst-removed solution to 270 mL of agitated acetone with 50 g of the obtained catalyst-removed solution. The precipitated cyclic olefin-based copolymer was recovered by suction filtration and dried in a vacuum dryer at 130 ° C. for 10 hours to obtain 0.75 g of the cyclic olefin-based copolymer.

[Comparative Example 5]
A cyclic olefin-based copolymer solution was obtained in the same manner as in Example 1 except for the following points.
-The point where the reagent of the above (i-1) was replaced with the reagent of the following (i-5')-The point where the reagent of the above (ii-1) was replaced with the reagent of the following (ii-5')-Reaction The point where the solution collected from the container was brought into contact with 2.0 g of methanol.

(I-5')
Cyclohexane / hexane (3/1) mixed solvent: 926 ml
Toluene solution of methylaluminoxane (concentration 6.5% by mass as the content of organoaluminum oxy compound): 6 ml
TD: 22 ml
BNBD: 29 ml

(Ii-5')
Cyclohexane / hexane (3/1) mixed solvent: 1853 ml / hr
Toluene solution of methylaluminoxane (concentration 6.5% by mass as the content of organoaluminum oxy compound): 12 ml / hr
TD: 45 ml / hr
BNBD: 57 ml / hr
Toluene solution of transition metal compound (7) (concentration 1.90 g / L): 33 ml / hr

From 500 mL of the obtained cyclic olefin-based copolymer solution, a catalyst-removed solution was obtained in the same manner as in Example 1.

To 50 g of the obtained catalyst-removed solution, 100 g of cyclohexane was charged and diluted. Then, a diluted catalyst-removed solution was gradually added to 800 mL of agitated acetone to precipitate a cyclic olefin-based copolymer. The precipitated cyclic olefin-based copolymer was recovered by suction filtration and dried in a vacuum dryer at 130 ° C. for 10 hours to obtain 2.25 g of the cyclic olefin-based copolymer.

Various physical properties of Examples 1 to 9 and Comparative Examples 1 to 5 were evaluated by the following methods. The results obtained are shown in Table 1.

(Comonomer (cyclic olefin) content of cyclic olefin copolymer)
The comonomer (cyclic olefin) content of the polymer was determined by 13C-NMR spectrum according to the description in paragraph [0132] of WO2019 / 107363.

(Glass transition temperature Tg (° C))
The glass transition temperature Tg of the cyclic olefin-based copolymer was measured in an _N2 (nitrogen) atmosphere using DSC-6220 manufactured by Shimadzu Science Co., Ltd. The cyclic olefin copolymer was heated from room temperature to 250 ° C. at a heating rate of 10 ° C./min and then held for 5 minutes, and then cooled to -20 ° C. at a temperature decreasing rate of 10 ° C./min and then held for 5 minutes. .. Then, the glass transition point (Tg) of the cyclic olefin-based copolymer was obtained from the endothermic curve when the temperature was raised to 250 ° C. at a heating rate of 10 ° C./min.

(Ultimate viscosity η)
Using a mobile viscometer (manufactured by Rigo Co., Ltd., type VNR053U type), a sample obtained by dissolving 0.25 to 0.30 g of a cyclic olefin copolymer in 25 ml of decalin was used as a sample. The specific viscosity of the cyclic olefin-based copolymer was measured at 135 ° C. according to ASTM J1601, and the ratio of this to the concentration was extrapolated to a concentration of 0 to obtain the ultimate viscosity η of the cyclic olefin-based copolymer.

(Concentration of cyclic olefin-based copolymer in the catalyst-removed solution)
The concentration of the cyclic olefin-based copolymer in the catalyst-removed solution was calculated from the weight of the cyclic olefin-based copolymer with respect to the weight of the catalyst-removed solution.

(Solidification behavior of the catalyst-removed solution)
After the catalyst-removed solution was placed in a glass container and allowed to stand for one day, the solidification behavior of the polymerization solution was evaluated by tilting the container 90 degrees and visually confirming the fluidity of the solution.
〇: With fluidity; The solution moves in the tilted direction and the liquid level spreads uniformly Δ: Decreased fluidity; The solution moves in the tilted direction, but the liquid level is not uniform
×: No fluidity; the solution does not move in the tilted direction

(Solubility of cyclic olefin copolymer)
The solubility of the cyclic olefin-based copolymer was evaluated by adding 0.12 g of the cyclic olefin-based copolymer and 1.5 ml of a cyclohexane / hexane (3/1) mixed solvent to the vial and shaking at room temperature.
〇: Soluble; Cyclic olefin copolymer dissolved ×: Insoluble; Cyclic olefin copolymer insoluble

(Solidification behavior of redissolved solution)
After allowing the solution prepared for evaluating the solubility of the cyclic olefin-based copolymer to stand for 24 hours, the solidification behavior of the polymerization solution was evaluated by tilting the container 90 degrees and visually confirming the fluidity of the solution. .. In the evaluation of the solubility of the cyclic olefin-based copolymer, the samples having an evaluation of × were excluded from the evaluation of the solidification behavior, and diagonal lines were drawn in the table.
〇: With fluidity; The solution moves in the tilted direction and the liquid level spreads uniformly Δ: Decreased fluidity; The solution moves in the tilted direction, but the liquid level is not uniform
×: No fluidity; the solution does not move in the tilted direction

(Elemental analysis)
Measurements were performed using ICP-MS (Agient 7500cs) manufactured by Agilent Technologies. For the quantitative analysis of aluminum, the sample was wet-decomposed with sulfuric acid and then diluted with a dilute acid containing an internal standard element for analysis.
The aluminum content was evaluated according to the following criteria.
◯: less than 50 ppm Δ: 50 ppm or more to 100 ppm or less ×: more than 100 ppm

As shown in Table 1, in the methods for producing the cyclic olefin-based copolymers of Examples 1 to 9 according to the embodiment of the present invention, the aluminum content of the obtained cyclic olefin-based copolymer was reduced to 100 ppm or less. ..

As shown in Table 1, in the methods for producing the cyclic olefin-based copolymers of Examples 1 to 9 according to the embodiment of the present invention, solidification of the cyclic olefin-based copolymer was suppressed. In addition, the cyclic olefin-based copolymer obtained by the method for producing the cyclic olefin-based copolymer of Examples 1 to 9 according to the embodiment of the present invention had excellent solubility. Therefore, in the method for producing a cyclic olefin-based copolymer according to the embodiment of the present invention, the catalyst can be efficiently removed even if the cyclic olefin-based copolymer has a high concentration, and the aluminum content can be reduced to 100 ppm or less. It is thought that it was.

Claims (10)

In the presence of an olefin polymerization catalyst containing the transition metal compound (A) and the compound (B), an α-olefin (X') having 2 to 20 carbon atoms and a cyclic olefin having no aromatic ring (Y). ´) and a polymerization step of copolymerizing a cyclic olefin (Z ′) having an aromatic ring;
With the catalyst removal step of removing the catalyst for olefin polymerization;
Is a method for producing a cyclic olefin-based copolymer comprising the above.
The cyclic olefin-based copolymer obtained by the production method has a structural unit (X) derived from the α-olefin (X'), a structural unit (Y) derived from the cyclic olefin (Y'), and the cyclic olefin. It has a structural unit (Z) derived from (Z') and has.
The aluminum content of the cyclic olefin-based copolymer is 100 ppm or less, and the content is 100 ppm or less.
The transition metal compound (A) is
The transition metal compound (A-1) represented by the following formula (I),
Contains one or more selected from the group consisting of the transition metal compound (A-2) represented by the following formula (II) and the transition metal compound (A-3) represented by the following formula (III). death,
The compound (B) is
Organometallic compound (B-1),
Cyclic containing one or more selected from the group consisting of the organic aluminum oxy compound (B-2) and the compound (B-3) that reacts with the transition metal compound (A) to form an ion pair. A method for producing an olefin-based copolymer.

In the formula (I),
M ¹ represents a transition metal atom of Group 4 of the Periodic Table.
^R0 indicates a group selected from the group consisting of an alkylene group, an alkylidene group, an arylene group and a silylene group, and a group consisting of their substitutions.
R ¹ and R ² each independently represent a cycloalkazienyl group or a substitution thereof.
R ³ and R ⁴ are independently hydrogen atom, halogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, silicon-containing group, boron-containing group and aluminum. An atom or group selected from the group consisting of containing groups and the group consisting of their substituents is shown.

In the formula (II),
M ² represents a transition metal atom of Group 4 of the periodic table.
n ¹ represents an integer of 1 to 3 and represents
L independently represents a monovalent anionic ligand in which an atom of Group 15 of the periodic table is a coordination atom.
X ¹ is independently composed of hydrogen atom, halogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, silicon-containing group, boron-containing group and aluminum-containing group. Group, as well as groups or atoms selected from the group consisting of their substitutions,
R ⁵ to R ⁹ are independently hydrogen atom, halogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, silicon-containing group, boron-containing group and aluminum. It represents a group or atom selected from the group consisting of containing groups and the group consisting of their substituents, and any two or three of R5 to ^R109 may be fused to form a ring ^. The ring to be formed may have aromaticity including a conjugated double bond.

In the above formula (III)
M ³ represents a transition metal atom of Group 4 of the Periodic Table.
n ² represents an integer from 1 to 4 and represents
X ² is independently composed of hydrogen atom, halogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, silicon-containing group, boron-containing group and aluminum-containing group. Represents an atom or group selected from the group consisting of, as well as their substitutions.
R ¹⁰ to R ¹⁷ are independently hydrogen atom, halogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, silicon-containing group, boron-containing group and aluminum. Indicates an atom or group selected from the group consisting of containing groups and the group consisting of their substituents, and adjacent ones of R ¹⁰ to R ¹⁷ may be bonded to each other to form a ring. The ring to be formed may have aromaticity including a conjugated double bond. The method for producing a cyclic olefin-based copolymer according to claim 1.
In the formula (I),
R ¹ and R ² are independently composed of a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, a dimethylcyclopentadienyl group, an indenyl group, a tetrahydroindenyl group and a fluorenyl group, respectively. A method for producing a cyclic olefin-based copolymer, which comprises a group selected from the group and a group consisting of a substituent thereof. The method for producing a cyclic olefin-based copolymer according to claim 1.
In the formula (II),
L is a method for producing a cyclic olefin-based copolymer, which is a monovalent anionic ligand represented by the following formula (IV).

In the above formula (IV)
Y indicates an atom of Group 15 of the periodic table.
Z represents one kind of atom selected from Group 14, Group 15, or Group 16 of the Periodic Table.
n ³ represents an integer of 1 to 3 and represents
R ¹⁸ is independently composed of hydrogen atom, halogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, silicon-containing group, boron-containing group and aluminum-containing group. Group, as well as groups or atoms selected from the group consisting of their substituents, each of which may be bonded to each other to form a ring, the ring of which is aromatic, including conjugated double bonds. The ring formed may be bonded to a cyclopentadienyl group. The method for producing a cyclic olefin-based copolymer according to claim 1.
In the above formula (III)
R ¹⁰ to R ¹⁴ and R ¹⁷ are independently selected atoms or groups from the group consisting of hydrogen atom, halogen atom, hydrocarbon group, halogen-containing group and silicon-containing group, and the group consisting of their substitutions. , And R ¹⁰ to R ¹⁴ adjacent to each other may be bonded to each other to form a ring, and the formed ring may have aromaticity including a conjugated double bond.
R ¹⁵ and R ¹⁶ each independently represent an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a halogen-containing group, and a group consisting of their substitutions. Method for producing a polymer. A structural unit (X) derived from an α-olefin (X') having 2 to 20 carbon atoms, a structural unit (Y) derived from a cyclic olefin (Y') having no aromatic ring, and a cyclic olefin having an aromatic ring. A cyclic olefin-based copolymer having a structural unit (Z) derived from (Z').
The cyclic olefin-based copolymer has an aluminum content of 100 ppm or less. The cyclic olefin-based copolymer according to claim 5.
When the total content of the structural unit (X), the structural unit (Y) and the structural unit (Z) in the cyclic olefin-based copolymer is 100 mol%, the cyclic olefin-based copolymer is contained. A cyclic olefin-based copolymer having a content of the structural unit (X) of 10 mol% or more and 80 mol% or less. The cyclic olefin-based copolymer according to claim 5 or 6.
When the total content of the structural unit (Y) and the structural unit (Z) in the cyclic olefin-based copolymer is 100 mol%, the structural unit (Z) in the cyclic olefin-based copolymer A cyclic olefin-based copolymer having a content of 5 mol% or more and 95 mol% or less. The cyclic olefin-based copolymer according to any one of claims 5 to 7.
A cyclic olefin-based copolymer in which the structural unit (Y) contains a structural unit derived from a compound represented by the following formula (V).

In the formula (V)
n ¹⁰¹ indicates 0 or 1 and represents
m ¹⁰¹ indicates 0 or a positive integer,
q ¹⁰¹ indicates 0 or 1 and represents
R ¹⁰¹ to R ¹¹⁸ and R ^a and R ^b each independently represent a hydrocarbon group which may be substituted with a hydrogen atom, a halogen atom or a halogen atom, and R ¹¹⁵ to R ¹¹⁸ are bonded to each other to form a single ring. Alternatively, a polycycle may be formed, and the monocyclic or polycycle may have a double bond, and an alkylidene group may be formed between R ¹¹⁵ and R ¹¹⁶ , or between R ¹¹⁷ and R ¹¹⁸ . May be formed. However, R ¹⁰¹ to R ¹¹⁸ and ^{Ra and R b do} not contain an aromatic ring. The cyclic olefin-based copolymer according to any one of claims 5 to 8.
The structural unit (Z) is one selected from the group consisting of a compound represented by the following formula (VI), a compound represented by the following formula (VII), and a compound represented by the following formula (VIII). A cyclic olefin-based copolymer containing a structural unit derived from two or more compounds.

In the formula (VI),
n ²⁰¹ and q ²⁰¹ are independently 0, 1 or 2, respectively.
R ²⁰¹ to R ²¹⁷ are hydrocarbon groups having 1 to 20 carbon atoms which may be independently substituted with a hydrogen atom, a halogen atom excluding a fluorine atom, or a halogen atom excluding a fluorine atom.
One of R ²¹⁰ to R ²¹⁷ is a bond,
When q ²⁰¹ = 0, R ²¹⁰ and R ²¹¹ , R ²¹¹ and R ²¹² , R ²¹² and R ²¹³ , R ²¹³ and R ²¹⁴ , R ²¹⁴ and R ²¹⁵ , R ²¹⁵ and R ²¹⁰ are monocyclic or are coupled to each other. It may form a polycycle,
When q ²⁰¹ = 1 or 2, R ²¹⁰ and R ²¹¹ , R ²¹¹ and R ²¹⁷ , R ²¹⁷ and R ²¹⁷ , R ²¹⁷ and R ²¹² , R ²¹² and R ²¹³ , R ²¹³ and R ²¹⁴ , R ²¹⁴ and R ^215. , R ²¹⁵ and R ²¹⁶ , R ²¹⁶ and R ²¹⁶ , R ²¹⁶ and R ²¹⁰ may be coupled to each other to form a monocyclic or polycyclic.
The monocyclic or polycyclic may have a double bond.
The monocyclic ring or the polycyclic ring may be an aromatic ring.

In the above formula (VII)
n ²⁰² and m ²⁰¹ are independently 0, 1 or 2, respectively.
q ²⁰² is 1, 2 or 3 and
R ²¹⁸ to R ²³¹ are hydrocarbon groups having 1 to 20 carbon atoms which may be independently substituted with a hydrogen atom, a halogen atom excluding a fluorine atom, or a halogen atom excluding a fluorine atom.
When q ²⁰² = 1, R ²²⁸ and R ²²⁹ , R ²²⁹ and R ²³⁰ , and R ²³⁰ and R ²³¹ may be bonded to each other to form a monocyclic or polycyclic ring.
When q ²⁰² = 2 or 3, R ²²⁸ and R ²²⁸ , R ²²⁸ and R ²²⁹ , R ²²⁹ and R ²³⁰ , R ²³⁰ and R ²³¹ and R ²³¹ and R ²³¹ combine with each other to form a monocyclic or polycyclic. You may be
The monocyclic or polycyclic may have a double bond.
The monocyclic ring or the polycyclic ring may be an aromatic ring.

In the above formula (VIII)
q ²⁰³ is 1, 2 or 3,
^R232 to ^R239 are hydrocarbon groups having 1 to 20 carbon atoms which may be independently substituted with a hydrogen atom, a halogen atom excluding a fluorine atom, or a halogen atom excluding a fluorine atom.
When q ²⁰³ = 1, R ²³⁶ and R ²³⁷ , R ²³⁷ and R ²³⁸ , and R ²³⁸ and R ²³⁹ may be bonded to each other to form a monocyclic or polycyclic ring.
When q ²⁰³ = 2 or 3, R ²³⁶ and R ²³⁶ , R ²³⁶ and R ²³⁷ , R ²³⁷ and R ²³⁸ , R ²³⁸ and R ²³⁹ , and R ²³⁹ and R ²³⁹ combine with each other to form a monocyclic or polycyclic. May be
The monocyclic or polycyclic may have a double bond.
The monocyclic ring or the polycyclic ring may be an aromatic ring. The cyclic olefin-based copolymer according to any one of claims 5 to 9.
A cyclic olefin-based copolymer having a glass transition temperature (Tg) of 120 ° C. or higher and 180 ° C. or lower as measured by a differential scanning calorimeter (DSC).