JP6886955B2 - Method for producing cyclic olefin polymer - Google Patents

Description

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

Cyclic olefin polymers such as cyclic olefin homopolymers and cyclic olefin copolymers have low moisture absorption and high transparency, and are used in various applications including the field of optical materials such as optical disk substrates, optical films, and optical fibers. It is used.
As a typical cyclic olefin copolymer, there is a copolymer of cyclic olefin and ethylene, which is widely used as a transparent resin. Since the glass transition temperature of the copolymer of cyclic olefin and ethylene can be changed according to the copolymerization composition of cyclic olefin and ethylene, the copolymer weight in which the glass transition temperature (Tg) is adjusted in a wide temperature range. Coalescence can be manufactured. Copolymers with high Tg generally have good heat resistance (see, for example, Non-Patent Document 1).

In addition to the copolymer of cyclic olefin and ethylene, a copolymer of cyclic olefin and α-olefin other than ethylene is known. The copolymer of cyclic olefin and ethylene has a good balance between heat resistance and mechanical properties, but the mechanical properties may deteriorate when the heat resistance is increased. By copolymerizing the cyclic olefin with an α-olefin other than ethylene, the balance between heat resistance and mechanical properties, which is a problem in the copolymer of the cyclic olefin and ethylene, can be improved.

Regarding the method for producing such a cyclic olefin polymer, the copolymerization reaction of cyclic olefin and ethylene and the copolymerization reaction of cyclic olefin and α-olefin other than ethylene are significantly different. Specifically, in the zirconocene-based metallocene-based transition metal catalyst preferably used in the copolymerization reaction between the cyclic olefin and ethylene, the chain transfer due to the α-olefin occurs in the copolymerization of the cyclic olefin and the α-olefin. It has been known that it is difficult to obtain a high molecular weight compound because a reaction occurs (see, for example, Non-Patent Document 2).

Therefore, research and development of catalysts capable of efficiently producing copolymers of cyclic olefins and α-olefins have been actively carried out. Through research, the copolymer of cyclic olefin and α-olefin has a titanosen-based metallocene-based transition, commonly known as half-metallocene (post-metallocene), which is different from the conventionally used zirconece-based metallocene-based transition metal catalysts. It was found that it can be efficiently produced by using a metal catalyst. As described above, it was necessary to select an appropriate metallocene catalyst according to the structure of the monomer that gives the desired cyclic olefin polymer (see, for example, Non-Patent Document 3).

As described above, the synthesis of cyclic olefin polymers such as cyclic olefin homopolymers and cyclic olefin copolymers is generally carried out using a catalyst typified by a metallocene-based transition metal catalyst. Regardless of whether it is a metallocene-based transition metal catalyst or a half-metallocene-based transition metal catalyst, the metallocene-based transition metal catalyst is generally expensive. Therefore, reducing the amount of the catalyst used reduces the cost of the entire production of the cyclic olefin polymer. Therefore, the development of a catalyst capable of producing a large amount of cyclic olefin polymer with a small amount of catalyst is an important issue.
For example, as a method for synthesizing a cyclic olefin copolymer with a small amount of catalyst, at least derived from the cyclic olefin monomer (A) derived from norbornene and α-olefins C4 to C12 in the presence of a metallocene-based transition metal catalyst. A method including a polymerization step of polymerizing the α-olefin monomer (B) to obtain a copolymer has been proposed (see Patent Document 1 and Patent Document 2).

International Publication No. 2015/178143 International Publication No. 2015/178144

Incoronata, Tritto et al., Coordination Chemistry Reviews, 2006, Vol. 250, p. 212-241 Jung, H.M. Y. Et al., Polyhedron, 2005, Vol. 24, p. 1269-1273 Takeshi Shiono et al., Macromolecules, 2008, Vol. 41, p. 8292-8294

However, when a cyclic olefin polymer is produced using a transition metal complex catalyst such as a metallocene catalyst, the polymerization yield expected under the common conditions is expected even though the polymerization reactions are carried out a plurality of times under the common conditions. Often, cyclic olefin polymers are only available in lower yields.

The present invention has been made in view of the above problems, and when a cyclic olefin polymer is produced using a transition metal complex catalyst such as a metallocene catalyst, the present invention is stable at an expected yield suitable for the polymerization conditions. It is an object of the present invention to provide a method for producing a cyclic olefin polymer capable of producing a cyclic olefin polymer.

The present inventors activate a crude norbornene compound containing an epoxide impurity in a method for producing a cyclic olefin polymer by polymerizing a monomer containing a norbornene compound containing an epoxide impurity in the presence of a transition metal catalyst. Treatment with a hybrid adsorbent consisting of a mixture of alumina and zeolite reduces epoxide impurities in the monomer, resulting in the inclusion of epoxide impurities in the total mass of the polymerization solution used for polymerization. We have found that the above problems can be solved by setting the ratio of the amount to the content of the catalyst (mass ppm / mass ppm) to 6 or less, and have completed the present invention.
More specifically, the present invention provides the following.

（式中、Ｒ^１〜Ｒ^１２は、それぞれ同一でも異なっていてもよく、水素原子、ハロゲン原子、及び、飽和脂肪族炭化水素基、アラルキル基、及び芳香族炭化水素基からなる群より選ばれる原子又は基であり、
Ｒ^９〜Ｒ^１２より選択される２つの基は、互いに結合して、飽和脂肪族炭化水素環、又は芳香族炭化水素環を形成してもよく、
また、ｎは、０又は正の整数を示し、
ｎが２以上の場合には、Ｒ^５〜Ｒ^８は、それぞれの繰り返し単位の中で、それぞれ同一でも異なっていてもよく、
ただし、ｎ＝０の場合、Ｒ^１〜Ｒ^４及びＲ^９〜Ｒ^１２の少なくとも１個は、水素原子ではない。）
で表される置換ノルボルネンからなる群より選択される１種以上の化合物であり、
エポキシド不純物が、２，３−エポキシノルボルナン、及び／又は式（Ｉ）で表される置換ノルボルネンにおける、炭素−炭素不飽和二重結合が酸化されたエポキシ化合物であり、
吸着剤が、活性アルミナとゼオライトとの混合物からなるハイブリッド系吸着剤であり、
重合に供される重合溶液の全質量に対するエポキシド不純物の含有量と触媒の含有量との比率（質量ｐｐｍ／質量ｐｐｍ）が、６以下であり、
重合溶液の全質量は、環状オレフィンポリマーの製造に使用される原料の質量の総量である、製造方法。 (1) A method for producing a cyclic olefin polymer by polymerizing a monomer containing a norbornene-based compound containing an epoxide impurity.
Purified norbornene compounds can be obtained by contacting crude norbornene compounds containing epoxide impurities with an adsorbent.
It comprises polymerizing a monomer containing a purified norbornene compound in the presence of a transition metal complex catalyst.
Norbornene-based compounds are norbornene, and the following formula (I):

(In the formula, R ^{1 to} R ¹² may be the same or different, respectively, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a saturated aliphatic hydrocarbon group, an aralkyl group, and an aromatic hydrocarbon group. It is an atom or a group
The ^{two groups selected from R 9 to} R ¹² may be bonded to each other to form a saturated aliphatic hydrocarbon ring or an aromatic hydrocarbon ring.
Further, n indicates 0 or a positive integer.
When n is 2 or more, R ^{5 to} R ⁸ may be the same or different in each repeating unit.
However, when n = 0, ^{at least one of R 1 to} R ⁴ and R ^{9 to} R ¹² is not a hydrogen atom. )
It is one or more compounds selected from the group consisting of substituted norbornene represented by.
The epoxide impurity is an epoxy compound in which the carbon-carbon unsaturated double bond is oxidized in 2,3-epoxynorbornane and / or the substituted norbornene represented by the formula (I).
The adsorbent is a hybrid adsorbent composed of a mixture of active alumina and zeolite.
The ratio of the content of epoxide impurities to the content of the catalyst (mass ppm / mass ppm) with respect to the total mass of the polymerization solution to be subjected to polymerization is 6 or less.
The production method, wherein the total mass of the polymerization solution is the total mass of the raw materials used in the production of the cyclic olefin polymer.

(2) The ratio (mass ppm / mass ppm) of the content of aldehyde impurities derived from the norbornene-based compound to the content of the catalyst with respect to the total mass of the polymerization solution to be subjected to polymerization is 2 or less (1). The method for producing a cyclic olefin polymer according to.

(3) The ratio (mass ppm / mass ppm) of the content of the ketone impurity derived from the norbornene-based compound to the content of the catalyst with respect to the total mass of the polymerization solution to be subjected to the polymerization is 2 or less (1). Alternatively, the method for producing a cyclic olefin polymer according to (2).

(4) The method for producing a cyclic olefin polymer according to any one of (1) to (3), wherein the amount of the adsorbent is 1 part by mass or more with respect to 100 parts by mass of the crude norbornene compound.

(5) The method for producing a cyclic olefin polymer according to any one of (1) to (4), wherein the transition metal complex catalyst is a metallocene catalyst.

(6) The method for producing a cyclic olefin polymer according to (5), wherein the metallocene catalyst is a transition metal complex containing a ligand containing a cyclopentadiene ring and a transition metal of Group IV of the periodic table.

(7) The cyclic according to claim (6), wherein the metallocene catalyst is reacted with one or more selected from the group consisting of aluminoxane (b1) and an ionic compound (b2) to produce a cationic transition metal compound. A method for producing an olefin polymer.

(8) group IV of the periodic table transition metals, Ti, Zr, or H f, (6) or (7) the production method of the cyclic olefin polymer according to.

(9) The method for producing a cyclic olefin polymer according to (1) to (8), wherein the monomer contains at least one selected from the group consisting of ethylene, 1-hexene, and 1-octene together with a norbornene-based compound. ..

According to the present invention, when a cyclic olefin polymer is produced using a transition metal complex catalyst such as a metallocene catalyst, the cyclic olefin polymer can be stably produced in an expected yield suitable for the polymerization conditions. A method for producing a polymer can be provided.

≪Manufacturing method of cyclic olefin polymer≫
In the method for producing a cyclic olefin polymer, a cyclic olefin polymer is produced by polymerizing a monomer containing a norbornene-based compound containing an epoxide impurity.

The manufacturing method is
Purified norbornene compounds can be obtained by contacting crude norbornene compounds containing epoxide impurities with an adsorbent.
It comprises polymerizing a monomer containing a purified norbornene compound in the presence of a transition metal complex catalyst.
In such a method, the amount of epoxide impurities in the monomer to be polymerized is significantly reduced by treating the crude norbornene-based compound with a specific adsorbent described later as an adsorbent to obtain a purified norbornene-based compound. can do.
As a result, the ratio (mass ppm / mass ppm) of the content of the epoxide impurity to the content of the catalyst with respect to the total mass of the polymerization solution to be subjected to the polymerization can be set to a low value of 6 or less.
When the ratio (mass ppm / mass ppm) of the content of the epoxide impurity to the content of the catalyst in the polymerization solution to be polymerized is equal to or less than the above-mentioned predetermined amount, the decrease in the activity of the transition metal complex catalyst is suppressed. It is considered that the cyclic olefin polymer can be stably produced in a desired yield.
The "total mass of the polymerization solution used for polymerization" is the total mass of the raw materials used in the production of the cyclic olefin polymer. Typically, the "total mass of the polymerization solution to be subjected to polymerization" is the mass of the "monomer containing a purified norbornene compound", the mass of the "transition metal complex catalyst", and the catalyst together with the transition metal complex catalyst. It is the sum of the mass of the "auxiliary catalyst" constituting the composition and the mass of the "solvent". When other materials other than these materials are used in the production of the cyclic olefin polymer, the mass of the other materials is also included in the "total mass of the polymerization solution to be subjected to the polymerization".

The norbornene-based compound contained in the monomer is one or more compounds selected from the group consisting of norbornene and substituted norbornene represented by the formula (I) described later.
Such a norbornene-based compound corresponds to a monoene compound.

The monomer used in the production of the cyclic olefin polymer contains epoxide impurities derived from norbornene-based compounds. Epoxide impurities are produced by the oxidation of norbornene compounds.
The epoxide impurity is an epoxy compound in which the carbon-carbon unsaturated double bond is oxidized in 2,3-epoxynorbornane and / or the substituted norbornene represented by the above formula (I).

As the adsorbent used for purifying the crude norbornene compound, a hybrid adsorbent composed of a mixture of activated alumina and zeolite is used.
By using such a hybrid adsorbent, it is easy to remove epoxide impurities satisfactorily while preventing the generation of impurities that may adversely affect the activity of the transition metal complex catalyst.

The content of the epoxide impurity in the monomer to be polymerized is preferably 200 mass ppm or less with respect to the mass of the norbornene-based compound. By using a monomer in which the content of the epoxide impurity is within such a range, the ratio of the content of the epoxide impurity to the content of the catalyst with respect to the total mass of the polymerization solution to be polymerized (mass ppm / mass ppm). Is easy to set to 6 or less. As a result, the cyclic olefin polymer can be stably produced in a desired yield.

Hereinafter, obtaining a purified norbornene compound by contacting a crude norbornene compound containing an epoxide impurity with an adsorbent is also referred to as a “purification step”.
Polymerizing a monomer containing a purified norbornene compound in the presence of a transition metal complex catalyst is also referred to as a "polymerization step".
Hereinafter, the steps included in the method for producing the cyclic olefin polymer will be described.

<Refining process>
In the purification step, a crude norbornene-based compound containing an epoxide impurity is brought into contact with an adsorbent to obtain a purified norbornene-based compound.

[Monomer]
The object of purification in the purification step is a crude product of a monomer containing a norbornene-based compound to be subjected to polymerization in the polymerization step described later. More specifically, at least a crude norbornene-based compound among the crude products of the monomer is purified.

The crude norbornene-based compound is a norbornene-based compound containing epoxide impurities and not treated with an adsorbent described later.
Norbornene-based compounds are one or more compounds selected from the group consisting of norbornene and substituted norbornene. As the norbornene-based compound, norbornene is preferable.

（式中、Ｒ^１〜Ｒ^１２は、それぞれ同一でも異なっていてもよく、水素原子、ハロゲン原子、及び、飽和脂肪族炭化水素基、アラルキル基、及び芳香族炭化水素基からなる群より選ばれる原子又は基であり、
Ｒ^９〜Ｒ^１２より選択される２つの基は、互いに結合して、飽和脂肪族炭化水素環、又は芳香族炭化水素環を形成してもよく、
また、ｎは、０又は正の整数を示し、
ｎが２以上の場合には、Ｒ^５〜Ｒ^８は、それぞれの繰り返し単位の中で、それぞれ同一でも異なっていてもよく、
ただし、ｎ＝０の場合、Ｒ^１〜Ｒ^４及びＲ^９〜Ｒ^１２の少なくとも１個は、水素原子ではない。）
で表される化合物である。 The substituted norbornene is represented by the following formula (I):

(In the formula, R ^{1 to} R ¹² may be the same or different, respectively, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a saturated aliphatic hydrocarbon group, an aralkyl group, and an aromatic hydrocarbon group. It is an atom or a group
The ^{two groups selected from R 9 to} R ¹² may be bonded to each other to form a saturated aliphatic hydrocarbon ring or an aromatic hydrocarbon ring.
Further, n indicates 0 or a positive integer.
When n is 2 or more, R ^{5 to} R ⁸ may be the same or different in each repeating unit.
However, when n = 0, ^{at least one of R 1 to} R ⁴ and R ^{9 to} R ¹² is not a hydrogen atom. )
It is a compound represented by.

The epoxide impurity is an epoxy compound in which the carbon-carbon unsaturated double bond is oxidized in 2,3-epoxynorbornane and / or the substituted norbornene represented by the above formula (I).

The amount of epoxide impurities in the crude norbornene-based compound is the ratio of the content of epoxide impurities to the content of the catalyst (mass ppm / mass ppm) with respect to the total mass of the polymerization solution subjected to polymerization by purification with an adsorbent. If it can be 6 or less, it is not particularly limited.
Typically, the amount of epoxide impurities in the crude norbornene-based compound is 200 mass ppm or more, 300 mass ppm or more, or 500 mass ppm or more, based on the mass of the norbornen-based compound. It may be 1500 mass ppm or more.
The amount of epoxide impurities in the crude norbornene compound is preferably 5000 mass ppm or less, preferably 3000 mass ppm or less, or 2000 mass ppm or less in that the crude norbornene compound can be easily purified. ..

Hereinafter, the substituted norbornene represented by the formula (I) will be described. ^{R 1 to} R ¹² in the formula (I) may be the same or different from each other, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group.

Preferable specific examples of R ^{1 to} R ⁸ include, for example, a hydrogen atom; a halogen atom such as fluorine, chlorine, and bromine; an alkyl group having 1 to 20 carbon atoms, and the like, which are different from each other. May be partially different, or all may be the same.

Specific examples of R ^{9 to} R ¹² include, for example, a hydrogen atom; a halogen atom such as fluorine, chlorine and bromine; an alkyl group having 1 to 20 carbon atoms; a cycloalkyl group such as a cyclohexyl group; a phenyl group and a trill. Substituent or unsubstituted aromatic hydrocarbon groups such as groups, ethylphenyl groups, isopropylphenyl groups, naphthyl groups and anthryl groups; benzyl group, phenethyl group and other alkyl groups substituted with aryl groups and the like. They can be different, partially different, or all identical.

When ^{two groups selected from R 9 to} R ¹² are bonded to each other to form a ring, the formed ring may be a monocyclic ring, a polycyclic ring, or a polycyclic ring having a crosslink. It may be a ring composed of a combination of these rings. Further, these rings may have a substituent such as a methyl group.
Examples of the saturated aliphatic hydrocarbon ring that can be formed by bonding two groups selected from R ^{9 to} R ¹² to each other include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cycloheptane ring.
Examples of the aromatic hydrocarbon ring that can be formed by bonding two groups selected from R ^{9 to} R ^{12 to each other include a benzene ring and a naphthalene ring.}

Specific examples of the substituted norbornene represented by the general formula (I) include 5-methyl-bicyclo [2.2.1] hepta-2-ene and 5,5-dimethyl-bicyclo [2.2.1] hepta-. 2-ene, 5-ethyl-bicyclo [2.2.1] hepta-2-ene, 5-butyl-bicyclo [2.2.1] hepta-2-ene, 5-hexyl-bicyclo [2.2. 1] Bicyclic olefins such as hepta-2-ene, 5-octyl-bicyclo [2.2.1] hepta-2-ene, 5-octadecyl-bicyclo [2.2.1] hepta-2-ene, etc. ;
Tricyclo [4.3.0.1 ^2,5 ] deca-3-ene; tricyclo [4.4.0.1 ^2,5 ] undeca-3-ene; 5-cyclopentyl-bicyclo [2.2.1] Hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1] hepta-2-ene, 5-cyclohexenylbicyclo [2.2.1] hepta-2-ene, 5-phenyl-bicyclo [2. 2.1] Three-ring cyclic olefins such as hepta-2-ene;
Tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodeca-3-ene (also simply referred to as tetracyclododecene), 8-methyltetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodeca-3-ene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodeca-3-ene, 8-methylidenetetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodeca-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] Dodeca-3-ene, 8-vinyltetracyclo [4,4.0.1, ^2,5 . ^{17 and 10} ] Dodeca-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 . ^17,10 ] Tetracyclic cyclic olefins such as dodeca-3-ene;
8-Cyclopentyl-tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodeca-3-ene, 8-cyclohexyl-tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodeca-3-ene, 8-cyclohexenyl-tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodeca-3-ene, 8-phenyl-cyclopentyl-tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodeca-3-ene; Pentacyclo [6.6.1.1 ^3,6 . 0 ^2,7 . ^09,14 ] -4-hexadecene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] -4-pentadecene, pentacyclo [7.4.0.0 ^2,7. 1 ^{3, 6} . 1 ^{10, 13} ] -4-pentadecene; heptacyclo [8.7.0.1 ^2,9 . 1 ^{4, 7 4} . 1 ^{11, 17} ． 0 ^3,8 . 0 ^12,16 ] -5-eikosen, heptacyclo [8.7.0.1 ^2,9 . 0 ^3,8 . 1 ^{4, 7 4} . 0 ^12,17 . Examples include polycyclic cyclic olefins such as ^{11 13, l6] -14-ecocene; and the like.}

Of these, alkyl-substituted norbornene (eg, bicyclo [2.2.1] hepta-2-ene substituted with one or more alkyl groups) and alkylidene-substituted norbornene are preferred.

In the purification step, the crude norbornene-based compound may be brought into contact with the adsorbent alone. When the monomer contains a monomer other than the norbornene compound together with the norbornene compound, a mixture containing the crude norbornene compound and the other monomer may be brought into contact with the adsorbent.

The other monomer is not particularly limited as long as it is a monomer compound copolymerizable with the norbornene-based compound, and is typically an α-olefin. The α-olefin may be substituted with at least one substituent such as a halogen atom.

As the α-olefin, C2-C12 α-olefins are preferable. The α-olefin of C2 to C12 is not particularly limited, and is, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 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, 3 -Ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene and the like can be mentioned. Of these, 1-hexene, 1-octene, and 1-decene are preferable.

As a combination of monomers for producing a cyclic olefin polymer, a combination of norbornene and ethylene is used because it has an excellent balance of availability, mechanical properties, thermal properties, manufacturability, etc. of the monomer. A combination of norbornene with 1-octene, 1-hexene, or a mixture thereof is preferred.
That is, it is preferable that the monomer contains at least one selected from the group consisting of ethylene, 1-hexene, and 1-octene together with the norbornene-based compound. The monomer is more preferably composed of a norbornene-based compound and one or more selected from the group consisting of ethylene, 1-hexene, and 1-octene.

When norbornene and ethylene are used in combination, the amount of norbornene in the monomer is 30 mol% or more and less than 70 mol% in order to obtain a cyclic olefin polymer having a good balance between mechanical properties and thermal properties. preferable.
When norbornene is used in combination with 1-octene, 1-hexene, or a mixture thereof, it is easy to obtain a cyclic olefin having good mechanical properties, so that the glass transition temperature of the cyclic olefin polymer can be raised. The amount of norbornene in the monomer is preferably 70 mol% or more.

[Adsorbent]
By contacting the crude norbornene-based compound contained in the monomer described above, a treatment for reducing the epoxide impurities contained in the crude norbornene-based compound is performed.
As the adsorbent, a hybrid adsorbent composed of a mixture of activated alumina and zeolite is used.
The hybrid adsorbent is typically in the form of powder or pellets, preferably in the form of pellets.
In the hybrid adsorbent, it is preferable that the activated alumina moiety and the zeolite moiety are inseparably complexed in the particles constituting the powder or pellet. In this case, the hybrid adsorbent has both an adsorption site as activated alumina and an adsorption site as zeolite in the same particle.
The hybrid adsorbent may be a mixture of powdered or pelletized activated alumina and powdered or pelletized zeolite as long as the desired adsorption and cure for epoxide impurities can be obtained.
In the hybrid adsorbent in which the active alumina moiety and the zeolite moiety are inseparably complexed in the particles constituting the powder or pellet, the powder or pellet-like active alumina and the powder or pellet-like zeolite are mixed. The adsorption performance of epoxide impurities and ketone impurities and aldehyde impurities, which will be described later, is better than that of the mixture.

In such a hybrid adsorbent, the content of activated alumina and the content of zeolite are usually preferably 20% by mass or more and 80% by mass or less with respect to the total of the mass of activated alumina and the mass of zeolite, respectively. , 30% by mass or more and 70% by mass or less is more preferable.

As the hybrid adsorbent, a conventionally known adsorbent can be used. As the hybrid adsorbent, a commercially available product may be used. Examples of commercially available hybrid adsorbents include AZ-300 (manufactured by UOP or Union Showa). In the commercially available product AZ-300, the activated alumina moiety and the zeolite moiety are inseparably compounded.

Activated alumina is a porous aluminum oxide particle having an adsorptive ability. Activated aluminum can be produced by transferring alumina hydroxide to porous aluminum oxide with low crystallinity.
The pore size of the activated alumina moiety in the hybrid adsorbent is preferably 1 nm or more and 100 nm or less, and more preferably 1 nm or more and 80 nm or less from the viewpoint of the ability to adsorb epoxide impurities.

The pore size of the zeolite moiety in the hybrid adsorbent is preferably 0.2 nm or more and 1 nm or less, and more preferably 0.5 nm or more and 1 nm or less, from the viewpoint of the ability to adsorb epoxide impurities.
Preferred zeolites include Zeolite X, Zeolite Y, Zeolite A and the like. Of these, zeolite X is preferred.

The shape of the hybrid adsorbent is not particularly limited, and as described above, a pellet shape is preferable. The shape of the pellet is not particularly limited. Hybrid-based adsorption in that when the crude norbornene-based compound is brought into contact with the hybrid-based adsorbent, impurities generated due to wear of the pellets of the hybrid-based adsorbent can be easily prevented from being mixed into the monomer and the cyclic olefin polymer. The shape of the pellets of the agent is preferably spherical or substantially spherical.

Before the hybrid adsorbent is used in the purification step, the hybrid adsorbent may be activated by heating for the purpose of enhancing the adsorptive capacity.
The activation treatment is usually carried out in an inert gas atmosphere. The heating temperature in the activation treatment is preferably 100 ° C. or higher and 650 ° C. or lower, more preferably 200 ° C. or higher and 600 ° C. or lower, further preferably 300 ° C. or higher and 600 ° C. or lower, and particularly preferably 400 ° C. or higher and 600 ° C. or lower.
The heating time is preferably 0.1 hour or more and 100 hours or less, more preferably 0.5 hours or more and 50 hours or less, and further preferably 1 hour or more and 25 hours or less.

[Operation of purification process]
In the purification step, the entire amount of the crude norbornene compound used in the production of the cyclic olefin polymer may be subjected to the treatment with an adsorbent, and a part of the crude norbornene compound used in the production of the cyclic olefin polymer may be treated with the adsorbent. May be offered to.
When a part of the crude norbornene-based compound is treated with an adsorbent, the purified norbornene-based compound and the remaining crude norbornene-based compound not treated with the adsorbent are mixed and subjected to polymerization in the polymerization step described later. A crude norbornene-based compound treated with an adsorbent as long as a polymerization solution in which the ratio of the content of epoxide impurities to the content of the catalyst (mass ppm / mass ppm) to the total mass of the polymerization solution can be prepared is 6 or less. The amount of is not particularly limited.
Since it is easy to surely reduce the amount of epoxide impurities in the monomer to be polymerized to a desired amount or less, it is preferable to subject the entire amount of the crude norbornene compound used in the production of the cyclic olefin polymer to the treatment with an adsorbent. ..

Crude norbornene compounds usually come into contact with the adsorbent in a liquid state. Such a liquid may be a melt of a crude norbornene-based compound or a mixture of a crude norbornene-based compound and another monomer, and may be a crude norbornene-based compound or a crude norbornene-based compound and another monomer. May be a solution in which the above is dissolved in a solvent.
Due to its low viscosity, good contact efficiency with the adsorbent, and the fact that there is no risk of solidification of the crude norbornene compound due to a decrease in temperature, the crude norbornene compound or the crude norbornene compound and other single amounts. It is preferable that the solution obtained by dissolving the body in a solvent is brought into contact with the adsorbent.

The type of the crude norbornene-based compound or the solvent that dissolves the crude norbornene-based compound and other monomers is not particularly limited as long as the adsorption of epoxide impurities by the adsorbent is not inhibited.
Preferred solvents include hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclohexane, mineral oil, benzene, toluene and xylene, and halogenated hydrocarbon solvents such as chloroform, methylene chloride, dichloroethane and chlorobenzene. ..

When the crude norbornene compound is brought into contact with the adsorbent as a solution or a melt, the concentration of the crude norbornene compound in the solution or the melt is not particularly limited.
Typically, the concentration of the crude norbornene-based compound in the solution or melt is preferably 1% by mass or more and 100% by mass or less, and more preferably 10% by mass or more and 100% by mass or less.

The contact between the crude norbornene-based compound and the adsorbent may be carried out in a batch manner or in a continuous manner.
The method of contacting the crude norbornene-based compound with the adsorbent is not particularly limited.
For example, after charging the liquid containing the crude norbornene compound and the adsorbent in the container, the liquid containing the crude norbornene compound in the container and the adsorbent are allowed to stand or stir for a predetermined time. You may.
Contact between the crude norbornene compound and the adsorbent under stirring is preferable because the contact efficiency between the two is good. On the other hand, contact between the crude norbornene-based compound and the adsorbent under static conditions is preferable because it is easy to prevent impurities derived from the adsorbent from being mixed into the monomer and the cyclic olefin polymer due to wear of the adsorbent and the like.

Further, a liquid containing a crude norbornene compound may be circulated in a container such as a column filled with an adsorbent. In this case, for the purpose of prolonging the contact time between the crude norbornene compound and the adsorbent, a circulation treatment is performed in which the liquid containing the crude norbornene compound that has flowed out of the container such as the column is again flowed into the container such as the column. You may.

The contact time between the crude norbornene compound and the adsorbent is preferably 0.01 hours or more and 50 hours or less, and is 0, in terms of achieving both a large amount of the crude norbornene compound and a high efficiency of removing epoxide impurities. . 1 hour or more and 40 hours or less is more preferable, and 1 hour or more and 30 hours or less is particularly preferable.

The amount of the adsorbent is preferably 1 part by mass or more, more preferably 10 parts by mass or more, and 20 parts by mass or more with respect to 100 parts by mass of the crude norbornene compound from the viewpoint that the epoxide impure part can be easily removed. More preferred.
There is no particular upper limit to the amount of the adsorbent, but 80 parts by mass or less is preferable with respect to 100 parts by mass of the crude norbornene compound because the cost of the adsorbent is suppressed and an excessively large device is not required for the purification process. , 60 parts by mass or less is more preferable, and 40 parts by mass or less is further preferable.

In the polymerization step described later, the content of the aldehyde impurity derived from the norbornene-based compound in the monomer to be polymerized is preferably 50% by mass or less, preferably 30% by mass or less, based on the mass of the norbornene-based compound. Is more preferable, and 20 mass ppm or less is further preferable.
Further, in the polymerization step described later, the content of the ketone impurity derived from the norbornene compound in the monomer to be polymerized is preferably 50% by mass or less, preferably 30% by mass or less, based on the mass of the norbornene compound. Is more preferable, and 20 mass ppm or less is further preferable.
Here, the aldehyde impurity and the ketone impurity are impurities that can be generated due to the oxidation of the norbornene-based compound, respectively. These impurities may be a factor in deteriorating the polymerization yield when producing the cyclic olefin polymer.
The method for reducing the amount of aldehyde impurities and the amount of ketone impurities is not particularly limited. When the above hybrid adsorbent is used as the adsorbent, the amount of aldehyde impurities contained in the purified norbornene compound and the amount of ketone impurities tend to be low.
Further, the amount of aldehyde impurities and the amount of ketone impurities can be reduced by preventing the crude norbornene-based compound and the purified norbornene-based compound from coming into contact with oxygen as much as possible.

The purified norbornene-based compound obtained by carrying out the above-described treatment is then subjected to a "polymerization step".
When the purified norbornene-based compound is a solution, the purified norbornene-based compound may be subjected to the polymerization step as it is, or may be subjected to the polymerization step in a state of being isolated from the solution.

<Polymerization process>
In the polymerization step, the monomer containing the purified norbornene-based compound obtained in the above purification step is polymerized in the presence of a transition metal complex catalyst to produce a cyclic olefin polymer.
Here, the monomer may be completely supplied to the polymerization apparatus at one time, may be divided into several degrees and supplied, or may be continuously supplied.
The method of the polymerization reaction is not particularly limited, and may be a batch type or a continuous type.

In the polymerization step, the ratio of the content of epoxide impurities to the content of the catalyst (mass ppm / mass ppm) with respect to the total mass of the polymerization solution is 6 or less, preferably 5 or less, more preferably 4 or less, still more preferably 3. It will be adjusted as follows.
When the ratio of the content of epoxide impurities to the total mass of the polymerization solution provided for the polymer and the content of the catalyst is within the above range, the yield is expected to be stable depending on the polymerization conditions. Cyclic olefin polymers can be produced.
The lower limit of the ratio of the content of epoxide impurities to the content of the catalyst with respect to the total mass in the polymerization solution is not particularly limited, but may be 0.1 or more, and may be 1 or more from the viewpoint of ease of purification operation. It's okay.

The polymerization reaction in the polymerization step may be living polymerization or non-living polymerization. When it is desired to obtain a larger amount of cyclic olefin polymer with a smaller amount of catalyst, non-living polymerization, which is a chain polymerization in which a chain transfer reaction is intentionally repeated, is generally preferable.

In order to proceed with chain polymerization, it is necessary to have a compound having an appropriate chain transfer ability present in the reaction system. The chain transfer agent is not particularly limited, and a known compound having a chain transfer ability can be used. Typical chain transfer agents generally include alkylaluminum compounds, alkylzinc compounds or hydrogen. As the alkylaluminum compound, those contained in aluminoxane may be used, or may be added as appropriate.

Whether the polymerization proceeded by non-living polymerization or by living polymerization can be determined by the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the obtained polymer. .. Typically, a polymer having a molecular weight distribution of 1.1 or less is produced by living polymerization, and a polymer having a molecular weight distribution of more than 1.1 is produced by non-living polymerization.
In non-living polymerization, the molecular weight distribution often exceeds 1.5 and is about 2.

[Transition metal complex catalyst]
The transition metal complex catalyst is not particularly limited as long as it can catalyze the polymerization reaction of a monomer containing a norbornene-based compound. Preferred transition metal complex catalysts include metallocene catalysts.

As the metallocene catalyst (a), for example, a transition metal complex containing a ligand containing a cyclopentadiene ring and a transition metal of Group IV of the periodic table is preferable. The metallocene catalyst (a) preferably contains a metal atom selected from the group consisting of Ti, Zr, and Hf as a central metal.
As the metallocene catalyst (a), for example, a transition metal complex represented by the following formula (1) is preferable.
(Cp) (ZR ⁰¹ _m ) _n (A) _r ML _p L' _q ... (1)

In formula (1), (ZR ⁰¹ _m ) _n is a divalent group that binds Cp and A.
Z is C, Si, Ge, N, or P.
R ⁰¹ may be a hydrogen atom, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a linear group. It is an aliphatic hydrocarbon group having 1 or more and 20 or less carbon atoms, which may be branched or may contain a cyclic skeleton and may have an unsaturated bond.
When there are a plurality of R ^01s in (ZR ⁰¹ _m ), the plurality of R ^01s may be the same or different.
When (ZR ⁰¹ _m ) is repeated a plurality of times, the plurality of (ZR ⁰¹ _m ) may be the same or different.
Cp is a cyclopentadienyl group which may have a substituent or a cyclic group containing a cyclopentadiene ring which may have a substituent.
A is a group similar to Cp, or -O-, -S-, or -N (R ⁰² )-.
R ⁰² may contain a hydrogen atom, a linear chain, a branched chain, a cyclic skeleton, and may have an unsaturated bond. The number of carbon atoms is 1 or more and 20 or less. It is an aliphatic hydrocarbon group, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
M is a metal atom selected from the group consisting of Ti, Zr, and Hf.
L is an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and a branched chain even if it is linear. It is a monoanionic sigma ligand selected from the group consisting of aliphatic hydrocarbon groups having 1 to 20 carbon atoms, which may contain a cyclic skeleton and may have an unsaturated bond.
L may contain one or more Si atoms or Ge atoms.
When there are a plurality of Ls, the plurality of Ls may be the same or different, and are preferably the same.
L'is a halogen atom, -OR ⁰³ , or -N = C (R ⁰³ ) R ⁰³ .
R ⁰³ may contain a hydrogen atom or a hetero atom, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a direct group. It is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may be chain-like, branched-chain-like, may contain a cyclic skeleton, and may have an unsaturated bond. When ^{there are a plurality of R 03s} , they may be the same or different.
When there are a plurality of L's, the plurality of L's may be the same or different.
m is 1 or 2. More specifically, if Z is N or P, m is 1, and if Z is C, Si, or Ge, m is 2.
n is an integer of 0 or more and 4 or less.
r is 0 or 1. If r is 0, then n is 0.
p is an integer of 0 or more and 3 or less.
q is an integer of 0 or more and 3 or less.
When r is 1, p + q is equal to the oxidation state of the metal M minus 2 (the oxidation state of the metal M-2).
When r is 0, p + q is equal to the oxidation state of the metal M minus 1 (the oxidation state of the metal M-1).
p + q is less than 4.

In the transition metal complex represented by formula (1), the divalent bridging group ^{_{(ZR 01 m) n, CR}} 01 2, (CR 01 2) 2, (CR 01 2) 3, SiR 01 2, GeR 01 _It is preferably selected from the group consisting of 2, NR ⁰¹ , and PR ^01.
The divalent cross-linking group is more preferably Si (CH ₃ ) ₂ , SiPh ₂ , CH ₂ , (CH ₂ ) ₂ , (CH ₂ ) ₃ , C (CH ₃ ) ₂ , or CPh ₂ . Ph is a phenyl group.
m is 1 or 2, and n is an integer of 0 or more and 4 or less.

The ligand Cp that π-bonds to the metal M is a cyclopentadienyl group that may have a substituent or a cyclic group that contains a cyclopentadiene ring that may have a substituent.
Preferable examples of Cp are cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, 4-tert-butylcyclopenta. Dienyl group, 4-adamantylcyclopentadienyl group, monomethylindenyl group, dimethylindenyl group, trimethylindenyl group, tetramethylindenyl group, 4,5,6,7-tetrahydroindenyl group, fluorenyl group, 5,10-dihydroindeno [1,2-b] indol-10-yl group, N-methyl-5,10-dihydroindeno [1,2-b] indol-10-yl group, N-phenyl- 5,10-dihydroindeno [1,2-b] indol-10-yl group, 5,6-dihydroindeno [2,1-b] indol-6-yl; N-methyl-5,6-dihydro Indeno [2,1-b] indole-6-yl and N-phenyl-5,6-dihydroindeno [2,1-b] indole-6-yl can be mentioned.

A is a group similar to Cp, or -O-, -S-, or -N (R ⁰² )-. A is preferably a group similar to Cp.

The metal M is Ti, Zr or Hf.

As L, a group selected from the group consisting of a methyl group, an ethyl group, an n-butyl group, a sec-butyl group, a phenyl group, a benzyl group, and -CH ₂ Si (CH ₃ ) ₃ is preferable, and among them, a group is preferable. Methyl groups are more preferred.
As L' ^{, a group selected from the group consisting of halogen, -OR 03} (R ⁰³ is as described above), or -N = C (R ⁰³ ) R ⁰³ is preferable, and among them, -Cl, -O -2,6- (t-Bu) _2- C ₆ H ₃ or -N = C (t-Bu) ₂ is more preferable.

n is an integer of 0 or more and 4 or less, preferably 0 or more and 2 or less.

For the transition metal complex represented by the formula (1), as a specific example when n is 0 and r is 0, CpdMCl ₂ (O-2,6- (t-Bu) _2- C ₆ H _{3), CpdMMe 2 (O-} 2,6- (t-Bu) 2 -C 6 H 3), CpdMMeCl (O-2,6- (t-Bu) 2 -C 6 H 3), tet-CpdMCl 2 _{(O-2,6- (t-Bu} ) 2 -C 6 H 3), tet-CpdMMe 2 (O-2,6- (t-Bu) 2 -C 6 H 3), tet-CpdMMeCl (O- _{2,6- (t-Bu) 2 -C} 6 H 3), CpdMCl 2 (O-2,6- (i-Pr) 2 -C 6 H 3), CpdMMe 2 (O-2,6- (i _{-Pr) 2 -C 6 H 3)} , CpdMMeCl (O-2,6- (i-Pr) 2 -C 6 H 3), tet-CpdMCl 2 (O-2,6- (i-Pr) 2 - _{C 6 H 3), tet-} CpdMMe 2 (O-2,6- (i-Pr) 2 -C 6 H 3), tet-CpdMMeCl (O-2,6- (i-Pr) 2 -C 6 H ₃ ), CpdMCl ₂ (N = C (t-Bu) ₂ ), CpdMMe ₂ (N = C (t-Bu) ₂ ), CpdMMeCl (N = C (t-Bu) ₂ ), (t-BuC ₅ H) ₄ ) MCl ₂ (N = C (t-Bu) ₂ ), (t-BuC ₅ H ₄ ) MMe ₂ (N = C (t-Bu) ₂ ), (t-BuC ₅ H ₄ ) MMeCl (N = C (t-Bu) ₂ ), tet-CpdMCl ₂ (N = C (t-Bu) ₂ ), tet-CpdMMe ₂ (N = C (t-Bu) ₂ ), tet-CpdMMeCl (N = C (t) -Bu) ₂ ), CpdMCl ₂ (N = C- (t-Bu-N-CH = CH-N-t-Bu) ₂ ), CpdMMe ₂ (N = C- (t-Bu-N-CH = CH) -N-t-Bu) ₂ ), CpdMMeCl (N = C- (t-Bu-N-CH = CH-N-t-Bu) ₂ ), tet-CpdMCl ₂ (N = C- (t-Bu-) N-CH = CH-N-t-Bu) ₂ ), tet-CpdMMe ₂ (N = C- (t-Bu-N-CH = CH-N-t-Bu) ₂ ), tet-CpdMMeCl (N = C- (t-Bu-N-CH = CH-N-t-Bu) ₂ ) can be mentioned.
In the above example, Me is a methyl group, t-Bu is a tert-butyl group, i-Pr is an iso-propyl group, Cpd is a cyclopentadienyl group and tt-Cpd is a tetramethyl. It is a cyclopentadienyl group, and M is as described in the formula (1), and Zr, Ti, or Hf is preferable, and Ti is more preferable.

The transition metal complex represented by formula (1), n is 0, specific examples of when r is _{1, (Me 3 Cpd) 2} MCl 2, (Me 3 Cpd) 2 MMe 2, ( _{Me 3 Cpd) 2 MMeCl, (} Me 3 Cpd) 2 MPh 2, (Me 3 Cpd) 2 MBz 2, (Me 4 Cpd) 2 MCl 2, (Me 4 Cpd) 2 MMe 2, (Me 5 Cpd) 2 MCl ₂ , (Me ₅ Cpd) ₂ MPh ₂ , (Me ₅ Cpd) ₂ MBz ₂ , (EtMe ₄ Cpd) _{2 MCl 2} , [(Ph) Me ₄ Cpd] ₂ MCl ₂ , (Et ₅ Cpd) ₂ MCl ₂ , _{(Ind) 2 MCl 2, (} Ind) 2 MMeCl, (Ind) 2 MPh 2, (Ind) 2 MMe 2, (Ind) 2 MMeCl, (H 4 Ind) 2 MCl 2, (H 4 Ind) 2 MMe 2 include _{(H 4 Ind) 2 MPh 2} , and _{(Me 4 Cpd) (Me 5} Cpd) MCl 2.
In the above illustration, Me is methyl, Et is ethyl group, Cpd is a cyclopentadienyl group, Ind is an indenyl _group, H 4 Ind is 4,5,6,7, - tetrahydro It is an indenyl group, Ph is a phenyl group, and Bz is a benzyl group. Further, M is as described in the formula (1), and Zr, Ti, or Hf is preferable, and Zr is more preferable.

Specific examples of the transition metal complex represented by the formula (1) in the case where n is 1 or 2 and r is 1 are Me ₂ C (Cp) (Ind) MCl ₂ and Me ₂ C (Cp). ) (Ind) MMe ₂ , Me ₂ C (Cp) (Ind) MPh ₂ , Me ₂ C (Cp) (Ind) MBz ₂ , Me ₂ C (Cp) (Ind) MMeCl, Ph ₂ C (Cp) (Ind) ) MCl ₂ , Ph ₂ C (Cp) (Ind) MMe ₂ , Ph ₂ C (Cp) (Ind) MPh ₂ , Ph ₂ C (Cp) (Ind) MBz ₂ , Ph ₂ C (Cp) (Ind) MMeCl , Me ₂ Si (Me ₄ Cpd) ₂ MCl ₂ , Me ₂ Si (Me ₄ Cpd) ₂ MMe ₂ , Me ₂ Si (Me ₄ Cpd) ₂ MPh ₂ , Me ₂ Si (Me ₄ Cpd) ₂ MBz ₂ , Me ₂ Si (Me ₄ Cpd) ₂ MMeCl, Me ₂ C (Me ₄ Cpd) (Me Cpd) MCl ₂ , Me ₂ C (Me ₄ Cpd) ( _{Me Cpd) MMe 2} , Me ₂ Si (Ind) ₂ MCl ₂ , Me ₂ Si (Ind) ₂ MMe ₂ , Me ₂ Si (Ind) ₂ MPh ₂ , Me ₂ Si (Ind) ₂ MBz ₂ , Me ₂ Si (Ind) ₂ MMeCl, Me ₂ Si (Me ₄ Cpd) ₂ MCl ₂ , Me ₂ Si (Me ₄ Cpd) ₂ MMe ₂ , C ₂ H ₄ (Ind) ₂ MMe ₂ , C ₂ H ₄ (Ind) ₂ MPh ₂ , C ₂ H ₄ (Ind) ₂ MBz ₂ , C ₂ H ₄ (H) ₄ Ind) ₂ MMe ₂ , Ph (Me) Si (Ind) ₂ MMe ₂ , Ph ₂ Si (Ind) ₂ MMe ₂ , Me ₂ C (Flu) (Cpd) MCl ₂ , Me ₂ C (Flu) (Cpd) MMe ₂ , Me ₂ C (Flu) (Cpd) MPh ₂ , Me ₂ C (Flu) (Cpd) MBz ₂ , Ph ₂ C (Flu) (Cpd) MCl ₂ , Ph ₂ C (Flu) (Cpd) MMe ₂ , Ph ₂ C (Flu) (Cpd) MPh ₂ , Ph ₂ C (Flu) (Cpd) MBz ₂ , C ₂ H ₄ (Me ₄ Cpd) ₂ MCl ₂ , C ₂ H ₄ (Me ₄ Cpd) ₂ MMe _{2, C 2 Me 4 (Ind} ) 2 MCl 2, C 2 Me 4 (Ind) 2 MMe 2, Me 2 SiCH 2 (Ind) 2 MCl 2, Me 2 SiCH 2 (Ind) 2 MMe 2, Me 2 SiCH 2 (Ind) ₂ MPh ₂ , Me ₂ SCH ₂ (Ind) ₂ MBz ₂ , Me ₂ SCH ₂ (Ind) ₂ MMeCl, C ₂ H ₄ (2-MeInd) _{2 MCl 2} , C ₂ H ₄ (2-MeInd) ₂ MMe ₂ , C ₂ H ₄ (3-MeInd) _{2 MCl 2} , C ₂ H ₄ (3-MeInd) ₂ MMe ₂ , C ₂ H ₄ (4,7-Me ₂ Ind) ₂ MCl ₂ , C ₂ H ₄ (4,7-Me ₂ Ind) ₂ MMe ₂ , C ₂ H ₄ (5,6-Me ₂ Ind) ₂ MCl ₂ , C ₂ H ₄ (5,6-Me ₂ Ind) ₂ MMe ₂ , C _{2 H 4 (2-MeH 4 Ind} ) 2 MCl 2, Me 2 C (H 4 Ind) 2 MCl 2, Me 2 C (H 4 Ind) 2 MMe 2, Me 2 C (H 4 Ind) 2 MPh 2, Me ₂ C (H ₄ Ind) ₂ MBz ₂ , Me ₂ C (H ₄ Ind) ₂ MMeCl, Ph ₂ C (H ₄ Ind) ₂ MCl ₂ , Ph ₂ C (H ₄ Ind) ₂ MMe ₂ , Ph ₂ C ( H ₄ Ind) ₂ MPh ₂ , Ph ₂ C (H ₄ Ind) ₂ MBz ₂ , Ph ₂ C (H ₄ Ind) ₂ MMeCl, C ₂ H ₄ (2-MeH ₄ Ind) ₂ MMe ₂ , C ₂ H _{4 (2,4,7-Me 3 H 4 Ind} ) 2 MCl 2, C 2 H 4 (2,4,7-Me 3 H 4 Ind) 2 MMe 2, C 2 H 4 (4,7-Me 2 H _{4 Ind) 2 MCl 2, C} 2 H 4 (4,7-Me 2 H 4 Ind) 2 MMe 2, C 2 H 4 (2,4,7-Me 3 Ind) 2 MCl 2, C 2 H 4 ( 2,4,7-Me ₃ Ind) ₂ MMe ₂ , C ₂ H ₄ (2-Me-Benz [e] Ind) ₂ MCl ₂ , C ₂ H ₄ (2-Me-Benz) [E] Ind) ₂ MMe ₂ , C ₂ H ₄ (Benz [e] Ind) ₂ MCl ₂ , C ₂ H ₄ (Benz [e] Ind) ₂ MMe ₂ , Me ₂ Si (2-MeInd) _{2 MCl 2} , Me ₂ Si (2-MeInd) ₂ MMe ₂ , Me ₂ Si (4,7-Me ₂ Ind) ₂ MCl ₂ , Me ₂ Si (4,7-Me ₂ Ind) ₂ MMe ₂ , Me ₂ Si (5) _{, 6-Me 2 Ind) 2} MCl 2, Me 2 Si (5,6-Me 2 Ind) 2 MMe 2, Me 2 Si (2,4,7-Me 3 Ind) 2 MCl 2, Me 2 Si (2 , 4,7-Me ₃ Ind) ₂ MMe ₂ , Me ₂ Si (2-MeH ₄ Ind) _{2 MCl 2} , Me ₂ Si (2-MeH ₄ Ind) ₂ MMe ₂ , Me ₂ Si (4,7-Me) ₂ H ₄ Ind) ₂ MCl ₂ , Me ₂ Si (4,7-Me ₂ H ₄ Ind) ₂ MMe ₂ , Me ₂ Si (2,4,7-Me ₃ H ₄ Ind) ₂ MCl ₂ , Me ₂ Si _{(2,4,7-Me 3 H 4 Ind} ) 2 MMe 2, (t-BuNSiMe 2) (tet-Cpd) MCl 2, (t-BuNSiMe 2) (tet-Cpd) MMe 2, (t-BuNSiMe 2 _{) (tet-Cpd) MPh 2} , (t-BuNSiMe 2) (tet-Cpd) MBz 2, (t-BuNSiMe 2) (tet-Cpd) MMeCl, 1,1 '- (Me 2 C) 2 -2, _{2 '- (Me 2 C)} 2 (Cpd) 2 MCl 2, 1,1' - (Me 2 C) 2 -2,2 '- (Me 2 C) 2 (Cpd) 2 MMe 2 and the like.
In the above illustration, Me is a methyl group, Cpd is a cyclopentadienyl group, tet-Cpd is tetramethylcyclopentadienyl group, Ind is an indenyl _group, H 4 Ind is 4,5 , 6,7, -Tetrahydroindenyl group, Flu is a fluorenyl group, Ph is a phenyl group and Bz is a benzyl group. Further, M is as described in the formula (1), and Zr, Ti, or Hf is preferable, and Zr is more preferable.

Among the metallocene compounds represented by the formula (1) described above, for example, Me ₂ C (Flu) (Cpd) ZrCl ₂ , Me ₂ C (Flu) (Cpd) ZrMe ₂ , Me ₂ C (Flu) ( Cpd) ZrPh ₂ , Me ₂ C (Flu) (Cpd) ZrBz ₂ , Ph ₂ C (Flu) (Cpd) ZrCl ₂ , Ph ₂ C (Flu) (Cpd) ZrMe ₂ , Ph ₂ C (Flu) (Cpd) ZrPh ₂ and Ph ₂ C (Flu) (Cpd) ZrBz ₂ are preferably used for copolymerization of norbornene-based compounds and ethylene, which will be described later, and are preferably used for copolymerization of norbornene and ethylene.

Further, as another preferable example of the metallocene compound represented by the formula (1), a compound represented by the following formula (a1) can be mentioned.

In the formula (a1), Ra ¹ , Ra ² , Ra ³ , and Ra ⁴ are each independently a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom.
R ^a1 and R ^a2 are bonded to a silicon atom by a C—Si bond, an O—Si bond, a Si—Si bond, or an N—Si bond, respectively.
^Ra3 is bonded to a nitrogen atom by a CN bond, an ON bond, a Si—N bond, or an NN bond.
^Ra4 is bonded to the metal atom M by a CM bond.
R ^a5 and R ^a6 are organic substituents or inorganic substituents having 1 or more and 20 or less carbon atoms which may independently contain heteroatoms, and p and q are 0 or more and 4 or less, respectively. Is an integer of.
When ^{there are a plurality of R a5} and R ^a6 , respectively, the plurality of R ^a5 and R ^a6 may be different groups.
When two groups of two groups or more R ^a6, among the plurality of R ^a5 are bonded to adjacent positions on the aromatic ring, to form a ring the two groups are bonded to each other May be good.
M is a Group IV transition metal of the Periodic Table, preferably Ti, Zr, or Hf.

The metal atom M in the formula (a1) can take any coordination form with a ligand having a fluorene skeleton in the range of hapticity 1 or more and 5 or less.

R ^a1 , R ^a2 , R ^a3 , and R ^a4 are hydrocarbon groups having 1 to 20 carbon atoms which may independently contain a heteroatom.

Regarding a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, when the hydrocarbon group contains a hetero atom, the type of the hetero atom is not particularly limited as long as the object of the present invention is not impaired. Specific examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a selenium atom, a halogen atom and the like.

R ^a1 and R ^a2 are bonded to a silicon atom by a C—Si bond, an O—Si bond, a Si—Si bond, or an N—Si bond, respectively.
Preferable examples of ^{R a1} and R ^a2 bonded to a silicon atom by an O—Si bond include groups represented by ^{−OR a7} and −OC (= O) −R ^a7.
Preferable examples of ^{R a1} and R ^a2 bonded to a silicon atom by a Si-Si bond ^{are -SiR a7} ₃ , -Si (OR ^a7 ) R ^a7 ₂ , -Si (OR ^a7 ) ₂ R ^a7 , and -Si. ^Examples include the group represented by (OR a7) _3.
Suitable examples of ^{R a1} and ^{R a2} bonded to the silicon atom by N-Si bonds, -NHR ^a7, and include groups represented by ^{-NR a7} _2.
Here, both the above R ^a7 is a hydrocarbon group.

^Ra3 is bonded to a nitrogen atom by a CN bond, an ON bond, a Si-N bond, or an NN bond.
Preferable examples of ^{R a3} bonded to a nitrogen atom by an ON bond include groups represented by ^{-OR a7} and -OC (= O) -R ^a7.
Preferable examples of ^{R a3} that binds to a nitrogen atom by a Si-N bond ^{are -SiR a7} ₃ , -Si (OR ^a7 ) R ^a7 ₂ , -Si (OR ^a7 ) ₂ R ^a7 , and -Si (OR ^a7). ) The group represented by _{3 is mentioned.}
Preferable examples of ^{R a3} bound to the nitrogen atom by N-N bonds, -NHR ^a7, and include groups represented by ^{-NR a7} _2.
Here, both the above R ^a7 is a hydrocarbon group.

Since the preparation and availability of the compound used as a ligand is easy, preferably the R ^a1 and R ^a2 are the same group.

As R ^a1 , R ^a2 , R ^a3 , and R ^a4 , hydrocarbon groups containing no heteroatom are preferable because they are excellent in chemical stability.
Examples of such hydrocarbon groups include linear or branched alkyl groups, linear or branched unsaturated aliphatic hydrocarbon groups which may have double bonds and / or triple bonds, and cycloalkyls. Groups, cycloalkylalkyl groups, aromatic hydrocarbon groups, and aralkyl groups are preferred.

Specific examples of the linear or branched alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group and n-. Pentyl group, isopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group. , N-Tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecil group, and n-icosyl group.

Preferred examples of the linear or branched unsaturated aliphatic hydrocarbon group which may have a double bond and / or a triple bond include specific examples of the linear or branched alkyl group. Examples of the group include a group in which one or more single bonds are replaced with double bonds and / or triple bonds.
More preferably, a vinyl group, an allyl group, a 1-propenyl group, a 3-butenyl group, a 2-butenyl group, a 1-butenyl group, an ethenyl group, and a propargyl group can be mentioned.

Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cycloundecyl group, a cyclododecyl group, a cyclotridecyl group, and the like. Examples thereof include a cyclotetradecyl group, a cyclopentadecyl group, a cyclohexadecyl group, a cycloheptadecyl group, a cyclooctadecyl group, a cyclononadecil group, and a cycloicosyl group.

Specific examples of the cycloalkylalkyl group include cyclopropylmethyl group, cyclobutylmethyl group, cyclopentylmethyl group, cyclohexylmethyl group, cycloheptylmethyl group, cyclooctylmethyl group, cyclononylmethyl group, cyclodecylmethyl group, and cycloun. Decylmethyl group, cyclododecylmethyl group, cyclotridecylmethyl group, cyclotetradecylmethyl group, cyclopentadecylmethyl group, cyclohexadecylmethyl group, cycloheptadecylmethyl group, cyclooctadecylmethyl group, cyclononadecilmethyl group, 2-Cyclopropylethyl group, 2-cyclobutylethyl group, 2-cyclopentylethyl group, 2-cyclohexylethyl group, 2-cycloheptylethyl group, 2-cyclooctylethyl group, 2-cyclononylethyl group, 2-cyclo Decylethyl group, 2-cycloundecylethyl group, 2-cyclododecylethyl group, 2-cyclotridecylethyl group, 2-cyclotetradecylethyl group, 2-cyclopentadecylethyl group, 2-cyclohexadecylethyl group , 2-Cycloheptadecylethyl group, 2-Cyclooctaethyldecyl group, 3-Cyclopropylpropyl group, 3-Cyclobutylpropyl group, 3-Cyclopentylpropyl group, 3-Cyclohexylpropyl group, 3-Cycloheptylpropyl group, 3-Cyclooctylpropyl group, 3-cyclononylpropyl group, 3-cyclodecylpropyl group, 3-cycloundecylpropyl group, 3-cyclododecylpropyl group, 3-cyclotridecylpropyl group, 3-cyclotetradecylpropyl group Group, 3-cyclopentadecylpropyl group, 3-cyclohexadecylpropyl group, 3-cycloheptadecylpropyl group, 4-cyclopropylbutyl group, 4-cyclobutylbutyl group, 4-cyclopentylbutyl group, 4-cyclohexylbutyl Group, 4-cycloheptylbutyl group, 4-cyclooctylbutyl group, 4-cyclononylbutyl group, 4-cyclodecylbutyl group, 4-cyclododecylbutyl group, 4-cyclotridecylbutyl group, 4-cyclotetradecyl Examples thereof include a butyl group, a 4-cyclopentadecylbutyl group, and a 4-cyclohexadecylbutyl group.

Specific examples of the aromatic hydrocarbon group include phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group and 2,5-dimethyl. Phenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3 , 6-trimethylphenyl group, 2,4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, o-ethylphenyl group, m-ethylphenyl group, p -Ethylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl group, o-tert-butylphenyl group, 2,3-diisopropylphenyl group, 2,4-diisopropylphenyl group, 2,5 -Diisopropylphenyl group, 2,6-diisopropylphenyl group, 3,4-diisopropylphenyl group, 3,5-diisopropylphenyl group, 2,6-di-tert-butylphenyl group, 2,6-di-tert-butyl -4-Methylphenyl group, α-naphthyl group, β-naphthyl group, biphenyl-4-yl group, biphenyl-3-yl group, biphenyl-2-yl group, anthracene-1-yl group, anthracen-2-yl group Group, anthracene-9-yl group, phenylentren-1-yl group, phenylentren-2-yl group, phenylentren-3-yl group, phenylentren-4-yl group, phenylentren-9-yl group, pyrene-1-yl group , Pyrene-2-yl group, Pyrene-3-yl group, and Pyrene-4-yl group.

Specific examples of the aralkyl group include a benzyl group, a phenethyl group, a 1-phenylethyl group, a 3-phenylpropyl group, a 2-phenylpropyl group, a 1-phenylpropyl group, a 2-phenyl-1-methylethyl group, and a 1-. Phenyl-1-methylethyl group (cumyl group), 4-phenylbutyl group, 3-phenylbutyl group, 2-phenylbutyl group, 1-phenylbutyl group, 3-phenyl-2-methylpropyl group, 3-phenyl- 1-Methylpropyl group, 2-phenyl-1-methylpropyl group, 2-methyl-1-phenylpropyl group, 2-phenyl-1,1-dimethylethyl group, 2-phenyl-2,2-dimethylethyl group, Examples thereof include α-naphthylmethyl group, β-naphthylmethyl group, 2-α-naphthylethyl group, 2-β-naphthylethyl group, 1-α-naphthylethyl group, and 1-β-naphthylethyl group.

As R ^a1 and R ^a2 , an alkyl group having 1 or more and 20 or less carbon atoms and an aromatic hydrocarbon group having 6 or more and 20 or less carbon atoms are preferable, and an alkyl group having 1 or more and 10 or less carbon atoms and an number of carbon atoms are preferable. An aromatic hydrocarbon group having 6 or more and 10 or less is more preferable, an alkyl group having 1 or more and 6 or less carbon atoms and a phenyl group are further preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.

R ^a3 includes an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and 7 to 20 carbon atoms. Aralkyl group is preferred.

R ^a4 includes an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and aromatic carbonation having 6 to 20 carbon atoms. Hydrogen groups and aralkyl groups having 7 or more and 20 or less carbon atoms are preferable.

In the formula (a1), R ^a5 and R ^a6 are each independently an organic substituent or an inorganic substituent having 1 to 20 carbon atoms which may contain a heteroatom, and p and q are respectively. It is an integer of 0 or more and 4 or less independently.
When ^{there are a plurality of R a5} and R ^a6 , respectively, the plurality of R ^a5 and R ^a6 may be different groups.

Examples of the organic substituent include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and 2 to 20 carbon atoms. Examples thereof include an aliphatic acyl group, a benzoyl group, an α-naphthylcarbonyl group, a β-naphthylcarbonyl group, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.

Among these organic substituents, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and 2 to 6 carbon atoms. The aliphatic acyl group, the benzoyl group, the phenyl group, the benzyl group, and the phenethyl group of the above are preferable.

Among the organic substituents, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a methoxy group, an ethoxy group and an n-propyloxy group. , Isobutyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, acetyl group, propionyl group, butanoyl group, and phenyl group are more preferable.

The inorganic substituent is not particularly limited as long as it is an inorganic group conventionally known to be capable of substituting on an aromatic ring and does not inhibit the formation reaction of the metallocene compound represented by the above formula (a1). ..
Specific examples of the inorganic group include a halogen atom, a nitro group, a cyano group and the like.

When two groups of two groups or more R ^a6, among the plurality of R ^a5 are bonded to adjacent positions on the aromatic ring, to form a ring the two groups are bonded to each other May be good. Such a ring is a fused ring that condenses with the aromatic ring contained in the fluorene skeleton in the formula (a1). The fused ring may be an aromatic ring or an aliphatic ring, and an aliphatic ring is preferable. The fused ring may have a hetero atom such as an oxygen atom, a nitrogen atom, and a sulfur atom in the ring.

Specific examples of a fluorene skeleton having a fused ring formed by ^{two Ra5} and / or two ^{Ra6 include the skeleton of the following formula.}

In the formula (a1), M is a Group IV transition metal of the periodic table, and Ti, Zr, or Hf is preferable, and Ti is more preferable.

A preferable example of the metallocene compound represented by the formula (a1) described above is a metallocene compound having the following structure.

The metallocene compound represented by the above formula (a1) is preferably used for homopolymerization of norbornene-based compounds and copolymerization of norbornene-based compounds with 1-octene, 1-hexene, or a mixture thereof. And 1-octene, 1-hexene, or a mixture thereof are preferably used by copolymerization.

When the metallocene catalyst (a) described above is a solvent, the solvent contained in the solution is not particularly limited. Preferred solvents include hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclohexane, mineral oil, benzene, toluene and xylene, and halogenated hydrocarbon solvents such as chloroform, methylene chloride, dichloroethane and chlorobenzene. ..
The concentration of the metallocene catalyst (a) in the solution of the metallocene catalyst (a) is not particularly limited. The concentration of the metallocene catalyst (a) is, for example, preferably 0.1 mmol / L or more and 0.5 mol / L or less, and more preferably 1 mmol / L or more and 0.25 mol / L or less.

[Catalyst composition]
The metallocene catalyst (a) described above is preferably used as a catalyst composition as described below.
The catalyst composition is typically produced by mixing a solution of the metallocene catalyst (a) with one or more selected from the group consisting of aluminoxane (b1) and an ionic compound (b2).
Here, the ionic compound (b2) is a compound that produces a cationic transition metal compound by reacting with the metallocene catalyst (a).

Mixing a solution of the metallocene catalyst (a) with one or more selected from the group consisting of aluminoxane (b1) and an ionic compound (b2) for preparing a catalyst composition is a polymerization reaction before polymerization. It may be carried out in a device different from the tank, or may be carried out in the polymerization reaction tank before or during the polymerization.

Hereinafter, the materials used for preparing the catalyst composition and the preparation conditions for the catalyst composition will be described.

[Aluminoxane (b1)]
As the alkynexane (b1), various aluminoxanes conventionally used as co-catalysts in the polymerization of various olefins can be used without particular limitation. Typically, the aluminoxane is an organic aluminoxane.
In the production of the catalyst composition, one type of aluminoxane (b1) may be used alone, or two or more types may be used in combination.

As the aluminoxane (b1), an alkylaluminoxane is preferably used. Examples of the alkylaluminoxane include compounds represented by the following formulas (b1-1) or (b1-2). The alkylaluminoxane represented by the following formula (b1-1) or (b1-2) is a product obtained by reacting trialkylaluminum with water.

（式（ｂ１−１）及び式（ｂ１−２）中、Ｒは炭素原子数１以上４以下のアルキル基、ｎは０以上４０以下、好ましくは２以上３０以下の整数を示す。）

(In the formulas (b1-1) and (b1-2), R represents an alkyl group having 1 or more and 4 or less carbon atoms, and n represents an integer of 0 or more and 40 or less, preferably 2 or more and 30 or less.)

Examples of the alkylaluminoxane include methylaluminoxane and modified methylaluminoxane in which a part of the methyl group of the methylaluminoxane is replaced with another alkyl group. As the modified methylaluminoxane, for example, as the substituted alkyl group, a modified methylaluminoxane having an alkyl group having 2 to 4 carbon atoms such as an ethyl group, a propyl group, an isopropyl group, a butyl group and an isobutyl group is preferable, and methyl is particularly preferable. A modified methylaluminoxane in which a part of the group is replaced with an isobutyl group is more preferable. Specific examples of the alkylaluminoxane include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, methylisobutylaluminoxane and the like, and among them, methylaluminoxane and methylisobutylaluminoxane are preferable.

Alkyl aluminoxane can be prepared by a known method. Further, as the alkylaluminoxane, a commercially available product may be used. Examples of commercially available alkylaluminoxane products include MMAO-3A, TMAO-200 series, TMAO-340 series (all manufactured by Toso Finechem Co., Ltd.) and methylaminenoxane solution (manufactured by Albemarle Corporation).

[Ionic compound (b2)]
The ionic compound (b2) is a compound that produces a cationic transition metal compound by reacting with the metallocene catalyst (a).
Such ionic compounds include tetrakis (pentafluorophenyl) borate anions, amine cations with active cations such as _{(CH 3} ) ₂ N (C ₆ H ₅ ) H ⁺ _{, and (C 6} H ₅ ) ₃ C ^+. Ionic compounds such as trisubstituted carborane cations, carborane cations, metal carborane cations, and ferrosenium cations with transition metals can be used.

[solvent]
The metallocene catalyst (a), aluminoxane (b1), and the ionic compound (b2) described above are usually used in a state of being dissolved or suspended in a solvent, preferably dissolved.
The type of solvent is not particularly limited as long as it does not interfere with the object of the present invention.
Preferred solvents include hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclohexane, mineral oil, benzene, toluene and xylene, and halogenated hydrocarbon solvents such as chloroform, methylene chloride, dichloroethane and chlorobenzene. ..

The amount of the solvent used is not particularly limited as long as the catalyst composition having the desired performance can be produced. Typically, the concentrations of the metallocene catalyst (a), aluminoxane (b1), and the ionic compound (b2) are preferably 0.00000001 to 100 mol / L, more preferably 0.00000005 to 50 mol / L, and particularly preferably. An amount of solvent of 0.000000001 to 20 mol / L is used.

When mixing the liquid containing the raw material of the catalyst composition, the number of moles of transition metal elements in the metallocene catalyst (a) and M _a, the number of moles of aluminum in the aluminoxane (b1) and M _b1, ionic compounds (b2 the number of moles of) in the case of the _{M b2,} (the value of _{M b1 + M b2) / M} a is preferably from 1 to 200,000, more preferably 100 to 100000, as particularly preferably at from 1,000 to 80,000, the catalyst It is preferable that the liquid containing the raw material of the composition is mixed.

The temperature at which the liquid containing the raw material of the catalyst composition is mixed is not particularly limited, but is preferably -100 to 100 ° C, more preferably -50 to 50 ° C.
It is possible.

[Polymerization conditions]
The polymerization conditions are not particularly limited as long as a desired cyclic olefin polymer can be obtained, and known conditions can be used, and the polymerization temperature, polymerization pressure, polymerization time and the like are appropriately adjusted. The amount of each monomer component used when copolymerizing a norbornene-based compound with another monomer is exemplified as follows.
The amount of the other monomer added to 1 mol of the norbornene-based compound is preferably 0.001 mol or more and 30 mol or less, and more preferably 0.01 mol or more and 20 mol or less.
The amount of the catalyst composition used is derived from the amount of the transition metal complex catalyst used in its preparation. The amount of the transition metal complex catalyst used in the preparation of the catalyst composition is preferably 0.000000001 mol or more and 0.005 mol or less, and 0.00000001 mol or more and 0. More preferably, it is 0005 mol or less.

The polymerization temperature is not particularly limited as long as the polymerization reaction proceeds at a desired rate. The polymerization temperature is typically 0 ° C. or higher and 120 ° C. or lower, preferably 10 ° C. or higher and 100 ° C. or lower, and more preferably 20 ° C. or higher and 90 ° C. or lower.
The polymerization time is not particularly limited, and the polymerization is carried out until a desired yield is reached or the molecular weight of the polymer increases to a desired degree.
The polymerization time varies depending on the temperature, the composition of the catalyst composition, and the monomer composition, but is typically 0.01 hours or more and 120 hours or less, preferably 0.1 hours or more and 80 hours or less, and is 0. . More preferably 2 hours or more and 10 hours or less.

From the viewpoint that it is easy to produce a cyclic olefin polymer in a good yield, the norbornene-based compound or the polymerization system containing the norbornene-based compound and other monomers is subjected to aluminoxane and alkylaluminum before adding the catalyst composition. It is preferable to have one or more selected from the compounds.

Alminoxane is as described in the method for producing the catalyst composition.
As the alkylaluminum compound, those conventionally used for polymerization of olefins and the like can be used without particular limitation. Examples of the alkylaluminum compound include compounds represented by the following general formula (II).
(R ¹⁰ ) _z AlX _3-z (II)
(In formula (II), R ¹⁰ is an alkyl group having 1 or more and 15 or less carbon atoms, preferably 1 or more and 8 or less, X is a halogen atom or a hydrogen atom, and z is an integer of 1 or more and 3 or less. is there.)

Examples of the alkyl group having 1 or more and 15 or less carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and an n-octyl group.

Specific examples of the alkylaluminum compound include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, trisec-butylaluminum and trin-octylaluminum; dimethylaluminum chloride, Examples thereof include dialkylaluminum halides such as diisobutylaluminum chloride; dialkylaluminum hydrides such as diisobutylaluminum hydride; and dialkylaluminum alkoxides such as dimethylaluminummethoxyde.

Such an alkylaluminum compound acts as a chain transfer agent and promotes chain polymerization catalyzed by the catalyst composition described above.

When aluminoxane is added to the polymerization system before adding the catalyst composition, the amount of aluminum used in the aluminoxane per 1 mol of the transition metal complex catalyst is preferably 10 mol or more and 1,000,000 mol or less, and 100 mol or more and 100,000 mol. The following is more preferable.
When the alkylaluminum compound is added to the polymerization system before adding the catalyst composition, the number of moles of aluminum per 1 mol of the transition metal complex catalyst is preferably 5 mol or more and 500,000 mol or less, and 50 mol or more and 50,000 mol or less. Is more preferable.

It is preferable that at least a part, preferably all of the catalyst composition is continuously added to the polymerization system.
By continuously adding the catalyst composition, the cyclic olefin polymer can be continuously produced, and the production cost of the cyclic olefin polymer can be reduced.

According to the method described above, the crude norbornene-based compound containing the epoxide impurity is treated with a hybrid-based adsorbent composed of a mixture of active alumina and zeolite to reduce the epoxide impurity in the monomer. As a result, the ratio (mass ppm / mass ppm) of the content of the epoxide impurity to the content of the catalyst with respect to the total mass of the polymerization solution to be subjected to the polymerization is set to 6 or less, which is expected to meet the polymerization conditions. The cyclic olefin polymer can be stably produced in the yield obtained.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.

[Examples 1 to 3, Comparative Example 1, Comparative Example 2, and Reference Example 1]
Toluene solution (concentration 75% by mass) of norbornene compound (norbornene) containing the amounts of epoxide impurities (2,3-epoxynorbornene) shown in Table 1 and 20% by mass based on the mass of norbornene compound (norbornene) The types of adsorbents listed in Table 1 of the above were mixed in a glass container having an inert gas atmosphere. Next, the contents of the glass container were allowed to stand at room temperature for 24 hours to adsorb epoxide impurities.

The adsorbents listed in Table 1 are as follows.
AB1: Hybrid adsorbent consisting of activated alumina and zeolite (AZ-300, manufactured by Union Showa)
AB2: Molecular Sheave (MS-4A)
The impurities listed in Table 1 are as follows.
EP: Epoxide impurities (2,3-epoxy norbornane)
AL: Aldehyde impurities derived from norbornene KE: Ketone impurities derived from norbornene

The amount of impurities before the adsorbent treatment shown in Table 1 is the amount of each impurity (mass ppm) with respect to the mass of the norbornene compound in the toluene solution of the norbornene compound.
The amount of each impurity (mass ppm) with respect to the mass of the norbornene compound in a toluene solution of the norbornene compound was measured using the following apparatus according to the following conditions.
<Impurity amount measuring device and measuring conditions>
[apparatus]
Analyzer: GC / MS (7890A / 5975C)
Injector: 7683B
Injection volume: 1 μl
Carrier gas: He
[GC (Gas Chromatograph) Information]
(Inlet)
Mode: Split Split ratio: 30: 1
Heater temperature: 300 ℃
(column)
Column name: FRONTIER UltraALLOY + -5
Dimensions: 30m x 250μm x 0.25μm
Flow rate: 1 mL / min.
[MS (Mass Spectrometer) Information]
Measurement mode: Scan method Solvent waiting time: 5.5 min
Scan range 15-650 m / z
Ion source temperature: 230 ° C
Quadrupole temperature: 150 ° C
Qualitative method: Measure EP standard sample and judge from retention time and MS spectrum.
Quantification method: A calibration curve was prepared from the EP standard sample and quantified. The AL and KE were also quantified from the EP calibration curve on the assumption that they were about the same as the EP sensitivity.

The amount of each impurity (mass ppm) with respect to the mass of the norbornene compound in the toluene solution of the norbornene compound after the treatment with the adsorbent for 24 hours was also measured in the same manner as in the toluene container before the treatment.
The measurement results are shown in Table 1.

Then, a toluene solution of a metallocene catalyst having a concentration of 7.3 mmol / L was prepared. The structure of the metallocene catalyst is as follows. Then, using a metallocene-catalyzed toluene solution, copolymerization of norbornene (2-norbornene) and 1-hexene was carried out according to the following method.

A mixture of 2-norbornene and 1-hexene (molar ratio: 2-norbornene / 1-hexene = 36/64) was added to a 200 mL two-mouth glass reactor kept in a dry and nitrogen atmosphere at a concentration of 54% by mass. Was added as a toluene solution.
MMAO-3A and TMAO-211 were added to the glass reactor so that MMAO-3A / metallocene catalyst = 1250 (molar ratio) and TMAO-211 / metallocene catalyst = 1100 (molar ratio), respectively. After sufficiently immersing the glass reactor in a water bath at 40 ° C., polymerization was started by adding a toluene solution of a metallocene catalyst into the glass reactor.
At the start of polymerization, EP in a "polymerization solution" consisting of a monomer (2-norbornene and 1-hexene), a solvent (toluene), a co-catalyst (two types of MAO), and a metallocene catalyst. , AL, and KE (mass ppm) were measured according to the method described above, and the impurity content in the polymerization solution was based on the calculated value of the metallocene catalyst content (mass ppm) in the "polymerization solution". / The catalyst content ratio (mass ppm / mass ppm) was determined. The ratio of impurity content / catalyst content (mass ppm / mass ppm) in the polymerization solution is shown in Table 1.

After a polymerization time of 5 hours, 2-propanol was added to terminate the reaction. Next, the obtained polymerization reaction solution was poured into a large amount of hydrochloric acid acidic acetone to completely precipitate the polymer, and after filtering and washing, the polymer was dried under reduced pressure at 110 ° C. for 1 day or more to obtain a copolymer. ..
The yield after polymerization was determined from the yield of the copolymer. The yields are shown in Table 1.

MMAO-3A is methyl represented by _{[(CH 3} ) _0.7 (iso-C ₄ H _{9 ) 0.3} AlO] _n having a concentration of 6.5% by mass (as the content of Al atom). It is a toluene solution of isobutylaluminoxane (manufactured by Toso Finechem Co., Ltd., and still contains 6 mol% of trimethylaluminum with respect to total Al), and TMAO-111 has a concentration of 9.0% by mass (as the content of Al atoms). ) Intoluene solution of methylaluminoxane (manufactured by Toso Finechem Co., Ltd., still containing 26 mol% of trimethylaluminum with respect to total Al).

※表１中、「Ｎ．Ｄ．」は、不純物量が検出限界以下であったことを意味し、「不純物Ｎ．Ｄ．」は、不純物量が検出限界以下であったことにより、不純物量／触媒量の比率を算出しなかったことを意味する。

* In Table 1, "ND" means that the amount of impurities was below the detection limit, and "Objection N.D." means that the amount of impurities was below the detection limit. / It means that the ratio of the amount of catalyst was not calculated.

According to Examples 1 to 3, by using a hybrid adsorbent (AB1) composed of a mixture of activated alumina and zeolite as the adsorbent, the epoxy impurities (EP) are satisfactorily converted from norbornene containing the epoxy impurities (EP). It turns out that can be removed.
Further, according to Examples 1 to 3, if the ratio (mass ppm / mass ppm) of the content of the epoxide impurity (EP) to the content of the catalyst with respect to the polymerization solution to be subjected to the polymerization is 6 or less. It can be seen that the cyclic olefin polymer can be obtained in good yield.

On the other hand, according to Comparative Example 1 and Comparative Example 2, when the molecular sieve (AB2) is used as an adsorbent, it is difficult to satisfactorily remove the epoxy impurity (EP) from the norbornene containing the epoxy impurity (EP). It can be seen that the ratio of the content of the epoxide impurity (EP) to the content of the catalyst (mass ppm / mass ppm) is high, and as a result, it is difficult to obtain a cyclic olefin polymer in a good yield.

Further, according to Comparative Example 1, Comparative Example 2, and Reference Example 1, when the molecular sieve (AB2) is used as the adsorbent, the aldehyde impurity (AL) and the ketone impurity (KE) are treated with the adsorbent during the treatment with the adsorbent. It turns out that it can occur.
According to the comparison between Example 1 and Reference Example 1, in which the amounts of epoxy impurities (EP) in the toluene solution after the adsorbent treatment are close, the aldehyde impurity (AL) and the ketone impurity (KE) are cyclic olefins. It is presumed that this may be a factor in lowering the polymerization yield of the polymer.

Claims (7)

A method for producing a cyclic olefin polymer by polymerizing a monomer containing a norbornene-based compound containing an epoxide impurity.
By contacting the crude norbornene-based compound containing the epoxide impurity with an adsorbent, a purified norbornene-based compound can be obtained.
The above-mentioned monomer containing the purified norbornene-based compound is polymerized in the presence of a transition metal complex catalyst.
The norbornene-based compound is norbornene, and the following formula (I):

(In the formula, R ^{1 to} R ¹² may be the same or different, respectively, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a saturated aliphatic hydrocarbon group, an aralkyl group, and an aromatic hydrocarbon group. It is an atom or a group
The ^{two groups selected from R 9 to} R ¹² may be bonded to each other to form a saturated aliphatic hydrocarbon ring or an aromatic hydrocarbon ring.
Further, n indicates 0 or a positive integer.
When n is 2 or more, R ^{5 to} R ⁸ may be the same or different in each repeating unit.
However, when n = 0, ^{at least one of R 1 to} R ⁴ and R ^{9 to} R ¹² is not a hydrogen atom. )
It is one or more compounds selected from the group consisting of substituted norbornene represented by.
The epoxide impurity is an epoxy compound in which a carbon-carbon unsaturated double bond is oxidized in 2,3-epoxynorbornane and / or a substituted norbornene represented by the above formula (I).
The adsorbent is a hybrid adsorbent composed of a mixture of activated alumina and zeolite.
The transition metal complex catalyst has the following formula (a1):

(In the formula (a1), R ^a1 , R ^a2 , R ^a3 , and R ^a4 are hydrocarbon groups having 1 to 20 carbon atoms which may independently contain a heteroatom, and R ^a1 and R ^a2 is bonded to a silicon atom by C-Si bond, O-Si bond, Si-Si bond, or N-Si bond, respectively, and R ^a3 is bonded to a silicon atom by C-Si bond, ON bond, Si-N bond, respectively. Alternatively, it is bonded to a nitrogen atom by an NN bond, ^Ra4 is bonded to a metal atom M by a ^CM bond, and Ra5 and ^Ra6 are each independently having 1 carbon atom which may contain a heteroatom. 20 or more organic substituents or inorganic substituents, p and q are independently integers of 0 or more and 4 or less, and when R ^a5 and R ^a6 are each plural, a plurality of R ^a5 and R ^a6 may be a different group, when bound to a position where the two groups are adjacent on the aromatic rings of the two groups or more R ^a6, of the plurality of R ^a5, the two groups They may be coupled to each other to form a ring, where M is a Group IV transition metal of the periodic table.)
It is a compound represented by
The ratio (mass ppm / mass ppm) of the content of the epoxide impurity to the content of the catalyst with respect to the total mass of the polymerization solution to be subjected to the polymerization is 6 or less.
The production method, wherein the total mass of the polymerization solution is the total mass of the raw materials used for producing the cyclic olefin polymer. The cyclic olefin polymer according to claim 1, wherein the ratio (mass ppm / mass ppm) of the content of aldehyde impurities derived from the norbornene compound to the content of the catalyst with respect to the total mass of the polymerization solution is 2 or less. Manufacturing method. The cyclic according to claim 1 or 2, wherein the ratio (mass ppm / mass ppm) of the content of ketone impurities derived from the norbornene-based compound to the content of the catalyst with respect to the total mass of the polymerization solution is 2 or less. A method for producing an olefin polymer. The method for producing a cyclic olefin polymer according to any one of claims 1 to 3, wherein the amount of the adsorbent is 1 part by mass or more with respect to 100 parts by mass of the crude norbornene compound. The transition metal catalyst is a metallocene catalyst,
The cyclic olefin polymer according to claim 4 , wherein the metallocene catalyst is reacted with one or more selected from the group consisting of aluminoxane (b1) and an ionic compound (b2) to produce a cationic transition metal compound. Production method. The method for producing a cyclic olefin polymer according to claim 5 , wherein the Group IV transition metal of the periodic table is Ti, Zr, or HF. The cyclic olefin according to any one of claims 1 to 6 , wherein the monomer contains at least one selected from the group consisting of ethylene, 1-hexene, and 1-octene together with the norbornene-based compound. Method for producing polymer.