JP7101063B2 - A method for verifying the catalytic activity of a metallocene catalyst, a method for producing a catalyst composition for olefin monomer polymerization, and a method for producing a polymer. - Google Patents

Description

The present invention relates to a method for assaying the catalytic activity of a metallocene catalyst, a method for producing a catalyst composition for olefin monomer polymerization including the assay method, and a method for producing a polymer.

For example, so-called metallocene catalysts are widely used in the production of olefin-based polymers such as cyclic olefin homopolymers and cyclic olefin copolymers.
Various studies have been conducted on such metallocene catalysts, and various metallocene catalysts are known.

For example, a zirconocene-based metallocene catalyst is known as a metallocene catalyst that satisfactorily promotes a copolymerization reaction between a cyclic olefin and ethylene.
Further, when the cyclic olefin is copolymerized with an α-olefin other than ethylene, it is difficult to produce a high molecular weight substance with the above-mentioned zirconosen-based metallocene catalyst, so that the cyclic olefin and the α-olefin other than ethylene are co-polymerized. As a metallocene catalyst that promotes polymerization satisfactorily, the use of a titanosen-based metallocene-based transition metal catalyst, commonly known as so-called half metallocene (post-metallocene), has been proposed. As described above, it was necessary to select an appropriate metallocene catalyst according to the type of the monomer used for producing the olefin polymer (see, for example, Non-Patent Document 1).

Takeshi Shiono et al., Macromolecules, 2008, Vol. 41, p. 8292-8294

Regarding the above-mentioned metallocene catalysts, despite the fact that the metallocene catalysts are manufactured by the same formulation, the deterioration of raw materials or intermediates caused by slight differences in manufacturing conditions, the deterioration of the metallocene catalysts after production, etc. As a result, metallocene catalysts with the desired catalytic activity are often not available.
However, a simple and inexpensive method for testing the catalytic activity of a metallocene catalyst, which allows the catalytic activity of a metallocene catalyst to be known without actually performing polymerization, is not yet known.

The present invention has been made in view of the above problems, and is a simple and inexpensive method for determining the catalytic activity of a metallocene catalyst, which allows the catalytic activity of the metallocene catalyst to be known without actually performing polymerization. It is an object of the present invention to provide a method for producing a catalyst composition for olefin monomer polymerization including the assay method, and a method for producing a polymer using the catalyst composition for olefin monomer polymerization produced by the production method.

The present inventors measured the absorbance of the solution of the metallocene catalyst (a) with an ultraviolet-visible spectrophotometer, and specified the peak wavelength within the wavelength range of 350 nm to 500 nm in the absorbance spectrum obtained by the absorbance measurement. We have found that the above problems can be solved by determining the wavelength, acquiring the value of the specific absorbance, which is the absorbance at the specific wavelength, and using the value of the specific absorbance to test the catalytic activity of the metallocene catalyst, and complete the present invention. I arrived.
More specifically, the present invention provides the following.

(1) Preparing a solution of the metallocene catalyst (a) and
Using the above-mentioned solution or the above-mentioned solution whose concentration is adjusted as a sample, the absorbance can be measured by an ultraviolet-visible spectrophotometer.
In the absorbance spectrum obtained by the absorbance measurement, a specific wavelength, which is the wavelength of the peak in the wavelength range of 350 nm to 500 nm, is determined, and the value of the specific absorbance, which is the absorbance at the specific wavelength, is obtained.
A method for testing the catalytic activity of a metallocene catalyst, which comprises testing the catalytic activity of the metallocene catalyst (a) using a value of a specific absorbance.

(2) The test is performed by comparing the specific absorbance with the preset reference absorbance.
The method for testing the catalytic activity of a metallocene catalyst according to (1), which is acceptable when the specific absorbance is equal to or higher than the reference absorbance and fails when the specific absorbance is less than the reference absorbance.

(3) The standard absorbance is as follows: 1) -4):
1) Polymerization of the same type of monomer under the same conditions using 3 or more metallocene catalysts showing different specific absorbances is performed, and the yield of the polymer is measured.
2) Plot the specific absorbance and the polymer yield of each metallocene catalyst obtained in 1) on a coordinate plane with the specific absorbance as the horizontal axis and the polymer yield as the vertical axis.
3) Perform a linear approximation on the data plotted on the coordinate plane to obtain a calibration curve, and 4) obtain a specific absorbance value corresponding to the yield of the polymer, which is the lower limit of the pass value, from the calibration curve. , Obtained as pre-quasi-absorbance,
The method for determining the catalytic activity of a metallocene catalyst according to (2), which is defined by a method comprising.

（式（ａ１）中、Ｒ^ａ１、Ｒ^ａ２、Ｒ^ａ３、及びＲ^ａ４は、それぞれ独立に、ヘテロ原子を含んでいてもよい炭素原子数１以上２０以下の炭化水素基であり、
Ｒ^ａ１及びＲ^ａ２は、それぞれＣ－Ｓｉ結合、Ｏ－Ｓｉ結合、Ｓｉ－Ｓｉ結合、又はＮ－Ｓｉ結合によりケイ素原子に結合し、
Ｒ^ａ３はＣ－Ｎ結合、Ｏ－Ｎ結合、Ｓｉ－Ｎ結合、又はＮ－Ｎ結合により窒素原子に結合し、
Ｒ^ａ４はＣ－Ｍ結合により金属原子Ｍに結合し、
Ｒ^ａ５及びＲ^ａ６は、それぞれ独立に、ヘテロ原子を含んでいてもよい炭素原子数１以上２０以下の有機置換基、又は無機置換基であり、ｐ及びｑは、それぞれ独立に０以上４以下の整数であり、
Ｒ^ａ５及びＲ^ａ６がそれぞれ複数である場合、複数のＲ^ａ５及びＲ^ａ６は異なる基であってもよく、
複数のＲ^ａ５のうちの２つの基、又は複数のＲ^ａ６のうちの２つの基が芳香環上の隣接する位置に結合する場合、当該２つの基が相互に結合して環を形成してもよく、
Ｍは、周期律表第ＩＶ族遷移金属である。）
で表されるメタロセン化合物である、（１）～（３）のいずれか１つに記載のメタロセン触媒の触媒活性の検定方法。 (4) The metallocene catalyst has the following formula (a1):

(In the formula (a1), R ^a1 , R ^a2 , R ^a3 , and R ^a4 are each independently a hydrocarbon group having 1 or more and 20 or less carbon atoms which may contain a heteroatom.
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.
R ^a3 is bonded to a nitrogen atom by a CN bond, an ON bond, a Si—N bond, or an NN bond.
R ^a4 is bonded to the metal atom M by a CM bond, and is bonded to the metal atom M.
R ^a5 and R ^a6 are each independently an organic substituent or an inorganic substituent having 1 or more and 20 or less carbon atoms which may contain a heteroatom, and p and q are independently 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 a plurality of Ra ^5s or two groups of a plurality of Ra ^6s are bonded to adjacent positions on an aromatic ring, the two groups are bonded to each other to form a ring. Well,
M is a Group IV transition metal of the Periodic Table. )
The method for determining the catalytic activity of a metallocene catalyst according to any one of (1) to (3), which is a metallocene compound represented by.

(5) One of (1) to (4), wherein the solution of the metallocene catalyst (a) is continuously prepared and the assay is performed in-line after the solution of the metallocene catalyst (a) is prepared. The method for determining the catalytic activity of a metallocene catalyst according to the above.

(6) Testing the suitability of the catalytic activity of the metallocene catalyst (a) by the method according to any one of (1) to (5).
The solution of the metallocene catalyst (a) after the assay is mixed with one or more selected from the group consisting of aluminoxane (b1) and an ionic compound (b2) to prepare a catalyst composition for olefin monomer polymerization. Including that
A method for producing a catalyst composition for olefin monomer polymerization, wherein the ionic compound (b2) is a compound that produces a cationic transition metal compound by reacting with a metallocene catalyst (a).

(7) A method for producing a polymer, wherein the olefin monomer is polymerized using the catalyst composition for polymerizing the olefin monomer produced by the production method according to (6).

(8) The method for producing a polymer according to (7), wherein the norbornene monomer is homopolymerized or the norbornene monomer is copolymerized with another monomer copolymerizable with the norbornene monomer. ..

(9) The method for producing a polymer according to (8), wherein the norbornene monomer is copolymerized with one or more selected from the group consisting of ethylene, 1-hexene, and 1-octene.

According to the present invention, a simple and inexpensive method for verifying the catalytic activity of a metallocene catalyst, which allows the catalytic activity of the metallocene catalyst to be known without actually performing polymerization, and a method for olefin monomer polymerization including the verification method. It is possible to provide a method for producing a catalyst composition and a method for producing a polymer using a catalyst composition for polymerizing an olefin monomer produced by the production method.

It is a figure which shows the spectrum of the absorbance for a specific metallocene catalyst. It is a figure which shows the graph which shows the relationship between the value of the specific absorbance about the solution of 4 kinds of metallocene catalysts produced in an Example, and the yield of a polymer for polymerization using 4 kinds of metallocene catalysts.

≪Method for testing the catalytic activity of metallocene catalysts≫
The method for testing the catalytic activity of a metallocene catalyst is as follows.
Preparing a solution of the metallocene catalyst (a) and
Using the solution of the metallocene catalyst (a) or the solution whose concentration is adjusted as a sample, the absorbance can be measured by an ultraviolet-visible spectrophotometer.
In the absorbance spectrum obtained by the absorbance measurement, a specific wavelength, which is the wavelength of the peak in the wavelength range of 350 nm to 500 nm, is determined, and the value of the specific absorbance, which is the absorbance at the specific wavelength, is obtained.
It comprises testing the catalytic activity of the metallocene catalyst (a) using the value of the specific absorbance.

Hereinafter, the preparation of the solution of the metallocene catalyst (a) is also referred to as a “solution preparation step”. Using a solution of the metallocene catalyst (a) or a solution having an adjusted concentration of the solution as a sample, measuring the absorbance with an ultraviolet-visible spectrophotometer is also referred to as "absorbance measurement step". In the absorbance spectrum obtained by the absorbance measurement, a specific wavelength which is the wavelength of the peak in the wavelength range of 350 nm to 500 nm is determined, and the value of the specific absorbance which is the absorbance at the specific wavelength is acquired. It is also written. Testing the catalytic activity of the metallocene catalyst (a) using the value of the specific absorbance is also referred to as "testing step".

The present inventors have stated that for a metallocene catalyst, there is a correlation between the absorbance (specific absorbance) at a specific wavelength, which is the wavelength of the peak in the wavelength range of 350 nm to 500 nm in the absorbance spectrum, and the catalytic activity of the metallocene catalyst. discovered.
Based on this discovery, the present inventors have found that the catalytic activity of a metallocene catalyst can be easily tested by an inexpensive and easy means of measuring absorbance according to the above method.

Hereinafter, each step included in the above-mentioned method for determining the catalytic activity of a metallocene catalyst will be described in order.

<Solution preparation process>
In the solution preparation step, a solution of the metallocene catalyst (a) is prepared. The method for preparing the solution of the metallocene catalyst (a) is not particularly limited, and a method according to the type of the metallocene catalyst (a) is adopted with reference to a well-known method.
The method for producing the metallocene catalyst (a) is described in, for example, JP-A-09-048790, JP-A-2001-516367, JP-A-2018-002803, JP-A-2018-001073, and the like. .. The structure of the metallocene catalyst (a) and the method for producing the metallocene catalyst (a) are not limited to the structures and methods described in these documents. Many other documents other than these documents also disclose methods for producing metallocene catalysts having various structures.

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 or more and 20 or less carbon atoms, an alkylaryl group having 7 or more and 20 or less carbon atoms, an aralkyl group having 7 or more and 20 or less 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 in the form of a branched chain, 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 is -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 or more and 20 or less carbon atoms, an alkylaryl group having 7 or more and 20 or less carbon atoms, or an aralkyl group having 7 or more and 20 or less carbon atoms.
M is a metal atom selected from the group consisting of Ti, Zr, and Hf.
L is an aryl group having 6 or more and 20 or less carbon atoms, an alkylaryl group having 7 or more and 20 or less carbon atoms, an aralkyl group having 7 or more and 20 or less 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 or more and 20 or less 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 L's, the plurality of L's may be the same or different, and it is preferable that the L's are 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 or more and 20 or less carbon atoms, an alkylaryl group having 7 or more and 20 or less carbon atoms, an aralkyl group having 7 or more and 20 or less carbon atoms, or a direct group. It is an aliphatic hydrocarbon group having 1 or more and 20 or less carbon atoms which may be chain-shaped, branched-chain-shaped, 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.
p + q is equal to the oxidation state of the metal M minus 2 (oxidation state of the metal M-2) when r is 1.
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 the formula (1), the _divalent cross-linking group (ZR ⁰¹ _m ) _n is CR ⁰¹² , (CR ⁰¹² ) ₂ , (CR ⁰¹² ) _{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 π-bonded to the metal M is a cyclopentadienyl group which may have a substituent or a cyclic group containing a cyclopentadiene ring which may have a substituent.
Suitable 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 Examples thereof include indeno [2,1-b] indole-6-yl and N-phenyl-5,6-dihydroindeno [2,1-b] indole-6-yl.

A is a group similar to Cp, or is -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. 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 6H ₃ ), _CpdMMeCl (O-2,6- (t-Bu) ₂ -C 6H ₃ ), tet- _{CpdMCl 2} (O-2,6- (t-Bu) ₂ -C 6H ₃ ), tet-CpdMMe ₂ (O-2,6- (t-Bu) ₂ -C ₆ H ₃ ), tet _- CpdMMeCl (O-) 2,6- (t-Bu) ₂ -C 6H ₃ ), _{CpdMCl 2} (O-2,6- (i-Pr) ₂ -C 6H ₃ ), _{CpdMMe 2} (O-2,6- (i) -Pr) ₂ -C 6H ₃ ), _CpdMMeCl (O-2,6- (i-Pr) ₂ -C 6H 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 group. 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.

Specific examples of the transition metal complex represented by the formula (1) in the case where n is 0 and r is 1 include (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 , (H ₄ Ind) ₂ MPh ₂ , and (Me ₄ Cpd) (Me ₅ Cpd) MCl ₂ .
In the above example, Me is a methyl group, Et is an ethyl group, Cpd is a cyclopentadienyl group, Ind is an indenyl group, and _H4 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 SiC (Ind) ₂ MPh ₂ , Me ₂ SiC ₂ (Ind) ₂ MBz ₂ , Me ₂ SiCH 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 _{3H 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 (4 Ind) 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 _{3H 4} Ind) ₂ MMe ₂ , (t-BuNSiMe ₂ ) (tet-Cpd) MCl ₂ , (t-BuNSiMe ₂ ) (tt-Cpd) MMe ₂ , (t-BuNSiMe ₂ ) ) (Tet-Cpd) MPh ₂ , (t-BuNSiMe ₂ ) (tt-Cpd) MBz ₂ , (t-BuNSiMe ₂ ) (tt-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 .
In the above example, Me is a methyl group, Cpd is a cyclopentadienyl group, tet-Cpd is a tetramethylcyclopentadienyl group, Ind is an indenyl group, and H4 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 the copolymerization of norbornene monomer and ethylene described later, and are preferably used for the 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 ), Ra1, ^Ra2 , ^Ra3 , and ^Ra4 are each independently a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom.
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.
R ^a4 is bonded to the metal atom M by a CM bond.
R ^a5 and R ^a6 are each independently an organic substituent or an inorganic substituent having 1 or more and 20 or less carbon atoms which may contain a heteroatom, and p and q are independently 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 a plurality of Ra ^5s or two groups of a plurality of Ra ^6s are bonded to adjacent positions on an aromatic ring, the two groups are bonded to each other to form a ring. May be good.
M is a Group IV transition metal of the Periodic Table, and Ti, Zr, or Hf is preferable.

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 each independently a hydrocarbon group having 1 to 20 carbon atoms which may 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 .
Suitable 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. (OR ^a7 ) The group represented by ₃ can be mentioned.
Preferable examples of ^Ra1 and ^Ra2 bonded to a silicon atom by an N—Si bond include groups represented by —NHR ^a7 and —NR ^a7 ₂ .
Here, all of the above Ra ^7s are hydrocarbon groups.

^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 bonded to a nitrogen atom by an NN bond include groups represented by -NHR ^a7 and -NR ^a7 ₂ .
Here, all of the above Ra ^7s are hydrocarbon groups.

Since it is easy to prepare and obtain a compound to be used as a ligand, it is preferable that ^Ra1 and ^Ra2 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 the hydrocarbon group include a linear or branched alkyl group, a linear or branched unsaturated aliphatic hydrocarbon group which may have a double bond and / or a triple bond, and a cycloalkyl. 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-nonadecyl 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 are given as specific examples of the linear or branched alkyl group. Examples thereof include groups 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 and a cyclotridecyl group. Included are a cyclotetradecyl group, a cyclopentadecyl group, a cyclohexadecyl group, a cycloheptadecyl group, a cyclooctadecyl group, a cyclononadesyl 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, cyclononadecylmethyl 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, anthracene-2-yl Group, anthracene-9-yl group, phenylnentren-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 or more and 4 or less 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 an aromatic hydrocarbon having 6 to 20 carbon atoms. A hydrogen group and an aralkyl group 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 or more and 6 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, a cycloalkyl group having 3 or more and 8 or less carbon atoms, and 2 or more and 6 or less 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 reaction for producing a 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 a plurality of Ra ^5s or two groups of a plurality of Ra ^6s are bonded to adjacent positions on an aromatic ring, the two groups are bonded to each other to form a ring. May be good. Such a ring is a condensed ring that is condensed with an 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 heteroatom such as an oxygen atom, a nitrogen atom, and a sulfur atom in the ring.

Specific examples of the 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 preferred 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, for example, a copolymerization of a norbornene monomer described later, or a copolymerization of the norbornene monomer described later with 1-octene, 1-hexene, or a mixture thereof. It is preferably used for polymerization, and is preferably used by copolymerizing norbornene with 1-octene, 1-hexene, or a mixture thereof.

The solvent contained in the solution of the metallocene catalyst (a) described above 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) prepared in the solution preparation step 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.

<Absorbance measurement process>
In the absorbance measurement step, the absorbance of the metallocene catalyst (a) or the solution having the adjusted concentration of the solution is used as a sample to measure the absorbance with an ultraviolet-visible spectrophotometer.
As the ultraviolet-visible spectrophotometer, a well-known device used for measuring the absorbance of various solutions can be used without particular limitation. As the ultraviolet-visible spectrophotometric diameter, for example, JASCO V-570 manufactured by JASCO Corporation can be used.
Further, the cell for measuring the absorbance is not particularly limited. Normally, a measurement cell corresponding to each model of the ultraviolet-visible spectrophotometer is used.

The concentration of the metallocene catalyst (a) in the solution of the metallocene catalyst (a) as a sample used for the absorbance measurement is not particularly limited as long as the absorbance can be measured without any problem. The concentration of the metallocene catalyst (a) is preferably, for example, 0.1 mmol / L or more and 20 mmol / L or less, and 1 mmol / L, because it is easy to obtain a specific absorbance that can be easily tested particularly well in the specific absorbance acquisition step described later. More preferably, it is L or more and 10 mmol / L or less.

The method for adjusting the concentration of the solution of the metallocene catalyst (a) as a sample is not particularly limited. The solution of the metallocene catalyst (a) prepared in the solution preparation step may be concentrated using a rotary evaporator or the like under the condition that the metallocene catalyst (a) does not deteriorate, or may be diluted by the addition of a solvent.

The measurement wavelength range for the absorbance measurement is not particularly limited as long as it includes a wavelength range of 350 nm to 500 nm.

<Specific absorbance acquisition process>
In the specific absorbance acquisition step, in the absorbance spectrum obtained by the absorbance measurement in the absorbance measurement step, a specific wavelength which is the wavelength of the peak in the wavelength range of 350 nm to 500 nm is determined, and the value of the specific absorbance which is the absorbance at the specific wavelength is determined. get.
Regarding the absorbance spectrum, the peak in the wavelength range of 350 nm to 500 nm is considered to be based on the charge transfer between the metal and the ligand in the metallocene catalyst (a).

The specific wavelength, which is the wavelength of the peak in the wavelength range of 350 nm to 500 nm, is specified as the wavelength showing the maximum absorbance at the peak.

As an example, FIG. 1 shows a spectrum of absorbance of a metallocene-catalyzed toluene solution represented by the following structural formula. From the spectrum shown in FIG. 1, it can be seen that the metallocene catalyst represented by the following structural formula has a peak having a peak top wavelength (specific wavelength) of 430 nm in the wavelength range of 350 nm to 500 nm in the absorbance spectrum. ..

As described above, for the metallocene catalyst (a), after determining the specific wavelength which is the wavelength of the peak in the wavelength range of 350 nm to 500 nm, the value of the specific absorbance which is the absorbance at the specific wavelength is obtained.

<Certification process>
In the verification step, the catalytic activity of the metallocene catalyst (a) is tested using the value of the specific absorbance obtained in the specific absorbance acquisition step.
As described in detail in Examples and FIG. 2, when the same kind of monomer is polymerized under the same conditions, the value of the specific absorbance of the metallocene catalyst (a) having the same concentration and the value of the specific absorbance are used. It has been found that the yield of the polymer obtained by the polymerization (that is, the catalytic activity) shows a linearly functional relationship.
That is, it was found that the larger the value of the specific absorbance, the higher the catalytic activity of the metallocene catalyst (a), and the smaller the value of the specific absorbance, the lower the catalytic activity of the metallocene catalyst (a).
Based on this discovery, it became possible to test the catalytic activity of the metallocene catalyst (a) by using the value of the specific absorbance.

The test method is not particularly limited. As an example of the test method, there is a track record of repeatedly producing a polymer by batch polymerization, and in the repeated production, the value of the specific absorbance of the metallocene catalyst (a) used for the polymerization and the yield of the polymer are used. If a record of the relationship has been made, it is possible to predict from the record what the specific absorbance value for the metallocene catalyst (a) should be to produce the polymer in the desired yield.
In this way, it is possible to test whether or not the catalytic activity of the metallocene catalyst (a) is as high as desired by using the value of the specific absorbance of the metallocene catalyst (a) to be used.

Further, as the assay method, a method is preferable in which the specific absorbance is compared with the preset reference absorbance. In this case, if the specific absorbance is equal to or higher than the reference absorbance, it can be determined to be acceptable, and if the specific absorbance is less than the reference absorbance, it can be determined to be unacceptable.
The reference absorbance is usually defined as a specific absorbance value at which the minimum polymer yield desired to be achieved can be expected when the metallocene catalyst (a) is used for polymerization.
The specific absorbance and the reference absorbance are compared with each other after converting both values into the measured values when the concentration of the metallocene catalyst (a) in the sample for measuring the absorbance is the same. The relationship between the concentration of the measurement sample and the absorbance is a proportional relationship.
When the concentration of the metallocene catalyst (a) is the same between the sample used for measuring the specific absorbance and the sample used for measuring the absorbance used for setting the reference absorbance, the above conversion is not necessary.

The method for setting the reference absorbance is not particularly limited. As a method for setting the reference absorbance, for example, as described above, there is a track record of repeatedly producing a polymer by batch polymerization, and in the repeated production, the value of the specific absorbance of the metallocene catalyst (a) used for the polymerization. When a record of the relationship between the polymer yield and the polymer yield is made, the reference absorbance is referred to from the record with reference to the specific absorbance value for the metallocene catalyst (a) that has achieved the desired polymer yield. Can be set.

Further, as a preferable setting method of the reference absorbance, the following 1) to 4):
1) Polymerization of the same type of monomer under the same conditions using 3 or more metallocene catalysts showing different specific absorbances is performed, and the yield of the polymer is measured.
2) Plot the specific absorbance and the polymer yield of each metallocene catalyst obtained in 1) on a coordinate plane with the specific absorbance as the horizontal axis and the polymer yield as the vertical axis.
3) Perform a linear approximation on the data plotted on the coordinate plane to obtain a calibration curve, and 4) obtain a specific absorbance value corresponding to the yield of the polymer, which is the lower limit of the pass value, from the calibration curve. , Obtained as the reference absorbance,
The method including is mentioned.

In the above-mentioned method for setting the reference absorbance, the method for performing linear approximation is not particularly limited. For example, in 3) above, software having a function of plotting a specific absorbance value and a polymer yield value on a two-axis coordinate plane and then performing a linear approximation to the plotted data is provided. It can be used for linear approximation.
Specifically, a calibration curve can be derived by performing a linear approximation using Microsoft (registered trademark) Excel (registered trademark).

The method for determining the catalytic activity of a metallocene catalyst described above can be applied regardless of whether the metallocene catalyst (a) is produced by a batch reaction or the metallocene catalyst (a) is produced by a continuous reaction. ..
When the solution of the metallocene catalyst (a) is continuously prepared, the suitability of the catalytic activity of the metallocene catalyst (a) to be produced can be known from the production of the metallocene catalyst (a) without any time lag. Is preferably performed inline.
In this case, typically, a sorting device for separating the solution of the metallocene catalyst (a) from the production line of the metallocene catalyst (a) and an ultraviolet-visible spectrophotometer are used in the production line of the metallocene catalyst (a). It is attached to and tested in-line.
When the catalytic activity of the metallocene catalyst (a) is predicted to be lower than the desired catalytic activity by in-line assay, the solvent used for producing the metallocene catalyst (a) includes the amount of dissolved oxygen and the content of dissolved oxygen. It is manufactured by switching to a solvent that has a low water content and does not easily deteriorate the metallocene catalyst, or by adjusting the atmosphere of the gas phase of the environment in which the metallocene catalyst (a) is manufactured so that oxygen and water content are reduced. It is possible to take measures to improve the catalytic activity of the metallocene catalyst (a).

<< Production method of catalyst composition for olefin monomer polymerization >>
The catalyst composition for olefin monomer polymerization is
By the above-mentioned method, the suitability of the catalytic activity of the metallocene catalyst (a) is verified.
The solution of the metallocene catalyst (a) after the assay is mixed with one or more selected from the group consisting of aluminoxane (b1) and an ionic compound (b2) to prepare a catalyst composition for olefin monomer polymerization. It is preferable to manufacture by a method including the above.
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 a metallocene catalyst (a) for preparing a catalyst composition with one or more selected from the group consisting of aluminoxane (b1) and an ionic compound (b2) is a polymerization reaction before polymerization. It may be carried out in a device separate from the tank, or may be carried out in the polymerization reaction tank before or during the polymerization.

According to such a method, the catalytic activity of the obtained catalytic composition for olefin monomer polymerization can be predicted.
Therefore, when the catalytic activity of the catalyst composition is predicted to be lower than desired, the amount of the catalyst composition used for polymerization of the olefin monomer may be increased or the polymerization time may be extended when the polymerization is carried out. You can take actions such as going.

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

[Aluminoxane (b1)]
Alminoxane (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１～４のアルキル基、ｎは０～４０、好ましくは２～３０の整数を示す。）

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

Examples of the alkylaluminoxane include methylaluminoxane and modified methylaluminoxane in which a part of the methyl group of 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 substituted 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 products of alkylaluminoxane include MMAO-3A, TMAO-200 series, TMAO-340 series (all manufactured by Toso Finechem Co., Ltd.) and methylaluminoxane 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 an anion of a tetrakis (pentafluorophenyl) borate, an amine cation having an active proton such as (CH ₃ ) ₂ N (C ₆ H ₅ ) H ⁺ , (C ₆ H ₅ ) ₃ C ^+. Ionic compounds such as trisubstituted carbonium 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 impair 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 0.00000005 to 50 mol / L. An amount of solvent of 0.000000001 to 20 mol / L is used.

When the liquid containing the raw material of the catalyst composition is mixed, the number of moles of the transition metal element in the metallocene catalyst ( _a ) is defined as Ma, the number of moles of aluminum in the aluminoxane (b1) is defined as M _b1 , and the ion compound (b2) is used. ) Is M _b2 , and the value of (M _b1 + M _b2 ) / _Ma is preferably 1 to 200,000, more preferably 100 to 100,000, and particularly preferably 1000 to 80,000. 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.

≪Polymer manufacturing method≫
In the method for producing a polymer, the olefin monomer is polymerized using the catalyst composition for polymerizing the olefin monomer produced by the above-mentioned method.
According to such a method, the catalytic activity of the catalytic composition for olefin monomer polymerization can be predicted.
Therefore, when the catalytic activity of the catalyst composition is predicted to be lower than desired, the amount of the catalyst composition used for polymerization of the olefin monomer may be increased or the polymerization time may be extended when the polymerization is carried out. You can take actions such as going.

Regarding the polymerization of the olefin monomer, the type of the monomer and the polymerization method are not particularly limited, and a well-known olefin monomer and a polymerization method can be appropriately adopted.

Hereinafter, as a preferable example of the polymerization of the olefin monomer, when the norbornene monomer is homopolymerized or when the norbornene monomer is copolymerized with another monomer copolymerizable with the norbornene monomer. Will be described.

A so-called cyclic olefin polymer is produced by homopolymerizing a norbornene monomer or by copolymerizing a norbornene monomer with another monomer copolymerizable with the norbornene monomer.
The homopolymerization of the norbornene monomer and the copolymerization of the norbornene monomer and other monomers 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 has 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.

Hereinafter, the monomer compound and the specific polymerization method will be described with respect to the method for producing the cyclic olefin polymer.

[Norbornene monomer]
Examples of the norbornene monomer include norbornene and substituted norbornene, and norbornene is preferable. The norbornene monomer can be used alone or in combination of two or more.

The substituted norbornene is not particularly limited, and examples of the substituent contained in the substituted norbornene include a halogen atom and a monovalent or divalent hydrocarbon group. Specific examples of the substituted norbornene include those represented by the following general formula (I).

（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、炭化水素基からなる群より選ばれるものであり、
Ｒ^９とＲ^１０、Ｒ^１１とＲ^１２は、一体化して２価の炭化水素基を形成してもよく、
Ｒ^９又はＲ^１０と、Ｒ^１１又はＲ^１２とは、互いに環を形成していてもよい。
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い。
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。）

(In the formula, R ¹ to R ¹² 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.
R ⁹ and R ¹⁰ and R ¹¹ and R ¹² may be integrated to form a divalent hydrocarbon group.
R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may form a ring with each other.
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. )

The substituted norbornene represented by the general formula (I) will be described. R ¹ to R ¹² in the general 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.

Specific examples of R ¹ to R ⁸ include hydrogen atoms; halogen atoms such as fluorine, chlorine and bromine; alkyl groups having 1 or more and 20 or less carbon atoms, which may be different from each other. , 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 groups, phenethyl groups and other alkyl groups substituted with aryl groups such as aralkyl groups. They can be different, partially different, or all identical.

Specific examples of the case where R ⁹ and R ¹⁰ or R ¹¹ and R ¹² are integrated to form a divalent hydrocarbon group include, for example, an alkylidene group such as an ethylidene group, a propyridene group, and an isopropylidene group. Can be mentioned.

When R ⁹ or R ¹⁰ and R ¹¹ or R ¹² form a ring with each other, the formed ring may be a monocyclic ring, a polycyclic ring, or a polycyclic ring having a crosslink. , It may be a ring having a double bond, or it may be a ring composed of a combination of these rings. Further, these rings may have a substituent such as a methyl group.

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-ethylidene-bicyclo [2.2. 1] Hepta-2-ene, 5-hexyl-bicyclo [2.2.1] hepta-2-ene, 5-octyl-bicyclo [2.2.1] hepta-2-en, 5-octadecil-bicyclo [ 2.2.1] Hepta-2-ene, 5-methylidene-bicyclo [2.2.1] hepta-2-ene, 5-vinyl-bicyclo [2.2.1] hepta-2-ene, 5- Bicyclic cyclic olefins such as propenyl-bicyclo [2.2.1] hepta-2-ene;
Tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (common name: dicyclopentadiene), tricyclo [4.3.0.1 ^2,5 ] deca-3-ene; tricyclo [ 4.4.0.1 ^2,5 ] Undeca-3,7-diene or tricyclo [4.4.0.1 ^2,5 ] Undeca-3,8-diene or a partially hydrogenated additive thereof (or cyclopentadiene) Tricyclo [4.4.0.1 ^2,5 ] undeca-3-ene; 5-cyclopentyl-bicyclo [2.2.1] hepta-2-ene, 5-cyclohexyl-bicyclo 3 such as [2.2.1] hepta-2-ene, 5-cyclohexenylbicyclo [2.2.1] hepta-2-ene, 5-phenyl-bicyclo [2.2.1] hepta-2-ene. Cyclic olefin of the ring;
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-en, 8-methylidenetetracyclo [4.4.0.1 ^2,5 . 17 and ¹⁰ ] Dodeca-3-en, 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 and ¹⁰ ] 4-ring 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 . 1 ⁷ , 10] Dodeca-3-ene; Tetracyclo [7.4.1, ^3,6 . 0 ^{1,9 1} . 0 ^2,7 ] Tetradeca-4,9,11,13-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydrofluorene), tetracyclo [8.4.1, ^4,7 . 0 ^{1,10 1} . 0 ^3,8 ] Pentadeca-5,10,12,14-tetraene (also referred to as 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene); pentacyclo [6.6.1. 1 ^{3, 6} . 0 ^2,7 . ^09,14 ] -4-hexadecene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . ^09,13 ] -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 . ^{113, l6} ] -14-eicosene; polycyclic cyclic olefins such as cyclopentadiene tetramers can be mentioned.

Among them, alkyl-substituted norbornene (eg, bicyclo [2.2.1] hepta-2-ene substituted with one or more alkyl groups), alkylidene-substituted norbornene (eg, bicyclo substituted with one or more alkylidene groups). [2.2.1] hepta-2-ene) is preferred, 5-ethylidene-bicyclo [2.2.1] hepta-2-ene (common name: 5-ethylidene-2-norbornene, or simply ethylidene norbornene). ) Is particularly preferable.

[Other monomers]
The above-mentioned norbornene monomer may be polymerized alone or may be copolymerized with another monomer copolymerizable with the norbornene monomer.
The other monomer is not particularly limited as long as it is a monomer compound copolymerizable with the norbornene monomer, 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-olefins C2 to C12 are not particularly limited, and are, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, and 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 monomers. A combination of norbornene with 1-octene, 1-hexene, or a mixture thereof is preferred.
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 increased. The amount of norbornene in the monomer is preferably 70 mol% or more.

[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. Further, the amount of each monomer component used when copolymerizing the norbornene monomer with another monomer is exemplified as follows.
The amount of the other monomer added to 1 mol of the norbornene monomer 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 compound used in its preparation. The amount of the catalyst composition used 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 is increased 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 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 monomer or the polymerization system containing the norbornene monomer and other monomers is subjected to aluminoxane and aluminoxane before adding the catalyst composition. It is preferable to have at least one selected from the alkylaluminum compounds.

Alminoxane is as described in the method for producing a catalyst composition.
As the alkylaluminum compound, those conventionally used for the 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. be.)

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 dimethylaluminum methoxide.

The 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 compound is preferably 10 mol or more and 1,000,000 mol or less, preferably 100 mol or more and 100,000 mol or less. Is more preferable.
When the alkylaluminum compound is added to the polymerization system before adding the catalyst composition, the amount of aluminum used is preferably 5 mol or more and 500,000 mol or less, and 50 mol or more and 50,000 mol or less as the number of moles of aluminum with respect to 1 mol of the transition metal compound. More preferred.

It is preferable that at least a part, preferably all of the catalyst composition is continuously added to the norbornene monomer or a polymerization system containing the norbornene monomer and another monomer.
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, since the catalyst composition prepared by the above-mentioned method is used, the catalytic activity of the catalyst composition can be predicted.
Therefore, when the catalytic activity of the catalyst composition is predicted to be lower than desired, the amount of the catalyst composition used for polymerization of the olefin monomer may be increased or the polymerization time may be extended when the polymerization is carried out. You can take actions such as going.

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

〔Example〕
A metallocene-catalyzed toluene solution having a concentration of 7.3 mmol / L was prepared using four types of toluene having the water content and dissolved oxygen concentration shown in Table 1 below as solvents. The molar ratio of water / oxygen / metallocene catalyst at the time of preparation of the metallocene catalyst is shown in Table 1. The water-containing condition, oxygen-containing condition, and water-containing-oxygen-containing condition are conditions intentionally adjusted in order to reduce the catalytic activity of the metallocene catalyst. The structure of the metallocene catalyst is as follows.

The absorbance of each of the metallocene-catalyzed toluene solutions produced under the four conditions shown in Table 1 was measured under the following conditions. In the absorbance spectrum obtained as a result of the absorbance measurement, a peak having a peak top was observed at a wavelength of about 430 nm for the metallocene-catalyzed toluene solution obtained under any condition. The specific absorbance, which is the absorbance at the peak top of this peak, is shown in Table 1.

The conditions for measuring the absorbance are as follows.
Spectrophotometer: JASCO V-570 (manufactured by JASCO Corporation)
Light source: Deuterium discharge tube (ultraviolet region), tungsten iodine lamp (visible to near infrared)
Detection unit: Photomultiplier tube and PbS detector Metallocene catalyst concentration: 7.3 mmol / L
Measurement mode: Absorbance

Then, using a toluene solution of a metallocene catalyst produced under the four conditions shown in Table 1, copolymerization of 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 that had been dried and maintained in a 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., the polymerization was started by adding a toluene solution of the metallocene catalyst prepared by the method shown in Table 1 into the glass reactor. At this time, at the same timing as the start of the polymerization, the absorbance of the catalyst solution was measured according to the above-mentioned absorbance measurement conditions, and the absorbance of the catalyst was measured.
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. ..
MMAO-3A is methyl represented by [(CH ₃ ) _0.7 (iso-C ₄ H ₉ ) _0.3 AlO] _n at 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 has a concentration of 9.0% by mass (as the content of Al atoms) with TMAO-211. ) Intoluene solution of methylaluminoxane (manufactured by Toso Finechem Co., Ltd., still containing 26 mol% of trimethylaluminum with respect to total Al).

The relationship between the specific absorbance of the metallocene-catalyzed toluene solution produced under the four conditions shown in Table 1 and the yield of the polymer of 2-norbornene and 1-hexene is shared with the specific absorbance as the horizontal axis. FIG. 2 shows a graph plotted on a coordinate plane having the yield of the polymer as the vertical axis.
FIG. 2 shows an approximate straight line obtained by performing a linear approximation on the data plotted in the graph. The R- ^squared value for the approximate straight line was 0.976, and it was found that the relationship between the specific absorbance and the yield of the copolymer was linearly functional.

According to FIG. 2, it can be seen that the larger the value of the specific absorbance, the higher the yield of the polymer, and the smaller the value of the specific absorbance, the lower the yield of the polymer. Therefore, from FIG. 2, it can be seen that the catalytic activity of the metallocene catalyst can be tested by the value of the specific absorbance.

Claims (8)

Preparing a solution of the metallocene catalyst (a) and
Using the solution or a solution in which the concentration of the solution is adjusted as a sample, the absorbance can be measured by an ultraviolet-visible spectrophotometer.
In the absorbance spectrum obtained by the absorbance measurement, a specific wavelength which is the wavelength of the peak in the wavelength range of 350 nm to 500 nm is determined, and the value of the specific absorbance which is the absorbance at the specific wavelength is obtained.
Including testing the catalytic activity of the metallocene catalyst (a) using the specific absorbance value.
The metallocene catalyst has the following formula (a1):

(In the formula (a1), R ^a1 , R ^a2 , R ^a3 , and R ^a4 are each independently a hydrocarbon group having 1 or more and 20 or less carbon atoms which may contain a heteroatom.
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.
R ^a3 is bonded to a nitrogen atom by a CN bond, an ON bond, a Si—N bond, or an NN bond.
R ^a4 is bonded to the metal atom M by a CM bond, and is bonded to the metal atom M.
R ^a5 and R ^a6 are each independently an organic substituent or an inorganic substituent having 1 or more and 20 or less carbon atoms which may contain a heteroatom, and p and q are independently 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 a plurality of Ra ^5s or two groups of a plurality of Ra ^6s are bonded to adjacent positions on an aromatic ring, the two groups are bonded to each other to form a ring. Well,
M is a Group IV transition metal of the Periodic Table. )
A method for testing the catalytic activity of a metallocene catalyst, which is a metallocene compound represented by . The test is performed by comparing the specific absorbance with a preset reference absorbance.
The method for testing the catalytic activity of a metallocene catalyst according to claim 1, wherein the specific absorbance is acceptable when the absorbance is equal to or higher than the reference absorbance, and the specific absorbance is unacceptable when the specific absorbance is less than the reference absorbance. The reference absorbance is as follows 1) -4) :.
1) Polymerization of the same type of monomer under the same conditions is performed using three or more metallocene catalysts having different specific absorbances, and the yield of the polymer is measured.
2) Coordinate plane with the specific absorbance and the yield of the polymer of each metallocene catalyst obtained in 1) above, with the specific absorbance on the horizontal axis and the yield of the polymer on the vertical axis. To plot on,
3) Linear approximation is performed on the data plotted on the coordinate plane to obtain a calibration curve, and 4) the specification corresponding to the yield of the polymer, which is the lower limit of the pass value, from the calibration curve. Obtaining the value of absorbance as the reference absorbance,
The method for verifying the catalytic activity of a metallocene catalyst according to claim 2, which is defined by a method comprising. The invention according to any one of claims 1 to 3 , wherein the solution of the metallocene catalyst (a) is continuously prepared, and the assay is performed in-line after the solution of the metallocene catalyst (a) is prepared. A method for testing the catalytic activity of a metallocene catalyst. To test the suitability of the catalytic activity of the metallocene catalyst (a) by the method according to any one of claims 1 to 4 .
The solution of the metallocene catalyst (a) after the assay is mixed with one or more selected from the group consisting of aluminoxane (b1) and an ionic compound (b2) to prepare a catalyst composition for olefin monomer polymerization. Including,
A method for producing a catalyst composition for olefin monomer polymerization, wherein the ionic compound (b2) is a compound that produces a cationic transition metal compound by reacting with the metallocene catalyst (a). A method for producing a polymer, which comprises polymerizing an olefin monomer using the catalyst composition for polymerizing an olefin monomer produced by the production method according to claim 5 . The method for producing a polymer according to claim 6 , wherein the norbornene monomer is homopolymerized or the norbornene monomer is copolymerized with another monomer copolymerizable with the norbornene monomer. The method for producing a polymer according to claim 7 , wherein the norbornene monomer is copolymerized with one or more selected from the group consisting of ethylene, 1-hexene, and 1-octene.

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