JP7073100B2 - Method for Producing Cyclic Olefin Resin Composition - Google Patents

Description

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

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.
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 the cyclic olefin and ethylene can be changed according to the copolymerization composition of the cyclic olefin and ethylene, the coweight in which the glass transition temperature (Tg) is adjusted in a wide temperature range. Coagulation can be produced. 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 resin composition, 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 caused by the α-olefin is carried out 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 substance because a reaction occurs (see, for example, Non-Patent Document 2).

Therefore, research and development of a catalyst capable of efficiently producing a resin composition of a high molecular weight cyclic olefin and an α-olefin have been actively carried out. Through research, the resin composition of cyclic olefins and α-olefins is a titanosen-based metallocene, commonly called half-metallocene (post-metallocene), which is different from the conventionally used zirconosen-based metallocene-based transition metal catalysts. It was found that it can be produced by a system transition metal catalyst. As described above, it was necessary to select an appropriate metallocene catalyst according to the monomer structure of the target cyclic olefin resin composition (see, for example, Non-Patent Document 3).

As described above, the synthesis of cyclic olefin resin compositions 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 resin composition. Therefore, the development of a catalyst capable of producing a large amount of cyclic olefin resin composition 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, it is derived from at least the cyclic olefin monomer (A) derived from norbornene and the α-olefin of 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. et al. Y. Et al., Polyhedron, 2005, Vol. 24, p. 1269-1273 Takeshi Shiono et al., Macromolecules, 2008, Vol. 41, p. 8292-8294

However, in the examples of Patent Documents 1 and 2, after adding a cyclic olefin monomer, an α-olefin monomer, and an aluminoxane as a co-catalyst to the reaction vessel and heating the contents of the reaction vessel to a predetermined polymerization temperature. , The transition metal compound dissolved in toluene and the aluminoxane are added to the reaction vessel to activate the transition metal compound. When the cyclic olefin copolymer is produced by such a method, the yield of the cyclic olefin copolymer is not always good.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for producing a cyclic olefin resin composition capable of producing a cyclic olefin resin composition in a high yield.

The present inventors have in the production of a cyclic olefin resin composition using a transition metal complex containing a ligand containing a cyclopentadiene ring and a transition metal of Group IV of the periodic table as the transition metal compound (a). At the time of initiating the polymerization, the transition metal compound (a), one or more selected from the group consisting of the aluminoxane (b1) and the ionic compound (b2), and the monomer are continuously connected in the tube flow path. It has been found that the above-mentioned problems can be solved by a method including mixing the above-mentioned substances, and the present invention has been completed.
More specifically, the present invention provides the following.

(1) A method for producing a cyclic olefin resin composition.
The polymerization reaction for producing the cyclic olefin resin composition is a monomer in the presence of one or more selected from the group consisting of the transition metal compound (a), the aluminoxane (b1), and the ionic compound (b2). Is done by polymerizing
The transition metal compound (a) is a transition metal complex containing a ligand containing a cyclopentadiene ring and a transition metal of Group IV of the periodic table.
At the time of initiating the polymerization, a mixture of one or more selected from the group consisting of the transition metal compound (a), the aluminoxane (b1), and the ionic compound (b2) and the monomer is continuously mixed in the tube. How to do it.

(2) The method according to (1), wherein the wetted area in the tube is 0.4 mm ² or more per 1 mm ³ volume.

(3) Before mixing the monomer with one or more selected from the group consisting of the transition metal compound (a), the aluminoxane (b1), and the ionic compound (b2).
In (1) or (2), the transition metal compound (a) and one or more selected from the group consisting of aluminoxane (b1) and an ionic compound (b2) are mixed in a microreactor. The manufacturing method described.

(4) The production method according to any one of (1) to (3), wherein the Group IV transition metal of the periodic table is Zr and / or Ti.

(5) A cyclic olefin resin composition is produced by homopolymerization of a norbornene monomer or copolymerization of a norbornene monomer and another monomer copolymerizable with the norbornene monomer, (1) to The manufacturing method according to any one of (4).

(6) The cyclic olefin resin composition is a copolymer of one or more selected from the group consisting of ethylene, 1-hexene, and 1-octene and a norbornene monomer, (1) to (5). ). The manufacturing method according to any one of.

According to the present invention, it is possible to provide a method for producing a cyclic olefin resin composition capable of producing the cyclic olefin resin composition in a high yield.

It is a figure which shows a preferable aspect of the shape of the flow path in the case of performing multistage mixing in a microreactor. It is a figure which shows a preferable aspect which is different from the aspect shown in FIG. 1 of the shape of the flow path in the case of performing multistage mixing in a microreactor. It is a figure which shows typically the shape of the microreactor which has a T-shaped flow path in a case. It is a figure which shows typically the shape of the microreactor which has a Y-shaped flow path in a case. It is a figure which shows the outline of the whole image of the manufacturing apparatus of a cyclic olefin resin composition used in the preferable 1st embodiment of the manufacturing method of a cyclic olefin resin composition.

<< Manufacturing method of cyclic olefin resin composition >>
In the method for producing a cyclic olefin resin composition, the polymerization reaction for producing the cyclic olefin resin composition is selected from the group consisting of a transition metal compound (a), an aluminoxane (b1), and an ionic compound (b2). It is carried out by polymerizing the monomer in the presence of the above.
Hereinafter, the combination of the transition metal compound (a) and one or more selected from the group consisting of the aluminoxane (b1) and the ionic compound (b2) is also referred to as a “catalyst composition”.
As the transition metal compound (a), a transition metal complex containing a ligand containing a cyclopentadiene ring and a transition metal of Group IV of the periodic table is used.

As a result of diligent studies by the present inventors, it is speculated that the reason why the yield of the cyclic olefin resin composition is limited in the polymerization reaction by the above method is the deactivation of the catalyst due to the heat generation at the start of the polymerization reaction. Was done.
Based on the above estimation, the present inventors have proceeded with studies to improve the efficiency of heat removal at the start of the polymerization reaction in the production of the cyclic olefin resin composition. As a result, the present inventors have a single amount of one or more selected from the group consisting of the transition metal compound (a), the aluminoxane (b1), and the ionic compound (b2) when initiating the polymerization reaction. It has been found that the yield of the cyclic olefin resin composition is improved by continuously mixing with the body in a tube.

Hereinafter, a method for preparing the catalytic composition and a method for polymerizing the cyclic olefin resin composition will be described.

<Catalyst composition preparation method>
In the above method, the transition metal compound (a) and one or more selected from the group consisting of the aluminoxane (b1) and the ionic compound (b2) are mixed before being mixed with the monomer. It may be made into a catalyst composition by the above, or it may be made into a catalyst composition by individually mixing with a monomer.

In that the activity as a catalyst is enhanced, one or more selected from the group consisting of the transition metal compound (a), the aluminoxane (b1), and the ionic compound (b2) before being mixed with the monomer are selected. It is preferable to mix.

The method of mixing the transition metal compound (a) with one or more selected from the group consisting of the aluminoxane (b1) and the ionic compound (b2) is not particularly limited.
From the viewpoint of increasing the activity as a catalyst, the transition metal compound (a) and one or more selected from the group consisting of aluminoxane (b1) and an ionic compound (b2) are mixed in a microreactor. Is preferable.
When the transition metal compound (a) is mixed with one or more selected from the group consisting of aluminoxane (b1) and an ionic compound (b2) to generate an activated catalyst composition, heat generation during mixing is generated. Due to such influences, not only desired cation species having high polymerization activity but also cation species having low polymerization activity and being thermally unstable are produced.
On the other hand, when the transition metal compound (a) is mixed with one or more selected from the group consisting of the aluminoxane (b1) and the ionic compound (b2) using a microreactor, the heat is transmitted relative to the volume. Since the heat area is very large, the heat generated during mixing is well removed.
Therefore, it is considered that the ratio of producing a desired cationic species having high polymerization activity increases, and a catalyst composition that gives a polymer in high yield can be produced.

Hereinafter, the materials used for producing the catalyst composition, the microreactor, and the specific method for producing the catalyst composition will be described in order.

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

In formula (1), (ZR ¹ _m ) _n is a divalent group that binds Cp and A.
Z is C, Si, Ge, N, or P.
R ¹ is 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 branched chain even if it is linear. However, it is an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may contain a cyclic skeleton and may have an unsaturated bond.
When there are a plurality of R ^1s in (ZR ¹ _m ), the plurality of R ^1s may be the same or different.
When (ZR ¹ _m ) is repeated a plurality of times, the plurality of (ZR ¹ _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 ² )-.
^R2 is a hydrogen atom, a fat having 1 to 20 carbon atoms which may be linear, branched, may contain a cyclic skeleton, and may have an unsaturated bond. It is a group 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 whether it is linear or branched. , 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 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 ⁵ or -N = C (R ⁵ ) R ⁵ .
R5 may contain a hydrogen atom or a hetero atom, and may contain 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 to 20 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 ^R5s , 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 from 0 to 4.
r is 0 or 1. If r is 0, then n is 0.
p is an integer of 0 to 3.
q is an integer from 0 to 3.
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 ¹ _m ) _n is CR ¹ ₂ , (CR ¹ ₂ ) ₂ , (CR ¹ ₂ ) ₃ , SiR ¹ ₂ and GeR ¹ . It is preferably selected from the group consisting of ₂ , NR ¹ , and PR ¹ .
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 to 4.

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 ² )-. 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 ⁵ (R ⁵ is as described above), or -N = C (R ⁵ ) R ⁵ 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 to 4, preferably 0 to 2.

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 ) (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 .
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 transition metal 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 transition metal 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 hydrocarbon groups having 1 to 20 carbon atoms which may independently 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 or inorganic substituent having 1 to 20 carbon atoms which may contain a heteroatom, and p and q are independently integers of 0 to 4, respectively. Is.
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 to 5.

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 the 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 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms are preferable, and an alkyl group having 1 to 10 carbon atoms and 6 to 10 carbon atoms are preferable. The aromatic hydrocarbon group of 1 to 6 is more preferable, an alkyl group having 1 to 6 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 an aralkyl group having 7 to 20 carbon atoms. preferable.

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, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and an aromatic hydrocarbon group. An aralkyl group having 7 to 20 carbon atoms is preferable.

In the formula (a1), ^Ra 5 and Ra ⁶ are independently organic substituents or inorganic substituents having 1 to 20 carbon atoms which may contain heteroatoms, and p and q are independent of each other. Is an integer from 0 to 4.
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 an aliphatic acyl group having 2 to 20 carbon atoms. , Benzoyl group, α-naphthylcarbonyl group, β-naphthylcarbonyl group, aromatic hydrocarbon group having 6 to 20 carbon atoms, and 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 an aliphatic acyl having 2 to 6 carbon atoms. Groups, benzoyl groups, phenyl groups, benzyl groups, and phenethyl groups are preferred.

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 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 transition metal compound represented by the above formula (a1). Not done.
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.

Preferable examples of the transition metal compound represented by the above-described formula (a1) include a transition metal complex having the following structure.

The transition metal complex represented by the above formula (a1) is, for example, a copolymerization of a norbornene monomer described later, or a norbornene monomer described later and 1-octene, 1-hexene, or a mixture thereof. It is preferably used for copolymerization, and is preferably used by copolymerization of norbornene with 1-octene, 1-hexene, or a mixture thereof.

[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 generally a product obtained by the reaction of trialkylaluminum with water, but a method of synthesizing by thermal decomposition is also known. ..

（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, propylaluminoxan, butylaluminoxane, isobutylaluminoxan, methylethylaluminoxan, methylbutylaluminoxane, methylisobutylaluminoxan and the like, and among them, methylaluminoxane and methylisobutylaluminoxan 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 transition metal compound (a).
Such ionic compounds include an anion of tetrakis (pentafluorophenyl) borate, an amine cation having an active proton such as (CH ₃ ) ₂ N (C ₆ H ₅ ) H ⁺ , and (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 transition metal compound (a), the aluminoxane (b1), and the ionic compound (b2) described above are usually used in a state of being dissolved or suspended in a solvent, preferably in a dissolved state.
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 transition metal compound (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. A solvent of 0.000000001 to 20 mol / L is used.

[Microreactor]
The microreactor is an inlet that introduces two or more liquids into the microreactor, a minute mixing field that can mix two or more liquids, and an outlet that takes out a mixed liquid obtained by mixing two or more liquids. A microreactor that has been conventionally used for various purposes can be used without particular limitation as long as the device is equipped with the above.

For example, a Y-shaped flow path or a microreactor having a T-shaped flow path inside can be preferably used. Such a microreactor has three openings on its sides corresponding to the ends of a Y-shaped or T-shaped flow path, two of which are used as inlets and the other one is used as an outlet.
When such a microreactor is used, the liquid introduced from the two inlets is well mixed near the intersection of the Y-shaped flow path and the T-shaped flow path, and then the mixed liquid is taken out from one outlet. Will be done.
The number of inlets of the microreactor is not particularly limited as long as it is 2 or more, and the number of outlets is not particularly limited as long as it is 1 or more.

The shape of the microreactor provided with the Y-shaped flow path and the T-shaped flow path is not particularly limited. The microreactor may be a non-chip-shaped device in which small-diameter tubes are simply connected by joints and a Y-shaped flow path or a T-shaped flow path is provided. Further, the microreactor may be a chip-shaped device in which a Y-shaped flow path or a T-shaped flow path is formed inside a plate-shaped or block-shaped chip.

Further, for example, it is also preferable to perform multi-stage mixing using a microreactor having a flow path as shown in FIG. 1 inside. In the flow path shown in FIG. 1, the liquid to be mixed is supplied from the two inlets 1, and after the liquid has passed through the plurality of fine flow paths, the liquid is mixed in the mixing field 3a. The liquid mixed in the first mixing field 3a passes through the fine flow path again and then is mixed again in the second mixing field 3b. After such mixing is repeated, the mixed liquid is taken out from the outlet 2. Although 5 mixing fields 3a to 3e are shown in FIG. 1, the number of mixing fields is not particularly limited.
It is also preferable to use the microreactor having the shape shown in FIG. 2 instead of the microreactor having the shape shown in FIG. In the microreactor shown in FIG. 1, the liquids supplied from the two inlets 1 collide horizontally before entering the microchannel.
On the other hand, in the microreactor shown in FIG. 2, the liquids supplied from the two inlets 1 collide with each other before entering the microchannel so that the angle formed by the two flow directions is an acute angle.

In the microreactor, the angle formed by the two flow paths communicating the inlet and the mixing field is preferably 1 to 179 °, preferably 30 to 150 °, and more preferably 60 to 120 °. When there are three or more channels communicating the inlet and the mixing field, it is preferable that the angle formed by any two of the plurality of channels is within the above range.

It is also possible to sequentially perform multi-stage mixing by using the above-mentioned Y-shaped flow path or a microreactor having a T-shaped flow path inside.
As an example, two microreactors having a Y-shaped flow path are used as a first-stage mixing device, and an outlet of two microreactors used as a first-stage mixing device has a Y-shaped flow path. Two-stage mixing can be performed by connecting to each of the two inlets of another microreactor.
By increasing the number of microreactors used as the first-stage mixing device, the number of stages of multi-stage mixing can be increased.

The diameter of the flow path of the microreactor used when mixing one or more selected from the group consisting of the transition metal compound (a), the aluminoxane (b1), and the ionic compound (b2) in the microreactor is desired. The catalyst composition is not particularly limited as long as it can produce a catalyst composition having the same performance. The width of the flow path is generally 1 μm to 1000 μm, preferably 10 to 500 μm, and more preferably 50 to 200 μm. The depth of the flow path is generally 1 μm to 1000 μm, preferably 10 to 500 μm, and more preferably 50 to 200 μm.
Further, the number of flow paths provided in one microreactor is not particularly limited.
The cross-sectional shape of the flow path is not particularly limited. Further, the residence time of the liquid supplied to the microreactor in the microreactor is not particularly limited.

The liquid containing the raw material of the catalyst composition is pumped to the inlet provided in the microreactor described above. The amount of liquid containing the raw material may vary, but quantitative liquid feeding that does not cause pulsation is preferable.
The liquid feeding method is not particularly limited, but the liquid is usually sent using a pump. As the liquid feeding pump, any of the industrially used liquid feeding pumps can be used. It is desirable that the pump for liquid feeding is a model that causes as little pulsation as possible during liquid feeding. Preferred pumps include plunger pumps, gear pumps, rotary pumps, diaphragm pumps and the like.

Usually, a liquid containing a transition metal compound (a) and a liquid containing one or more selected from the group consisting of aluminoxane (b1) and an ionic compound (b2) are sent to the microreactor.
When the liquid containing the raw material of the catalyst composition is sent to the microreactor, the number of moles of the transition metal element in the transition metal compound ( _a ) is defined as Ma, and the number of moles of aluminum in the aluminoxane (b1) is defined as M _b1 . When the number of moles of the ionic compound (b2) is M _b2 , 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. As such, it is preferable that the liquid containing the raw material of the catalyst composition is sent.

The temperature at which the liquid containing the raw material of the catalyst composition is introduced into the microreactor is not particularly limited, but is preferably -100 to 100 ° C, more preferably -50 to 50 ° C.
Since the heat transfer area per volume is large in the microreactor, the heat generated when the raw materials of the catalyst composition are mixed is satisfactorily removed.
If necessary, for the purpose of facilitating the removal of heat when the raw materials of the catalyst composition are mixed, cold air may be sent to the microreactor for air cooling, or the microreactor may be immersed in a refrigerant such as water for cooling. You may.

The catalyst composition produced by the method described above is a cyclic of a norbornene monomer homopolymerized or a copolymerization of a norbornene monomer and another monomer copolymerizable with the norbornene monomer, which will be described later. It is particularly preferably used in a method for producing an olefin resin composition.
Further, the catalyst composition can be suitably used in both living polymerization and non-living polymerization.

<Polymerization method>
A cyclic olefin resin composition is produced by polymerizing the monomer in the presence of the catalyst composition described above.
One selected from the group consisting of a transition metal compound (a), an aluminoxane (b1), and an ionic compound (b2) when initiating a polymerization reaction in the production of a cyclic olefin resin crude composition, as described above. The above and the monomer are continuously mixed in the tube.
By initiating the polymerization reaction in this way, it is possible to suppress the deactivation of the catalyst due to the heat generation at the start of the polymerization reaction. As a result, the cyclic olefin resin composition can be produced in high yield.

The wetted area of the tube flow path is not particularly limited as long as the yield of the cyclic olefin resin composition can be increased to a desired degree. The wetted area of the tube flow path is preferably 0.01 mm ² or more, more preferably 0.04 mm ² or more, and particularly preferably 0.4 mm ² or more per 1 mm ³ volume. The upper limit of the wetted area of the tube flow path is not particularly limited as long as the smooth delivery of the mixed polymerization reaction liquid is not hindered. The wetted area of the tube flow path is, for example, preferably 100 mm ² or less per 1 mm ³ volume, and more preferably 500 mm ² or less.

In the case of a cylindrical tube flow path, the wetted area per 1 mm ³ volume is 4 / D (mm ² ) when the inner diameter is D mm.
This is because when the length of the cylindrical tube is 1 mm, the volume is 0.25πD ² (mm ³ ) and the area of the inner surface of the tube is πD (mm ² ).
The specific relationship is as follows.
(Inner diameter (diameter, mm) / wetted area per ^{1 mm volume (mm 2 )} )
0.05mm / 80mm ²
0.1mm / 40mm ²
0.2mm / 20mm ²
0.5mm / 8mm ²
1mm / 4mm ²
2mm / 2mm ²
3mm / 1.33mm ²
4mm / 1mm ²
10mm / 0.4mm ²
100mm / 0.04mm ²

When the tube is cylindrical, the inner diameter (diameter) is preferably 0.05 mm or more and 100 mm or less, more preferably 0.1 mm or more and 50 mm or less, and particularly preferably 0.15 mm or more and 10 mm or less.
Therefore, the wetted area (mm ² ) per 1 mm ³ volume of the tube is preferably 0.04 mm ² or more and 80 mm ² or less, more preferably 0.08 mm ² or more and 40 mm ² or less, and 0.4 mm ² or more 26. 67 mm ² or less is particularly preferable.
In general, the smaller the inner diameter of the tube, the better the heat generated when the catalyst composition and the monomer are mixed can be removed, and a polymerization reaction in which the heat removal efficiency and the amount of polymer produced can be balanced can be realized. It will be like.
As the inner diameter of the tube becomes smaller, the amount of polymer produced tends to decrease, but one selected from the group consisting of the transition metal compound (a), the aluminoxane (b1), and the ionic compound (b2). By increasing the number of tube flow paths for mixing the above and the monomer, the heat removal efficiency can be improved without reducing the production amount of the polymer.

Although the cylindrical tube flow path has been described as an example as described above, the cross-sectional shape of the tube flow path is not limited to a circular shape. The cross-sectional shape of the tube flow path may be, for example, a quadrangle such as a square or a rectangle, a hexagon such as a regular hexagon, an octagon such as a regular octagon, or an ellipse.

The method of mixing the monomer with one or more selected from the group consisting of the transition metal compound (a), the aluminoxane (b1), and the ionic compound (b2) in the tube flow path is not particularly limited.
For example, a liquid containing a transition metal compound (a), a liquid containing one or more selected from the group consisting of an aluminoxane (b1) and an ionic compound (b2), and a liquid containing a monomer are 3 These may be supplied from one different flow path to one tube flow path and mixed in the tube flow path.
It also contains, for example, a catalyst composition prepared by mixing the transition metal compound (a) prepared by the above method and one or more selected from the group consisting of the aluminoxane (b1) and the ionic compound (b2). The liquid and the liquid containing the monomer may be supplied to one tube flow path from two different flow paths and mixed in the tube flow path.
Among the above methods, the latter method is obtained because the number of flow paths connected to the tube flow paths is small, the possibility of troubles such as blockage is low, and the catalytic activity as a catalytic composition is not easily impaired. Is preferable. In the latter method, as described above, it is preferable to prepare the catalyst composition using a microreactor.

The connection mode between the tube flow path and the component that constitutes the catalyst composition or the flow path that supplies the monomer to the tube flow path is not particularly limited.
For example, in a linear flow path in which a first flow path for supplying the catalyst composition to the tube flow path and a linear flow path in which the tube flow path is connected, a second flow path for supplying the monomer is provided to the linear flow path. It is preferable to connect to the connection point between the first flow path and the tube flow path or in the vicinity of the connection point so as to form an angle of 90 ° or about 90 °.
Further, when the liquid containing the catalyst composition and the liquid containing the monomer are supplied to the tube flow path from two different flow paths, the tube flow path and the liquid containing the catalyst composition are supplied. The first flow path to be supplied and the second flow path for supplying the liquid containing the monomer may be connected so that these flow paths form a Y-shape. The angle formed by the first flow path and the second flow path is preferably 1 to 179 °, preferably 30 to 150 °, and more preferably 60 to 120 °. When there are three or more flow paths, it is preferable that the angle formed by any two of the plurality of flow paths is within the above range. Further, as shown in the enlarged view in FIG. 5, by inserting the first flow path 14a inside the second flow path 14b, the liquid containing the catalyst composition is introduced in the cross section of the second flow path 14b. It is more preferable that the liquid containing the catalyst composition and the liquid containing the monomer are mixed so as to diffuse outward from the vicinity of the central portion. By mixing the liquid containing the catalyst composition and the liquid containing the monomer in this way, it is easy to remove the heat generated at the time of mixing particularly well.

The method of connecting the tube flow path and the flow path for supplying each material to the tube flow path is not particularly limited. These flow paths may be connected by simply connecting small diameter tubes by joints as long as the heat dissipation is not sacrificed, or may be formed in the chip in the same manner as the above-mentioned microreactor.

The material of the tube flow path is not particularly limited as long as it is a material that does not dissolve in the polymerization reaction solution or elute the component that inhibits the polymerization reaction into the polymerization reaction solution. A resin material such as fluororesin is preferable because it is easy to process and has abundant flexibility. Further, a metal material such as stainless steel (SUS material) is also preferable because of its excellent strength, excellent heat transferability, and easy removal of heat generated at the start of the polymerization reaction.

A polymerization reaction solution containing these components after the monomer is mixed with one or more selected from the group consisting of the transition metal compound (a), the aluminoxane (b1), and the ionic compound (b2). The residence time in the tube flow path is not particularly limited as long as the object of the present invention is not impaired. The residence time of the polymerization reaction solution immediately after mixing in the tube flow path is typically 1 microsecond or more and 60 minutes or less, and more preferably 1 microsecond or more and 30 minutes or less.

A liquid containing a catalyst composition or a liquid containing a monomer is sent to the tube flow path. The method of sending these liquids is not particularly limited, but usually the liquids are sent by a pump. The amount of these liquids to be sent may vary, but quantitative liquids that do not cause pulsation are preferable.
As the liquid feeding pump, any of the industrially used liquid feeding pumps can be used. It is desirable that the pump for liquid feeding is a model that causes as little pulsation as possible during liquid feeding. Preferred pumps include plunger pumps, gear pumps, rotary pumps, diaphragm pumps and the like.

Since there is little risk of blockage, etc., after the polymerization reaction solution is continuously retained in the tube flow path for the minimum required time, the polymerization reaction solution is transferred to various well-known reaction devices for the polymerization reaction. It is also preferable to do. Typical examples of well-known reactors include tube-type reactors, tank-type reactors, and forced thin-film reactors (eg, ULREA manufactured by Mtechnic).
In these reactors, the polymerization reaction can be carried out continuously, and a flexible material such as a Teflon (registered trademark) tube can be used, so that the flow path can be designed relatively freely. Reactor is preferred.
The size, shape, etc. of these reactors are not particularly limited. The size, shape, etc. of the reactor are appropriately selected in consideration of the reaction time (residence time of the reaction solution), the production amount of the cyclic olefin resin, and the like.

Hereinafter, a preferred embodiment of the method for producing the cyclic olefin resin composition will be described with reference to FIG.
Hereinafter, a method for producing a cyclic olefin resin composition containing the following a) to g) will be described.
a) Supply of monomer from monomer storage tank 10 b) Supply of transition metal compound (a) from first storage tank 11 c) Supply of aluminoxane (b1) from second storage tank 12 d) Transition in microreactor 13. Supply of catalyst composition by mixing metal compound (a) and aluminoxane (b1) e) Mixing of monomer and catalyst composition in tube flow path 14 f) Mixing in tube flow path 14. Reaction of the polymerized reaction solution in the tube reactor 15 g) Storage of the polymerization reaction solution discharged from the tube reactor 15 in the polymerization reaction solution storage container 16.

As described above, the apparatus shown in FIG. 5 includes a monomer storage tank 10, a first storage tank 11, a second storage tank 12, a microreactor 13, a tube flow path 14, a tube reactor 15, and a polymerization reaction liquid storage container 16.

The monomer storage tank 10 stores the monomer. The monomer is supplied from the monomer storage tank 10 to the tube flow path 14 using a pump (not shown). When the cyclic olefin resin composition is a copolymer, a monomer mixture containing a plurality of monomers may be contained in a single monomer storage tank 10 at a predetermined ratio. Further, a plurality of monomer storage tanks 10 may be provided, and different types of monomers may be stored in each of the plurality of monomer storage tanks 10. In this case, each single amount is supplied to the tube flow path 14 from each of the plurality of monomer storage tanks 10 so that the composition of the monomers to be subjected to the polymerization reaction has a desired composition. If necessary, aluminoxane may be mixed in order to reduce the influence of water and polar substances contained in a trace amount in the monomer. Further, in order to add the chain transfer agent to the polymerization system, an organoaluminum compound such as alkylaluminum or an organozinc compound may be mixed in the monomer, if necessary.

In FIG. 5, the method of supplying the monomer from the monomer storage tank 10 has been described, but the method of supplying the monomer is not limited to the method shown in FIG. For example, after charging a predetermined composition and amount of a monomer or a monomer mixture into a syringe pump, the syringe pump can supply the monomer or the monomer mixture to the tube flow path 14.

In parallel with the supply of the monomer to the tube flow path 14, the catalyst composition is prepared by the microreactor 13 and supplied to the tube flow path 14.
In the method using the apparatus shown in FIG. 5, the liquid containing the transition metal compound (a) is supplied to the microreactor 13 from the first storage tank 11, and the liquid containing the aluminoxane (b1) is supplied from the second storage tank 12 to the microreactor 13. The two are mixed in the microreactor 13 to prepare a catalyst composition. The prepared catalyst composition is discharged from the microreactor 13 and supplied to the tube flow path 14.
The supply of the transition metal compound (a) from the first storage tank 11 and the supply of the liquid containing the aluminoxane (b1) from the second storage tank 12 are performed by using a pump (not shown), respectively.

When the catalyst composition contains the ionic compound (b2), a third storage tank (not shown) for storing the liquid containing the ionic compound (b2) is further provided, and the ionic compound (b2) is added to the microreactor 13 from the third storage tank. ) May be supplied to mix the transition metal compound (a), the aluminoxane (b1), and the ionic compound (b2) in the microreactor 13.
Further, the second storage tank 12 may be charged with the ionic compound (b2) together with the aluminoxane (b1).

As described above, the monomer is supplied from the monomer storage tank 10 and the catalyst composition is supplied from the microreactor 13 to the tube flow path 14. At this time, the supply rate of the monomer and the supply rate of the catalyst composition are adjusted so that the amount of the catalyst composition used relative to the amount of the monomer is a desired amount.
By this method, the monomer and the catalyst composition are mixed in the tube flow path 14, thereby suppressing the deactivation of the catalyst due to the heat generation at the start of the polymerization reaction, and the cyclic olefin in a good yield. A resin composition can be produced.

The polymerization reaction liquid mixed in the tube flow path 14 is then supplied to the tube reactor 15. In the tube reactor 15, the polymerization reaction started in the tube flow path 14 is continued at a desired reaction temperature and reaction time.
In the reaction by the tube reactor 15, the method of adjusting the reaction temperature is not particularly limited. A preferred method is to place the tube reactor 15 in a temperature-adjustable thermostat (not shown).

After the polymerization reaction is carried out in the tube reactor 15 under desired conditions as described above, the polymerization reaction liquid discharged from the tube reactor is stored in the polymerization reaction liquid storage container 16. Then, the cyclic olefin resin composition is recovered from the polymerization reaction liquid stored in the polymerization reaction liquid storage container 16 according to a well-known method.
The polymerization reaction liquid discharged from the tube reactor may be directly used for the recovery operation of the cyclic olefin resin composition without being stored in the polymerization reaction liquid storage container 16.

In the method for producing the cyclic olefin resin composition, the norbornene monomer is homopolymerized using the catalyst composition for cyclic olefin polymerization produced by the above method, or the norbornene monomer and the norbornene monomer are used. Copolymerize with other copolymerizable monomers.
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, a monomer compound and a specific polymerization method will be described with respect to the method for producing the cyclic olefin resin composition.

[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 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 partially hydrogenated (or cyclopentadiene) thereof 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 . 1 ⁷ , 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-en, 8-vinyltetracyclo [4,4.0.1, ^2,5 . 17 and ¹⁰ ] Dodeca-3-en, 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-en, 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 resin composition, 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. And norbornene and 1-octene, 1-hexene, or a mixture thereof are preferred.
When norbornene and ethylene are used in combination, the amount of norbornene in the monomer is 30 mol% or more and 70 mol% in order to obtain a cyclic olefin resin composition having a good balance between mechanical properties and thermal properties. Less than is 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. Therefore, the glass transition temperature of the cyclic olefin resin composition should be increased. The amount of norbornene in the monomer is preferably 70 mol% or more.

It is preferable that the monomer used for mixing in the tube flow path contains all the other monomers, but if necessary, after mixing in the tube flow path, another monomer is used. The monomer may be supplied to the polymerization reaction solution.
For example, when the other monomer is ethylene, ethylene is usually gaseous under mixed conditions. For this reason, it is difficult to mix ethylene in the tube flow path. Under these circumstances, after mixing the monomers other than ethylene in the tube flow path, they are once collected and stored in a Schlenk tube, a glass eggplant flask or a metal kettle, and then, for example, a tank-type reaction. After charging a mixture of the catalyst composition and a monomer other than ethylene into the apparatus, ethylene may be supplied to carry out the polymerization reaction.

[Polymerization conditions]
The polymerization conditions are not particularly limited as long as a desired copolymer 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 after mixing by the tube flow path is not particularly limited as long as the polymerization reaction proceeds at a desired rate. The polymerization temperature is typically 0 to 120 ° C, preferably 10 to 100 ° C, more preferably 20 to 90 ° C.
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 after mixing by the tube flow path varies depending on the temperature, the composition of the catalyst composition, and the monomer composition, but is typically 0.01 to 120 hours, and is 0.1 to 0.1. 80 hours is preferable, and 0.2 to 10 hours is more preferable.

Since it is easy to produce a cyclic olefin resin composition in a good yield, the aluminoxane is added to the norbornene monomer or the polymerization system containing the norbornene monomer and other monomers before adding the catalyst composition. , And one or more selected from the alkylaluminum compounds are preferably present. The aluminoxane and the alkylaluminum compound may be mixed with the monomer in the tube flow path, may be added to the solution of the monomer supplied to the tube flow path, and may be added to the tank connected to the tube flow path. It may be pre-loaded in a mold reaction device or the like.

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 the formula (II), R ¹⁰ is an alkyl group having 1 to 15 carbon atoms, preferably 1 to 8 carbon atoms, X is a halogen atom or a hydrogen atom, and z is an integer of 1 to 3).

Examples of the alkyl group having 1 to 15 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 to 1 mol of the transition metal compound is preferably 10 to 1,000,000 mol, more preferably 100 to 100,000 mol.
When the alkylaluminum compound is added to the polymerization system before the catalyst composition is added, the number of moles of aluminum per 1 mol of the transition metal compound is preferably 5 to 500,000 mol, more preferably 50 to 50,000 mol.

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 resin composition can be continuously produced, and the production cost of the cyclic olefin resin composition can be reduced.

According to the method described above, at the time of initiating the polymerization reaction, one or more selected from the group consisting of the transition metal compound (a), the aluminoxane (b1), and the ionic compound (b2), and a monomer. Since the mixing with the compound is continuously performed in the tube flow path, the heat generated at the start of the polymerization reaction can be satisfactorily removed through the wide wetted surface provided in the tube flow path. As a result, the deactivation of the catalyst due to heat can be suppressed, and the cyclic olefin resin composition can be obtained in a high yield.

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

[Example 1]
A toluene solution of the transition metal compound having a concentration of 3.17 μmol / L was prepared. As the transition metal compound, a compound having the following structure was used.

As the aluminoxane solution, a TMAO-211 toluene solution (a solution of methylaluminoxane, manufactured by Toso Finechem Co., Ltd.) having a concentration of 9.0% by mass (as the content of Al atoms) was used.

A microreactor (product name: microvolume connector 1/16 "Y SUS 0.15 mm, VICI" having a Y-shaped flow path having a circular cross section and a diameter of 150 μm for a solution of a transition metal compound and a solution of aluminoxane. The molar ratio of Al / M is the value of "Al / M ratio (catalyst activation)" shown in Table 1, and the flow rates of the transition metal compound solution and the aluminoxane solution are 0. It was supplied using a syringe pump (KD SCIENTIFIC, KDS100) so as to be 05 mL / min. The discharged catalyst composition subsequently passed through a cylindrical Teflon® tube having an inner diameter of 1 mm and a length of 50 cm.

Here, M means the central metal of the transition metal compound, and is Ti or Zr.
The microreactor includes a Y-shaped flow path in which three flow paths are connected. Of the three channels, the angle formed by the two channels communicating the inlet and the mixing field is 90 °.
FIG. 4 schematically shows the shape of a microreactor having a Y-shaped flow path. The microreactor shown in FIG. 4 is provided with a Y-shaped flow path in the mixing field 3 inside the disk-shaped case 4. In FIG. 4, the dotted line portion is the outer edge of the flow path held in the case 4.
Further, the tube for supplying the catalyst composition and the tube flow path were linearly connected.

At the same time as the supply of the catalyst composition to the tube flow path was started, the supply of the monomer solution to the tube flow path was started. The flow rate of the monomer solution was 2.9 mL / min. As a monomer solution, a toluene solution of norbornene and 1-octene are contained at the concentrations shown in Table 2 and as 1-octene / norbornene (molar ratio) of 1.1, and methylaminoxane is contained. A monomer solution was used.
Here, the content of methylaluminoxane in the monomer solution is the center M of the transition metal compound in the catalyst composition supplied to the tube flow path and the methyl in the monomer solution supplied to the tube flow path. The ratio (molar ratio) with Al derived from alminoxane is an amount which is a value described as "Al / M ratio (in a monomer solution or a reaction tank)" in Table 1.

In a reaction vessel (eggplant-shaped flask), 40 mL of a mixed solution of the monomer and methylaluminoxane having the value described as "Al / M ratio (in the monomer solution or reaction vessel)" in Table 1 was prepared. bottom.
The catalyst composition and the monomer solution were mixed using a Teflon (registered trademark) tube having an inner diameter of 2.18 mm and a length of 5 cm into which a tube having an inner diameter of 1 mm was inserted. Specifically, while supplying the monomer solution into the Teflon (registered trademark) tube, the catalyst composition is supplied from the tube having an inner diameter of 1 mm, and the catalyst composition is supplied from the vicinity (inside) of the center of the cross section of the Teflon (registered trademark) tube. The catalyst composition is mixed so as to diffuse outward into the monomer solution, and the mixed solution of the catalyst composition and the monomer solution is passed through a 40 cm long Teflon (registered trademark) tube and then passed. It was added dropwise to the reaction vessel so as to have a total of 100 mL.
A total of 100 mL of the polymerization solution thus obtained was subjected to a polymerization reaction under the conditions of the polymerization temperature and the polymerization time shown in Table 2.

After the polymerization was carried out for a predetermined time, a small amount of 2-propanol was added to the polymerization system to terminate the reaction. Then, the polymer solution was poured into methanol containing hydrochloric acid to completely precipitate the copolymer. The precipitated copolymer was filtered off and the copolymer was washed with a large amount of methanol. Then, the wet body of the copolymer was dried under reduced pressure at 100 ° C. for 1 day or more to obtain a copolymer. The mass of the obtained copolymer was measured, and the ratio of the obtained copolymer to the transition metal compound used was calculated (“Copolymer per hour per “transition metal compound (1 g)” in Table 2). Production amount (g) ").

Further, for the obtained copolymer, the number average molecular weight (Mn) was obtained, and the molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn) was obtained from Mn and the weight average molecular weight (Mw). The glass transition temperature (Tg) was measured by the DSC method. By NMR measurement, the proportion of units derived from norbornene contained in the copolymer was measured. Table 2 shows the measurement results of the ratio of units derived from Mn, Mw / Mn, Tg and norbornene.

(Measuring conditions for copolymer molecular weight (Mn and Mw))
Device: Malvern Viscotek TDA302 detector + Pump autosampler device detector: RI
Solvent: Toluene Column: Tosoh TSKgel GMHHR-M (300 mm x 7.8 mmφ)
Flow velocity: 1 mL / min Temperature: 75 ° C
Sample concentration: 2.5 mg / mL
Injection volume: 100 μL
Standard sample: monodisperse polystyrene

(Measurement conditions for copolymer glass transition temperature (Tg))
Tg was measured by the DSC method (method described in JIS K7121).
DSC device: Differential scanning calorimeter (DSC-Q1000 manufactured by TA Instrument)
Measurement atmosphere: Nitrogen measurement mode: Modified
Heating conditions: 2 ° C / min

(Measurement conditions for the percentage of units derived from norbornene)
NMR device: BrukerAVANCE 600
Measuring solvent: 1,1,2,2-tetrachloroethane-d ₂
Nuclide to be measured: ¹³ C
Measurement temperature: 381K
Sample concentration: 70 mg / mL
Sample tube diameter: 10 mm
Measurement method: power gate method Decoupling: Complete decoupling Cumulative number: 18,000 times Chemical shift reference: 1,1,2,2 _- Tetrachloroethane-d2, non-deuterated 1,1,2 , 2-Tetrachloroethane peak was set to 74.47 ppm.
Percentage of units derived from norbornene: The copolymer of norbornene and ethylene was carried out with reference to Non-Patent Document 1. The copolymer of norbornene and 1-octene was carried out with reference to Non-Patent Document 3.

[Example 2]
A catalyst composition was prepared in the same manner as in Example 1. Further, the catalyst composition and the monomer solution were mixed in the same manner as in Example 1. The mixture of the obtained catalyst composition and the monomer solution was placed inside a constant temperature bath set to the polymerization temperature shown in Table 2 after passing through a 40 cm long Teflon (registered trademark) tube. The solution was continuously fed to a Teflon (registered trademark) tube reactor having an inner diameter of 2.18 mm and a diameter of 10 m. From 1 hour to 6 hours after the start of liquid transfer, the polymer solution is continuously dropped from the tube reactor into methanol containing hydrochloric acid through an 80 cm long Teflon (registered trademark) tube placed outside the constant temperature bath. By doing so, the copolymer was completely precipitated. Then, the copolymer was obtained by the method described in Example 1.

[Example 3]
Coweight in the same manner as in Example 2 except that trimethylaluminum having the values listed as "Al / M ratio (in monomeric solution or reaction tank)" was used instead of methylaluminoxane. I got a coalescence.

[Example 4]
A copolymer was obtained in the same manner as in Example 2 except that the catalyst composition and the monomer solution were mixed using a tube having an inner diameter of 4.57 mm.

[Example 5]
A copolymer was obtained in the same manner as in Example 1 except that the polymerization reaction temperature was changed to the temperature shown in Table 2.

[Example 6]
A copolymer was obtained in the same manner as in Example 1 except that the polymerization reaction temperature was changed to the temperature shown in Table 2.

[Example 7]
A copolymer was obtained in the same manner as in Example 2 except that the polymerization reaction temperature was changed to the temperature shown in Table 2.

[Example 8]
A toluene solution of the transition metal compound having a concentration of 0.215 μmol / L was prepared. As the transition metal compound, a compound having the following structure (Ph ₂ C (Cpd) (Flu) ZrCl ₂ ) was used.

A microreactor (product name: microvolume connector 1/16 "Y SUS 0.15 mm, VICI" having a Y-shaped flow path having a circular cross section and a diameter of 150 μm for a solution of a transition metal compound and a solution of aluminoxane. The molar ratio of Al / M is the value of "Al / M ratio (catalyst activation)" shown in Table 1, and the flow rates of the transition metal compound solution and the aluminoxane solution are 0. It was supplied using a syringe pump (KD SCIENTIFIC, KDS100) so as to be 05 mL / min. The discharged catalyst composition passed through a cylindrical Teflon (registered trademark) tube having an inner diameter of 1 mm and a length of 50 cm.

At the same time as the supply of the catalyst composition to the tube flow path was started, the supply of the monomer solution to the tube flow path was started. The flow rate of the monomer solution was 2.9 mL / min. As the monomer solution, a toluene solution of norbornene was used at the concentration shown in Table 2 and a monomer solution containing methylaminoxane was used.
Here, the content of methylaluminoxane in the monomer solution is the center M of the transition metal compound in the catalyst composition supplied to the tube flow path and the methyl in the monomer solution supplied to the tube flow path. The ratio (molar ratio) with Al derived from alminoxane is an amount which is a value described as "Al / M ratio (in a monomer solution or a reaction tank)" in Table 1.

The catalyst composition and the monomer solution were mixed in the same manner as in Example 1. The prepared mixed solution of the catalyst composition and the monomer solution was collected and stored in a Schlenk tube under a nitrogen atmosphere. In a reaction vessel (stainless autoclave), 40 mL of a toluene mixed solution of norbornene and methylaluminoxane having a value described as "Al / M ratio (in a monomer solution or reaction vessel)" in Table 1 was prepared. .. To this reaction vessel, a solution containing the catalyst composition stored in a Schlenk tube was added to a total of 100 mL. Then, the polymerization reaction was carried out by applying the polymerization temperature and ethylene pressure shown in Table 2. After 0.25 hours from the start of the polymerization, the ethylene pressure was released and a small amount of 2-propanol was added to the polymer solution to stop the reaction. Then, the copolymer was obtained in the same manner as in Example 1 except that the copolymer was obtained from the polymer solution by the method described in Example 1. The ethylene pressure shown in Table 2 means the pressure of ethylene in the autoclave polymerization.

[Example 9]
A copolymer was obtained in the same manner as in Example 8 except that the norbornene concentration and the ethylene pressure during the polymerization were changed to the monomer compositions shown in Table 2, respectively.

[Comparative Example 1]
The entire amount of the monomer solution is charged in the reaction vessel (nasal flask) in advance, and the catalyst composition is continuously supplied into the reaction vessel instead of the tube flow path to form the monomer in the flask. A copolymer was obtained in the same manner as in Example 1 except for mixing.

[Comparative Example 2]
The entire amount of the monomer solution is charged in the reaction vessel in advance, the temperature conditions shown in Table 1 are set to 40 ° C., and the catalyst composition is continuously supplied to the reaction vessel instead of the tube flow path. A copolymer was obtained in the same manner as in Example 1 except that the mixture was mixed with the monomer in the flask.

[Comparative Example 3]
Other than charging the entire amount of the monomer solution into the reaction vessel in advance, and continuously supplying the catalyst composition to the reaction vessel instead of the tube flow path and mixing it with the monomer in the flask. Obtained a copolymer in the same manner as in Example 5.

[Comparative Example 4]
Other than charging the entire amount of the monomer solution into the reaction vessel in advance, and continuously supplying the catalyst composition to the reaction vessel instead of the tube flow path and mixing it with the monomer in the flask. Obtained a copolymer in the same manner as in Example 6.

[Comparative Example 5]
Other than charging the entire amount of the monomer solution into the reaction vessel in advance, and continuously supplying the catalyst composition to the reaction vessel instead of the tube flow path and mixing it with the monomer in the flask. Obtained a copolymer in the same manner as in Example 8.

[Comparative Example 6]
Other than charging the entire amount of the monomer solution into the reaction vessel in advance, and continuously supplying the catalyst composition to the reaction vessel instead of the tube flow path and mixing it with the monomer in the flask. Obtained a copolymer in the same manner as in Example 9.

Hereinafter, Table 1 shows the mixing conditions of the catalyst composition and the monomer (mixing method, wetted area mm ² , temperature per 1 mm ³ volume of the tube flow path, temperature), the polymerization apparatus, the polymerization method, and Al /. The M ratio (in a monomer solution or in a reaction vessel) and the Al / M ratio (catalyst activation) are described.
The wetted area shown in Table 1 is the wetted area per 1 mm ³ of the volume of the tube flow path used for mixing the catalyst composition and the monomer.
The mixing methods shown in Table 1 are as follows.
TB: Tube flow path FL: Flask Further, the polymerization apparatus shown in Table 1 is as follows.
FL: Eggplant-shaped flask TR: Tube reactor AC: Autoclave

Hereinafter, Table 2 shows the polymerization temperature, the polymerization time, and the composition of the monomers used in the polymerization reaction.

Hereinafter, Table 3 shows the amount of copolymer produced (g) per transition metal compound (1 g) and the copolymer characteristics (number average molecular weight, molecular weight distribution, Tg, ratio of units derived from norbornene). ..

According to the comparison between Examples 1 to 9 and Comparative Examples 1 to 6, one or more selected from the group consisting of the transition metal compound (a), the aluminoxane (b1), and the ionic compound (b2). When the polymerization reaction is started by mixing the monomer in the tube flow path, the yield of the cyclic olefin resin composition per amount of the transition metal compound used is significantly higher than that in the case where the polymerization reaction is not started. I understand. Further, it can be seen that by carrying out the polymerization reaction in a tube reactor after the start of the polymerization reaction, it can be suitably used particularly in the polymerization reaction at a high temperature at which the catalyst composition is easily deactivated.

1: Inlet 2: Outlet 3: Mixing field 3a to 3e: Mixing field 4: Case 10: Monomer storage tank 11: First storage tank 12: Second storage tank 13: Microreactor 14: Tube flow path 15: Tube reactor 16: Polymerization reaction Liquid storage container

Claims (5)

A method for producing a cyclic olefin resin composition.
The polymerization reaction for producing the cyclic olefin resin composition is a single amount in the presence of one or more selected from the group consisting of the transition metal compound (a), the aluminoxane (b1), and the ionic compound (b2). It is done by polymerizing the body,
The transition metal compound (a) is a transition metal complex containing a ligand containing a cyclopentadiene ring and a transition metal of Group IV of the periodic table.
At the time of initiating the polymerization, a mixture of the transition metal compound (a), one or more selected from the group consisting of the aluminoxane (b1) and the ionic compound (b2), and the monomer is mixed. Perform continuously in the tube and
Before mixing the monomer with one or more selected from the group consisting of the transition metal compound (a), the aluminoxane (b1), and the ionic compound (b2).
A method of mixing the transition metal compound (a) with one or more selected from the group consisting of the aluminoxane (b1) and the ionic compound (b2) in a microreactor . The manufacturing method according to claim 1, wherein the wetted area in the tube is 0.4 mm ² or more per 1 mm ³ in volume. The production method according to claim 1 or 2 , wherein the Group IV transition metal in the periodic table is Zr and / or Ti. Claims 1 to 3 to produce the cyclic olefin resin composition by homopolymerization of the norbornene monomer or copolymerization of the norbornene monomer with another monomer copolymerizable with the norbornene monomer. The manufacturing method according to any one of the above items. Any one of claims 1 to 4 , wherein the cyclic olefin resin composition is a copolymer of one or more selected from the group consisting of ethylene, 1-hexene, and 1-octene and a norbornene monomer. The manufacturing method according to item 1.

Images