JP7150428B2 - Method for producing catalyst composition for cyclic olefin polymerization and method for producing cyclic olefin resin composition - Google Patents

Description

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

Cyclic olefin homopolymers and cyclic olefin copolymers have low hygroscopicity 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.
A representative cyclic olefin copolymer is a copolymer of cyclic olefin and ethylene, which is widely used as a transparent resin. A copolymer of cyclic olefin and ethylene can change its glass transition temperature according to the composition of the copolymer of cyclic olefin and ethylene. Coalescence can be produced. Copolymers with high Tg generally have good heat resistance (see, for example, Non-Patent Document 1).

In addition to copolymers of cyclic olefins and ethylene, copolymers of cyclic olefins and α-olefins other than ethylene are known. Copolymers of cyclic olefins and ethylene have a good balance between heat resistance and mechanical properties, but if the heat resistance is increased, the mechanical properties may deteriorate. By copolymerizing a cyclic olefin with an α-olefin other than ethylene, it is possible to improve the balance between heat resistance and mechanical properties, which is a problem with copolymers of cyclic olefins and ethylene.

Regarding the method for producing such a cyclic olefin resin composition, the copolymerization reaction of a cyclic olefin and ethylene differs greatly from the copolymerization reaction of a cyclic olefin and an α-olefin other than ethylene. Specifically, in a zirconocene-based metallocene-based transition metal catalyst that is suitably used in the copolymerization reaction of a cyclic olefin and ethylene, in the copolymerization of a cyclic olefin and an α-olefin, chain transfer caused by the α-olefin It has been known that it is difficult to obtain a high molecular weight compound due to the reaction (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, a resin composition of a cyclic olefin and an α-olefin is a titanocene-based metallocene commonly known as a so-called half-metallocene (post-metallocene), which is different from the conventionally used zirconocene-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, synthesis of cyclic olefin resin compositions such as cyclic olefin homopolymers and cyclic olefin copolymers is generally carried out using catalysts represented by metallocene transition metal catalysts. Regardless of whether it is a metallocene transition metal catalyst or a half-metallocene transition metal catalyst, metallocene transition metal catalysts are generally expensive, so reducing the amount of catalyst used reduces the cost of the entire production of the cyclic olefin resin composition. Therefore, 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, at least a cyclic olefin monomer (A) derived from norbornene and a C4 to C12 α-olefin are used in the presence of a metallocene transition metal catalyst. A method has been proposed that includes a polymerization step of obtaining a copolymer by polymerizing the α-olefin monomer (B) obtained (see Patent Documents 1 and 2).

WO2015/178143 WO2015/178144

Incoronata, Tritto et al., Coordination Chemistry Reviews, 2006, 250, p. 212-241 Jung, H.; 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, a cyclic olefin monomer, an α-olefin monomer, and an aluminoxane cocatalyst are added to a reaction vessel, and the contents of the reaction vessel are heated to a predetermined polymerization temperature. Activation of the transition metal compound is carried out by adding a transition metal compound and an aluminoxane, each dissolved in toluene, to a reaction vessel. When using a catalyst composition activated by such a method, the yield of cyclic olefin copolymer was not always good.

The present invention has been made in view of the above problems, and provides a method for producing an activated catalyst composition that produces a polymer at a high yield when polymerizing a monomer containing a cyclic olefin; The activated catalyst composition produced by the method is used to homopolymerize norbornene monomers or to co-polymerize norbornene monomers with other monomers copolymerizable with norbornene monomers. It aims at providing the manufacturing method of the cyclic olefin resin composition which superposes|polymerizes.

The present inventors used a transition metal complex containing a ligand containing a cyclopentadiene ring and a Group IV transition metal of the periodic table as the transition metal compound (a), and the transition metal compound (a) and an aluminoxane (b1) and one or more selected from the group consisting of ionic compounds (b2) are mixed in a microreactor to produce a catalyst composition for polymerizing cyclic olefins. The present inventors have found that the problem can be solved and completed the present invention.
More specifically, the present invention provides the following.

(1) A method for producing a catalyst composition for cyclic olefin polymerization, comprising:
A transition metal compound (a), an aluminoxane (b1), and one or more selected from the group consisting of an ionic compound (b2) are mixed in a microreactor,
The transition metal compound (a) is a transition metal complex containing a ligand containing a cyclopentadiene ring and a Group IV transition metal of the periodic table,
A method wherein the ionic compound (b2) is a compound that produces a cationic transition metal compound upon reaction with the transition metal compound (a).

(2) A method for producing a cyclic olefin resin composition in which a norbornene monomer is homopolymerized, or a norbornene monomer and another monomer copolymerizable with the norbornene monomer are copolymerized. hand,
(1) producing the catalyst composition for cyclic olefin polymerization by the method;
and homopolymerizing or copolymerizing in the presence of a catalyst composition.

(3) Presence of one or more selected from aluminoxanes and alkylaluminum compounds in a polymerization system containing a norbornene monomer or a norbornene monomer and other monomers before adding the catalyst composition. , a method for producing a cyclic olefin resin composition according to (2).

(4) The method according to (2) or (3), wherein at least part of the catalyst composition is continuously added to a polymerization system containing a norbornene monomer or a norbornene monomer and another monomer. A method for producing a cyclic olefin resin composition.

(5) 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, (2) to (4) ), the method for producing a cyclic olefin resin composition according to any one of

According to the present invention, there is provided a method for producing an activated catalyst composition that produces high yields of polymer when polymerizing monomers containing cyclic olefins, and the activated catalyst composition produced by the method. A cyclic olefin resin composition that uses a catalyst composition to homopolymerize a norbornene monomer or copolymerize a norbornene monomer with another monomer copolymerizable with the norbornene monomer. can provide a manufacturing method of

FIG. 4 is a diagram showing a preferred mode of the shape of a channel when multi-stage mixing is performed in a microreactor. FIG. 2 is a diagram showing a preferred embodiment, different from the embodiment shown in FIG. 1, of the shape of a channel when multi-stage mixing is performed in a microreactor. FIG. 4 is a diagram schematically showing the shape of a microreactor having a T-shaped channel inside a case; FIG. 4 is a diagram schematically showing the shape of a microreactor having a Y-shaped flow path inside a case;

<<Method for producing catalyst composition for cyclic olefin polymerization>>
A method for producing a catalyst composition for cyclic olefin polymerization comprises:
It includes 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.
When the transition metal compound (a), the aluminoxane (b1), and one or more selected from the group consisting of the ionic compound (b2) are mixed to produce an activated catalyst composition, heat generation during mixing Due to these effects, not only desired cationic species with high polymerization activity but also cationic species with low polymerization activity and thermally unstable are generated.
For these reasons, it is presumed that conventional methods such as the methods described in Examples of Patent Documents 1 and 2 are difficult to produce polymers with good yields.
On the other hand, when mixing the transition metal compound (a), the aluminoxane (b1), and one or more selected from the group consisting of the ionic compound (b2) using a microreactor, the transfer is Due to the very large heat area, the heat generated during mixing is well removed.
For this reason, it is believed that the proportion of the desired cationic species with high polymerization activity that is produced increases, and a catalyst composition that gives a polymer at a high yield can be produced.

The materials used in the production of the catalyst composition, the microreactor, and the specific production method of the catalyst composition will be described below 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 Group IV transition metal of the periodic table. Such a transition gold compound (a) is a so-called metallocene 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 connecting 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 linear or branched 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 is a plurality of R ¹ in (ZR ¹ _m ), the plurality of R ¹ may be the same or different.
When (ZR ¹ _m ) is repeated multiple times, the multiple (ZR ¹ _m ) may be the same or different.
Cp is an optionally substituted cyclopentadienyl group or an optionally substituted cyclopentadiene ring-containing cyclic group.
A is a group similar to Cp, or -O-, -S-, or -N(R ² )-.
R ² is a hydrogen atom, a linear or branched chain, an aliphatic having 1 to 20 carbon atoms which may contain a cyclic skeleton, and which may have an unsaturated bond; 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 a 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 is a plurality of L's, the plurality of L's may be the same or different, and are preferably the same.
L' is a halogen atom, -OR ⁵ , or -N=C(R ⁵ )R ⁵ .
R ⁵ 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, which may contain a heteroatom, or a linear It is an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may be linear, branched, may contain a cyclic skeleton, and may have an unsaturated bond. When R ⁵ is plural, they may be the same or different.
When there are multiple L's, the multiple L's may be the same or different.
m is 1 or 2; More specifically, m is 1 when Z is N or P, and m is 2 when Z is C, Si, or Ge.
n is an integer of 0-4.
r is 0 or 1; If r is 0, then n is 0.
p is an integer from 0 to 3;
q is an integer from 0 to 3;
p+q is equal to the oxidation state of metal M minus 2 (oxidation state of metal M −2) when r is 1.
p+q is equal to the oxidation state of metal M minus one (oxidation state of metal M minus one) when r is zero.
p+q is less than four.

In the transition metal complex represented by Formula (1), the divalent bridging group (ZR ¹ _m ) _n is CR ¹ ₂ , (CR ¹ ₂ ) ₂ , (CR ¹ ₂ ) ₃ , SiR ¹ ₂ , 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 0-4.

The ligand Cp π-bonded to the metal M is an optionally substituted cyclopentadienyl group or an optionally substituted cyclopentadiene ring-containing cyclic group.
Preferable examples of Cp include cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, 4-tert-butylcyclopenta dienyl group, 4-adamantylcyclopentadienyl group, monomethylindenyl group, dimethylindenyl group, trimethylindenyl group, tetramethylindenyl group, 4,5,6,7-tetrahydroindenyl group, fluorenyl group, 5,10-dihydroindeno[1,2-b]indol-10-yl group, N-methyl-5,10-dihydroindeno[1,2-b]indol-10-yl group, N-phenyl- 5,10-dihydroindeno[1,2-b]indol-10-yl group, 5,6-dihydroindeno[2,1-b]indol-6-yl; N-methyl-5,6-dihydro Indeno[2,1-b]indol-6-yl, and N-phenyl-5,6-dihydroindeno[2,1-b]indol-6-yl.

A is a group similar to Cp, or -O-, -S-, or -N(R ² )-. A is preferably the same group as Cp.

Metal M is Ti, Zr or Hf.

L is preferably a group selected from the group consisting of methyl group, ethyl group, n-butyl group, sec-butyl group, phenyl group, benzyl group and —CH ₂ Si(CH ₃ ) ₃ , and among them A methyl group is more preferred.
L′ is preferably a group selected from the group consisting of halogen, —OR ⁵ (R ⁵ is as described above), or —N═C(R ⁵ )R ⁵ , among which —Cl, —O -2,6-(t-Bu) ₂ -C ₆ H ₃ or -N=C(t-Bu) ₂ is more preferred.

n is an integer of 0-4, preferably 0-2.

A specific example of the transition metal complex represented by formula (1) in which n is 0 and r is 0 is CpdMCl ₂ (O-2,6-(t-Bu) ₂ -C ₆ H ₃ ), CpdMMe ₂ (O-2,6-(t-Bu) ₂ -C ₆ H ₃ ), CpdMMeCl (O-2,6-(t-Bu) ₂ -C ₆ H ₃ ), tet-CpdMCl ₂ (O-2,6-(t-Bu) ₂ -C ₆ H ₃ ), tet-CpdMMe ₂ (O-2,6-(t-Bu) ₂ -C ₆ H ₃ ), tet-CpdMMeCl(O- 2,6-(t-Bu) ₂ -C ₆ H ₃ ), CpdMCl ₂ (O-2,6-(i-Pr) ₂ -C ₆ H ₃ ), CpdMMe ₂ (O-2,6-(i -Pr) ₂ -C ₆ H ₃ ), CpdMMeCl(O-2,6-(i-Pr) ₂ -C ₆ H ₃ ), tet-CpdMCl ₂ (O-2,6-(i-Pr) ₂ - C ₆ H ₃ ), tet-CpdMMe ₂ (O-2,6-(i-Pr) ₂ -C ₆ H ₃ ), tet-CpdMMeCl(O-2,6-(i-Pr) ₂ -C ₆ H ₃ ), CpdMCl ₂ (N=C(t-Bu) ₂ ), CpdMMe ₂ (N=C(t-Bu) ₂ ), CpdMMeCl (N=C(t-Bu) ₂ ), (t-BuC ₅ H ₄ ) MCl ₂ (N=C(t-Bu) ₂ ), (t-BuC ₅ H ₄ )MMe ₂ (N=C(t-Bu) ₂ ), (t-BuC ₅ H ₄ )MMeCl(N= C(t-Bu) ₂ ), tet-CpdMCl ₂ (N=C(t-Bu) ₂ ), tet-CpdMMe ₂ (N=C(t-Bu) ₂ ), tet-CpdMMeCl (N=C(t -Bu) ₂ ), CpdMCl ₂ (N=C-(t-Bu-N-CH=CH-Nt-Bu) ₂ ), CpdMMe ₂ (N=C-(t-Bu-N-CH=CH -Nt-Bu) ₂ ), CpdMMeCl (N=C-(t-Bu-N-CH=CH-Nt-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 ).
In the above examples, Me is a methyl group, t-Bu is a tert-butyl group, i-Pr is an iso-propyl group, Cpd is a cyclopentadienyl group, tet-Cpd is a tetramethyl It is a cyclopentadienyl group, and M is as described for formula (1), preferably Zr, Ti, or Hf, more preferably Ti.

Specific examples of the transition metal complex represented by formula (1) where n is 0 and r is 1 include (Me ₃ Cpd) ₂ MCl _{2 ,} (Me ₃ Cpd) ₂ MMe 2 , ( _Me3Cpd ) _2MMeCl , ( _Me3Cpd ) _2MPh2 , ( _Me3Cpd ) _2MBz2 , _{( Me4Cpd} ) _{2MCl2 , ( Me4Cpd} ) _2MMe2 , _{( Me5Cpd} ) _{2MCl 2} , _{( Me5Cpd} ) _2MPh2 , _{( Me5Cpd} ) _2MBz2 , _{( EtMe4Cpd} ) _2MCl2 , [ ₍ Ph) _Me4Cpd ] _2MCl2 , _{( Et5Cpd} ) _2MCl2 , (Ind) _2MCl2 , (Ind) _2MMeCl , ₍ Ind) _2MPh2 , ₍ Ind) _2MMe2 , ₍ Ind) _2MMeCl , _{( H4Ind} ) _2MCl2 , _{( H4Ind} ) _2MMe2 , (H ₄ Ind) ₂ MPh ₂ , and (Me ₄ Cpd)(Me ₅ Cpd)MCl ₂ .
In the above examples, Me is a methyl group, Et is an ethyl group, Cpd is a cyclopentadienyl group, Ind is an indenyl group, H ₄ Ind is 4,5,6,7,-tetrahydro is an indenyl group, Ph is a phenyl group, and Bz is a benzyl group. Moreover, M is as described for formula (1), preferably Zr, Ti, or Hf, more preferably Zr.

Specific examples of the transition metal complex represented by formula (1) where n is 1 or 2 and r is 1 include Me ₂ C(Cp)(Ind)MCl ₂ , Me ₂ C(Cp ) (Ind) _MMe2 , _Me2C (Cp)(Ind) _MPh2 , _Me2C (Cp)(Ind) _MBz2 , _Me2C (Cp)(Ind)MMeCl, _Ph2C (Cp)(Ind) )MCl2, _{Ph2C (} Cp)(Ind) _MMe2 , _Ph2C (Cp)(Ind) _MPh2 , _Ph2C (Cp)(Ind) _MBz2 , _Ph2C (Cp)(Ind)MMeCl , _{Me2Si ( Me4Cpd} ) _2MCl2 , _{Me2Si ( Me4Cpd} ) _2MMe2 , _{Me2Si ( Me4Cpd} ) _2MPh2 , _{Me2Si ( Me4Cpd} ) _2MBz2 , Me _2Si ( _Me4Cpd ) _2MMeCl , _Me2C ( _Me4Cpd )( _MeCpd )MCl2, _{Me2C ( Me4Cpd} )( _MeCpd ) _MMe2 , _Me2Si (Ind) _2MCl2 , Me2 Si ₍ Ind) _2MMe2 , _{Me2Si (} Ind) _2MPh2 , _Me2Si (Ind) _2MBz2 , _{Me2Si (} Ind) _2MMeCl , _{Me2Si ( Me4Cpd} ) _2MCl2 , Me _{2Si ( Me4Cpd} ) _2MMe2 , _{C2H4 ( Ind} ) _2MMe2 , _{C2H4 ( Ind} ) _2MPh2 , _{C2H4 ( Ind} ) _2MBz2 , _{C2H4 (} H _4Ind ) _2MMe2 , Ph ₍ Me)Si(Ind) _2MMe2 , _{Ph2Si (} Ind) _2MMe2 , _{Me2C (} Flu)(Cpd)MCl2, _{Me2C (} Flu)(Cpd) _MMe2 , _Me2C (Flu)(Cpd) _MPh2 , _Me2C (Flu)(Cpd) _MBz2 , _Ph2C (Flu)(Cpd)MCl2, _{Ph2C (} Flu)(Cpd) _MMe2 , Ph2C(Flu)(Cpd) _MPh2 , _{Ph2C (} Flu) ₍ Cpd) _MBz2 , _{C2H4 ( Me4Cpd} ) _2MCl2 , _{C2H4 ( Me4Cpd} ) _{2MMe 2} , _{C2Me4 ( Ind} ) _2MCl2 , _{C2Me4 ( Ind} ) _2MMe2 , _{Me2SiCH2 ( Ind} ) _2MCl2 , _{Me2SiCH2 ( Ind} ) _{2MMe2 , Me2SiCH2} (Ind) ₂ MPh ₂ , Me ₂ SiCH 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) _2MMe2 , _C2H4 ( _{3 -} MeInd) _2MCl2 , _{C2H4 ( 3 - MeInd} ) _2MMe2 , _{C2H4 (} 4,7 _{- Me2Ind} ) _2MCl2 , C2H ₄ (4,7 _{- Me2Ind} ) _2MMe2 , _{C2H4 (} 5,6 _{- Me2Ind} ) _2MCl2 , _{C2H4 (} 5,6 _{- Me2Ind} ) _2MMe2 , _C2 H4( _{2 - MeH4Ind} ) _2MCl2 , _{Me2C ( H4Ind} ) _2MCl2 , _{Me2C ( H4Ind} ) _2MMe2 , _{Me2C ( H4Ind} ) _2MPh2 , Me _{2C ( H4Ind} ) _2MBz2 , _{Me2C ( H4Ind} ) _2MMeCl , _Ph2C ( _H4Ind ) _2MCl2 , _{Ph2C ( H4Ind} ) _2MMe2 , _Ph2C ( _H4Ind ) _2MPh2 , _{Ph2C ( H4Ind} ) _2MBz2 , _{Ph2C ( H4Ind} ) _2MMeCl , _{C2H4 ( 2 - MeH4Ind} ) _2MMe2 , _C2H4 (2,4,7-Me ₃ H ₄ Ind) ₂ MCl ₂ , C ₂ H ₄ (2,4,7-Me ₃ H ₄ Ind) ₂ MMe ₂ , C ₂ H ₄ (4,7-Me ₂ H 4Ind) ₂ MCl ₂ , C ₂ H ₄ (4,7-Me ₂ H ₄ Ind) ₂ MMe ₂ , C ₂ H ₄ (2,4,7-Me ₃ Ind) ₂ MCl ₂ , C ₂ H _{4 (} 2,4,7-Me ₃ Ind) ₂ MMe ₂ , C ₂ H ₄ (2-Me-Benz[e]Ind) ₂ MCl ₂ , C ₂ H ₄ (2-Me-Benz [e]Ind) _{2 MMe 2 , C 2 H 4 (Benz[e]Ind) 2 MCl 2 , C 2 H 4} (Benz[e]Ind) ₂ MMe ₂ , Me ₂ Si(2-MeInd) ₂ MCl ₂ , Me ₂ Si(2-MeInd) ₂ MMe ₂ , Me ₂ Si(4,7-Me ₂ Ind) ₂ MCl ₂ , Me ₂ Si(4,7-Me ₂ Ind) ₂ MMe ₂ , Me ₂ Si(5 ,6-Me ₂ Ind) ₂ MCl ₂ , Me ₂ Si(5,6-Me ₂ Ind) ₂ MMe ₂ , Me ₂ Si(2,4,7-Me ₃ Ind) ₂ MCl ₂ , Me ₂ Si(2 , 4,7-Me ₃ Ind) ₂ MMe ₂ , Me ₂ Si(2-MeH ₄ Ind) ₂ MCl ₂ , Me ₂ Si(2-MeH ₄ Ind) ₂ MMe ₂ , Me ₂ Si(4,7-Me _2H4Ind ) _2MCl2 , _{Me2Si ( 4,7 - Me2H4Ind} ) _2MMe2 , _{Me2Si ( 2,4,7 - Me3H4Ind} ) _2MCl2 , _Me2Si (2,4,7-Me ₃ H ₄ Ind) 2MMe ₂ , (t-BuNSiMe ₂ )(tet-Cpd)MCl ₂ , (t-BuNSiMe ₂ )(tet-Cpd)MMe ₂ , (t- _{BuNSiMe 2} )(tet-Cpd)MPh ₂ , (t-BuNSiMe ₂ )(tet-Cpd)MBz ₂ , (t-BuNSiMe ₂ )(tet-Cpd)MMeCl, 1,1′-(Me ₂ C) ₂ −2, 2′-(Me ₂ C) ₂ (Cpd) ₂ MCl _{2 ,} 1,1′-(Me ₂ C) ₂ -2,2′-(Me ₂ C) ₂ (Cpd) ₂ MMe ₂ .
In the above examples, Me is a methyl group, Cpd is a cyclopentadienyl group, tet-Cpd is a tetramethylcyclopentadienyl group, Ind is an indenyl group, H ₄ Ind is 4,5 ,6,7-tetrahydroindenyl, Flu is a fluorenyl group, Ph is a phenyl group, and Bz is a benzyl group. Moreover, M is as described for formula (1), preferably Zr, Ti, or Hf, more preferably Zr.

Among the transition metal compounds represented by 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) _ZrPh2 , _Me2C (Flu)(Cpd) _ZrBz2 , _Ph2C (Flu)(Cpd) _ZrCl2 , _Ph2C (Flu)(Cpd) _ZrMe2 , _Ph2C (Flu)(Cpd) ) ZrPh ₂ and Ph ₂ C(Flu)(Cpd)ZrBz ₂ are preferably used for the copolymerization of norbornene monomers and ethylene described below, and are more preferably used for the copolymerization of norbornene and ethylene.

Another preferred example of the transition metal compound represented by formula (1) is a compound represented by formula (a1) below.

In formula (a1), 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.
R ^a1 and R ^a2 are each bonded to the silicon atom via a C—Si bond, O—Si bond, Si—Si bond, or N—Si bond.
R ^a3 is bound to the nitrogen atom through a CN bond, an 0--N bond, a Si--N bond, or an NN bond.
R ^a4 is attached to metal atom M by a CM bond.
R ^a5 and R ^a6 are each independently an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom or an inorganic substituent, and p and q are each independently an integer of 0 to 4 is.
When each of R ^a5 and R ^a6 is plural, the plural R ^a5 and R ^a6 may be different groups.
When two groups out of a plurality of R ^a5 or two groups out of a plurality of R ^a6 are bonded to adjacent positions on an aromatic ring, the two groups are bonded to each other to form a ring. good too.
M is a group IV transition metal of the periodic table, preferably Ti, Zr, or Hf.

The metal atom M in the formula (a1) can take any coordination form with a ligand having a fluorene skeleton within the range of 1 to 5 haptic numbers.

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 heteroatom, when the hydrocarbon group contains a heteroatom, the type of heteroatom is not particularly limited as long as the object of the present invention is not impaired. Specific examples of heteroatoms include oxygen, nitrogen, sulfur, phosphorus, silicon, selenium, and halogen atoms.

R ^a1 and R ^a2 are each bonded to the silicon atom via a C—Si bond, O—Si bond, Si—Si bond, or N—Si bond.
Preferable examples of R ^a1 and R ^a2 bonded to a silicon atom via an O—Si bond include groups represented by —OR ^a7 and —OC(═O)—R ^a7 .
Preferable examples of R ^a1 and R ^a2 bonded to a silicon atom via a Si—Si bond include —SiR ^a7 ₃ , —Si(OR ^a7 )R ^a7 ₂ , —Si(OR ^a7 ) ₂ R ^a7 , and —Si A group represented by (OR ^a7 ) ₃ can be mentioned.
Preferred examples of R ^a1 and R ^a2 bonded to a silicon atom via an N—Si bond include groups represented by —NHR ^a7 and —NR ^a7 ₂ .
Here, all of the above R ^a7 are hydrocarbon groups.

R ^a3 is bound to the nitrogen atom through a CN bond, an 0--N bond, a Si--N bond, or a NN bond.
Preferable examples of R ^a3 bonded to a nitrogen atom via an ON bond include groups represented by —OR ^a7 and —OC(=O)—R ^a7 .
Preferable examples of R ^a3 bonded to a nitrogen atom via a Si—N bond include —SiR ^a7 ₃ , —Si(OR ^a7 )R ^a7 ₂ , —Si(OR ^a7 ) ₂ R ^a7 and —Si(OR ^a7 ) group represented by ₃ is mentioned.
Preferable examples of R ^a3 bonded to a nitrogen atom via an NN bond include groups represented by —NHR ^a7 and —NR ^a7 ₂ .
Here, all of the above R ^a7 are hydrocarbon groups.

R ^a1 and R ^a2 are preferably the same group because the compound used as the ligand is easy to prepare and obtain.

R ^a1 , R ^a2 , R ^a3 , and R ^a4 are preferably hydrocarbon groups containing no heteroatoms because of their excellent chemical stability.
Such hydrocarbon groups include linear or branched alkyl groups, linear or branched unsaturated aliphatic hydrocarbon groups which may have double and/or triple bonds, cycloalkyl groups, cycloalkylalkyl groups, aromatic hydrocarbon groups and aralkyl groups are preferred.

Specific examples of linear or branched alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, 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.

Preferable examples of linear or branched unsaturated aliphatic hydrocarbon groups which may have double bonds and/or triple bonds include specific examples of linear or branched alkyl groups. group in which one or more single bonds are replaced with double and/or triple bonds.
More preferred are vinyl group, allyl group, 1-propenyl group, 3-butenyl group, 2-butenyl group, 1-butenyl group, ethenyl group and propargyl group.

Specific examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, A cyclotetradecyl group, a cyclopentadecyl group, a cyclohexadecyl group, a cycloheptadecyl group, a cyclooctadecyl group, a cyclononadecyl group, and a cycloicosyl group can be mentioned.

Specific examples of cycloalkylalkyl groups include cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, cyclodecylmethyl, 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, 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 A butyl group, a 4-cyclopentadecylbutyl group, and a 4-cyclohexadecylbutyl group can be mentioned.

Specific examples of aromatic hydrocarbon groups include phenyl, o-tolyl, m-tolyl, p-tolyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 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, anthracen-1-yl group, anthracen-2-yl group, anthracen-9-yl group, phenanthren-1-yl group, phenanthren-2-yl group, phenanthren-3-yl group, phenanthren-4-yl group, phenanthren-9-yl group, pyren-1-yl group , pyren-2-yl group, pyren-3-yl group, and pyren-4-yl group.

Specific examples of aralkyl groups include benzyl, phenethyl, 1-phenylethyl, 3-phenylpropyl, 2-phenylpropyl, 1-phenylpropyl, 2-phenyl-1-methylethyl, 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, α-naphthylmethyl group, β-naphthylmethyl group, 2-α-naphthylethyl group, 2-β-naphthylethyl group, 1-α-naphthylethyl group, and 1-β-naphthylethyl group.

R ^a1 and R ^a2 are preferably an alkyl group having 1 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms. is more preferred, an alkyl group having 1 to 6 carbon atoms and a phenyl group are more preferred, and an alkyl group having 1 to 4 carbon atoms is particularly preferred.

R ^a3 is 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 is 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 Aralkyl groups having 7 to 20 carbon atoms are preferred.

In formula (a1), R ^a5 and R ^a6 are each independently an organic substituent or an inorganic substituent having 1 to 20 carbon atoms which may contain a hetero atom, and p and q are each independently is an integer from 0 to 4.
When each of R ^a5 and R ^a6 is plural, the plural R ^a5 and R ^a6 may be different groups.

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

Among these organic substituents, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, and aliphatic acyl groups having 2 to 6 carbon atoms. benzoyl, phenyl, benzyl and phenethyl groups are preferred.

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

The inorganic substituent is particularly limited as long as it is an inorganic group conventionally known to be able to substitute on the aromatic ring and does not inhibit the formation reaction of the transition metal compound represented by the above formula (a1). not.
Specific examples of inorganic groups include halogen atoms, nitro groups, cyano groups, and the like.

When two groups out of a plurality of R ^a5 or two groups out of a plurality of R ^a6 are bonded to adjacent positions on an aromatic ring, the two groups are bonded to each other to form a ring. good too. Such a ring is a condensed ring condensed with the aromatic ring contained in the fluorene skeleton in formula (a1). The condensed ring may be an aromatic ring or an aliphatic ring, preferably an aliphatic ring. The fused ring may have heteroatoms such as oxygen, nitrogen, and sulfur atoms in the ring.

Specific examples of the fluorene skeleton having a condensed ring formed by two R ^a5 and/or two R ^a6 include the skeleton of the following formula.

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

Preferred examples of the transition metal compound represented by formula (a1) described above include transition metal complexes having the following structures.

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

[Aluminoxane (b1)]
Aluminoxane (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 producing the catalyst composition, the aluminoxane (b1) may be used singly or in combination of two or more.

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

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

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

Examples of alkylaluminoxanes include methylaluminoxane and modified methylaluminoxane obtained by substituting a portion of the methyl groups of methylaluminoxane with other alkyl groups. As the modified methylaluminoxane, for example, 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 as an alkyl group after substitution is preferable, and particularly methyl Modified methylaluminoxane in which a portion of the group is substituted with an isobutyl group is more preferred. Specific examples of alkylaluminoxane include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, methylisobutylaluminoxane and the like. Among them, methylaluminoxane and methylisobutylaluminoxane are preferred.

Alkyl aluminoxanes can be prepared by known methods. Moreover, you may use a commercial item as an alkylaluminoxane. Examples of commercially available alkylaluminoxanes include MMAO-3A, TMAO-200 series, TMAO-340 series (all manufactured by Tosoh Finechem Co., Ltd.) and methylaluminoxane solution (manufactured by Albemarle).

[Ionic compound (b2)]
The ionic compound (b2) is a compound that produces a cationic transition metal compound by reaction with the transition metal compound (a).
Such ionic compounds include the anion of tetrakis(pentafluorophenyl)borate, amine cations with active protons such as ( _CH3 )2N _{( C6H5} )H ⁺ _{, ( C6H5} ) _3C ⁺ Ionic compounds such as trisubstituted carbonium cations, carborane cations, metal carborane cations, and ferrocenium cations having a transition metal can be used.

[solvent]
The transition metal compound (a), the aluminoxane (b1), and the ionic compound (b2) described above are usually dissolved or suspended, preferably dissolved, in a solvent before use.
The type of solvent is not particularly limited as long as it does not impair the purpose 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 solvent used is not particularly limited as long as a catalyst composition with desired performance can be produced. Typically, the concentrations of the transition metal compound (a), the aluminoxane (b1), and the ionic compound (b2) are preferably 0.00000001 to 100 mol/L, more preferably 0.00000005 to 50 mol/L, and particularly preferably 0.0000001 to 20 mol/L of solvent is used.

[Microreactor]
A microreactor has an inlet for introducing two or more liquids into the microreactor, a minute mixing field in which the two or more liquids can be mixed, and an outlet for taking out the mixed liquid obtained by mixing the two or more liquids. Any microreactor that has been used for various purposes can be used without any particular limitation, as long as it is a device comprising:

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

The shape of the microreactor having a Y-shaped channel or a T-shaped channel is not particularly limited. The microreactor may be a non-chip-shaped device in which small-diameter tubes are simply connected by a joint to provide a Y-shaped channel or a T-shaped channel. Further, the microreactor may be a chip-shaped device in which a Y-shaped channel or a T-shaped channel is formed inside a plate-shaped or block-shaped chip.

Further, it is also preferable to perform multi-stage mixing using a microreactor having a flow channel inside, for example, as shown in FIG. In the channel shown in FIG. 1, liquids to be mixed are supplied from two inlets 1, and after the liquids pass through a plurality of fine channels, mixing of the liquids occurs in the mixing field 3a. The liquid mixed in the first mixing field 3a is mixed again in the second mixing field 3b after passing through the fine flow path again. After such mixing is repeated, the mixed liquid is taken out from the outlet 2 . Although five 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 a 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 with each other in the horizontal direction 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 two flow directions form an acute angle.

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

Sequential multi-stage mixing can also be performed using a microreactor having the aforementioned Y-shaped channel or T-shaped channel inside.
As an example, two microreactors having Y-shaped channels are used as the first-stage mixing device, and the outlets of the two microreactors used as the first-stage mixing device are replaced with Y-shaped channels. Two-stage mixing can be performed by connecting to 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 channel of the microreactor is not particularly limited as long as a catalyst composition with desired performance can be produced. The width of the channel is generally 1 μm to 1000 μm, preferably 10 to 500 μm, more preferably 50 to 200 μm. The depth of the channel is generally 1 μm to 1000 μm, preferably 10 to 500 μm, more preferably 50 to 200 μm.
In addition, the number of channels provided in one microreactor is not particularly limited.
In addition, the cross-sectional shape of a flow path is not specifically limited. Moreover, the residence time of the liquid supplied to the microreactor in the microreactor is not particularly limited.

A liquid containing the raw material of the catalyst composition is sent by a pump to the inlet provided in the microreactor described above. Although the amount of the liquid containing the raw material to be fed may vary, it is preferable to feed the liquid quantitatively without causing pulsation.
Although the method of sending the liquid is not particularly limited, the liquid is usually sent using a pump. Any liquid-sending pump that is industrially used can be used as the liquid-sending pump. It is desirable for the pump for liquid transfer to be a model that causes as little pulsation as possible during liquid transfer. Preferred pumps include plunger pumps, gear pumps, rotary pumps, diaphragm pumps, and the like.

A liquid containing a transition metal compound (a) and a liquid containing one or more selected from the group consisting of an aluminoxane (b1) and an ionic compound (b2) are usually fed to the microreactor.
When the liquid containing the raw material of the catalyst composition is fed to the microreactor, the number of moles of the transition metal element in the transition metal compound (a) is M _a , and the number of moles of aluminum in the aluminoxane (b1) is M _b1 . , where M _b2 is the number of moles of the ionic compound (b2), the value of (M _b1 +M _b2 )/M _a is preferably 1 to 200,000, more preferably 100 to 100,000, and particularly preferably 1,000 to 80,000. As such, it is preferred that a liquid containing the raw material of the catalyst composition is fed.

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 microreactor has a large heat transfer area per unit volume, the heat generated when the raw materials of the catalyst composition are mixed can be removed satisfactorily.
If necessary, the microreactor may be air-cooled by blowing cold air for the purpose of facilitating the removal of heat generated when the raw materials of the catalyst composition are mixed, or the microreactor may be cooled by immersing it in a coolant such as water. may

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

<<Method for producing cyclic olefin resin composition>>
In the method for producing a cyclic olefin resin composition, the catalyst composition for cyclic olefin polymerization produced by the above method is used to homopolymerize a norbornene monomer, or a norbornene monomer and a norbornene monomer are combined. Copolymerization with other copolymerizable monomers is carried out.
The homopolymerization of the norbornene monomer and the copolymerization of the norbornene monomer and other monomers may be living polymerization or non-living polymerization. Non-living polymerization, which is chain polymerization in which a chain transfer reaction is intentionally allowed to proceed repeatedly, is generally preferred when it is desired to obtain a larger amount of cyclic olefin polymer with a smaller amount of catalyst.

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

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

A monomer compound and a specific polymerization method will be described below with respect to a method for producing a cyclic olefin resin composition.

[Norbornene monomer]
Norbornene monomers include, for example, norbornene and substituted norbornenes, with norbornene being preferred. A norbornene monomer can be used individually by 1 type or in combination of 2 or more types.

The above-mentioned substituted norbornene is not particularly limited, and examples of substituents possessed by this substituted norbornene include a halogen atom and a monovalent or divalent hydrocarbon group. Specific examples of substituted norbornenes 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。）

(Wherein, R ¹ to R ¹² may be the same or different, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group,
R ⁹ and R ¹⁰ , R ¹¹ and R ¹² may combine to form a divalent hydrocarbon group,
R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may form a ring together.
Also, n represents 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. )

Substituted norbornene represented by general formula (I) will be described. R ¹ to R ¹² in general formula (I) may be the same or different and are selected from the group consisting of hydrogen atoms, halogen atoms and hydrocarbon groups.

Specific examples of R ¹ to R ⁸ include hydrogen atoms; halogen atoms such as fluorine, chlorine and bromine; alkyl groups having 1 to 20 carbon atoms; , may be partially different, or all may be the same.

Specific examples of R ⁹ to R ¹² include hydrogen atom; halogen atom such as fluorine, chlorine and bromine; alkyl group having 1 to 20 carbon atoms; cycloalkyl group such as cyclohexyl group; substituted or unsubstituted aromatic hydrocarbon groups such as groups, ethylphenyl groups, isopropylphenyl groups, naphthyl groups, and anthryl groups; benzyl groups, phenethyl groups, and other aralkyl groups in which alkyl groups are substituted with aryl groups; These may be different, partially different, or all may be the same.

Specific examples of the case where R ⁹ and R ¹⁰ or R ¹¹ and R ¹² are combined to form a divalent hydrocarbon group include alkylidene groups such as ethylidene group, propylidene group and isopropylidene group. can be mentioned.

When R ⁹ or R ¹⁰ and R ¹¹ or R ¹² form a ring together, the ring formed may be monocyclic or polycyclic, or may be a polycyclic ring having a bridge. , a ring having a double bond, or a ring consisting of a combination of these rings. Moreover, these rings may have a substituent such as a methyl group.

Specific examples of substituted norbornenes represented by general formula (I) include 5-methyl-bicyclo[2.2.1]hept-2-ene, 5,5-dimethyl-bicyclo[2.2.1]hepta- 2-ene, 5-ethyl-bicyclo[2.2.1]hept-2-ene, 5-butyl-bicyclo[2.2.1]hept-2-ene, 5-ethylidene-bicyclo[2.2. 1]hept-2-ene, 5-hexyl-bicyclo[2.2.1]hept-2-ene, 5-octyl-bicyclo[2.2.1]hept-2-ene, 5-octadecyl-bicyclo[ 2.2.1]hept-2-ene, 5-methylidene-bicyclo[2.2.1]hept-2-ene, 5-vinyl-bicyclo[2.2.1]hept-2-ene, 5- bicyclic cyclic olefins such as propenyl-bicyclo[2.2.1]hept-2-ene;
tricyclo[4.3.0.1 ^2,5 ]deca-3,7-diene (common name: dicyclopentadiene), tricyclo[4.3.0.1 ^2,5 ]dec-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 products thereof (or cyclopentadiene and cyclohexene) which are tricyclo[4.4.0.1 ^2,5 ]undec-3-ene; 5-cyclopentyl-bicyclo[2.2.1]hept-2-ene, 5-cyclohexyl-bicyclo 3 such as [2.2.1]hept-2-ene, 5-cyclohexenylbicyclo[2.2.1]hept-2-ene, 5-phenyl-bicyclo[2.2.1]hept-2-ene cyclic olefins of the ring;
Tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene (also referred to simply as tetracyclododecene), 8-methyltetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, 8-ethyltetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, 8-methylidenetetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, 8-ethylidenetetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, 8-vinyltetracyclo[4,4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, 8-propenyl-tetracyclo[4.4.0.1 ^2,5 . 4-ring cyclic olefins such as 1 ^7,10 ]dodeca-3-ene;
8-Cyclopentyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, 8-cyclohexyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, 8-cyclohexenyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]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} . 0 ^2,7 ]tetradeca-4,9,11,13-tetraene (also called 1,4-methano-1,4,4a,9a-tetrahydrofluorene), tetracyclo[8.4.1 ^4,7 . 0 ^{1, 10} . 0 ^3,8 ]pentadeca-5,10,12,14-tetraene (also called 1,4-methano-1,4,4a,5,10,10a-hexahydroanthracene); pentacyclo[6.6.1. 1 ^{3, 6} . 0 ^{2, 7} . 0 ^9,14 ]-4-hexadecene, pentacyclo[6.5.1.1 ^3,6 . 0 ^{2, 7} . 0 ^9,13 ]-4-pentadecene, pentacyclo[7.4.0.0 ^2,7 . 1 ^{3, 6} . 1 ^10,13 ]-4-pentadecene; heptacyclo[8.7.0.1 ^2,9 . 1 ^{4, 7} . 1 ^{11, 17} . 0 ^{3, 8} . 0 ^12,16 ]-5-eicosene, heptacyclo[8.7.0.1 ^2,9 . 0 ^{3, 8} . 1 ^{4, 7} . 0 ^{12, 17} . 1 ^13,16 ]-14-eicosene; and polycyclic cyclic olefins such as tetramer of cyclopentadiene.

Among these are alkyl-substituted norbornenes (e.g., bicyclo[2.2.1]hept-2-ene substituted with one or more alkyl groups), alkylidene-substituted norbornenes (e.g., bicyclo[2.2.1]hept-2-ene substituted with one or more alkylidene groups). [2.2.1]hept-2-ene) is preferred, and 5-ethylidene-bicyclo[2.2.1]hept-2-ene (common name: 5-ethylidene-2-norbornene, or simply ethylidenenorbornene) ) is particularly preferred.

[Other monomers]
The aforementioned norbornene monomer may be polymerized alone or may be copolymerized with other monomers copolymerizable with the norbornene monomer.
Such other monomers are not particularly limited as long as they are monomeric compounds copolymerizable with norbornene monomers, and are typically α-olefins. The α-olefin may be substituted with at least one substituent such as a halogen atom.

As the α-olefin, C2 to C12 α-olefins are preferred. The C2 to C12 α-olefins are not particularly limited, but examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl -1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3 -ethyl-1-hexene, 1-octene, 1-decene, and 1-dodecene. Among them, 1-hexene, 1-octene and 1-decene are preferred.

As a combination of monomers for producing a cyclic olefin resin composition, a combination of norbornene and ethylene is used because of the excellent balance of monomer availability, mechanical properties, thermal properties, manufacturability, etc. and norbornene with 1-octene, 1-hexene, or mixtures 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 preferred.
When using norbornene in combination with 1-octene, 1-hexene, or a mixture thereof, it is easy to obtain a cyclic olefin having good mechanical properties, so the glass transition temperature of the cyclic olefin resin composition can be increased. and the amount of norbornene in the monomer is preferably 70 mol % or more.

[Polymerization conditions]
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, etc. are appropriately adjusted. Further, the amount of each monomer component to be used in the case of copolymerizing the norbornene monomer and other monomers 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, more preferably 0.01 mol or more and 20 mol or less.
The amount of catalyst composition used is derived from the amount of 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, preferably 0.00000001 mol or more and 0.005 mol or less, relative to 1 mol of norbornene monomer as the mass of the transition metal compound used for its preparation. 0005 mol or less is more preferable.

The polymerization temperature is not particularly limited as long as the polymerization reaction proceeds at the desired speed. 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 the desired yield is reached or the molecular weight of the polymer is increased to the desired extent.
The polymerization time varies depending on the temperature, composition of the catalyst composition, and monomer composition, but is typically 0.01 to 120 hours, preferably 0.1 to 80 hours, and 0.2 to 10 hours. time is more preferred.

In order to easily produce a cyclic olefin resin composition with a good yield, aluminoxane is added to a polymerization system containing a norbornene monomer or a norbornene monomer and other monomers before adding the catalyst composition. , and alkylaluminum compounds are preferably present.

The aluminoxane is as described in the method for producing the catalyst composition.
As the alkylaluminum compound, those conventionally used for polymerization of olefins and the like can be used without particular limitation. Examples of alkylaluminum compounds include compounds represented by the following general formula (II).
(R ¹⁰ ) _z AlX _3-z (II)
(In formula (II), R ¹⁰ is an alkyl group having 1 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 alkyl groups having 1 to 15 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and n-octyl group.

Specific examples of alkylaluminum compounds include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butylaluminum, and tri-n-octylaluminum; dimethylaluminum chloride; dialkylaluminum halides such as diisobutylaluminum chloride; dialkylaluminum hydrides such as diisobutylaluminum hydride; and dialkylaluminum alkoxides such as dimethylaluminum methoxide.

Such alkylaluminum compounds act as chain transfer agents to facilitate chain polymerizations catalyzed by the aforementioned catalyst compositions.

When the aluminoxane is added to the polymerization system before adding the catalyst composition, the amount used is preferably 10 to 1,000,000 mol, more preferably 100 to 100,000 mol, as the number of moles of aluminum in the aluminoxane per 1 mol of the transition metal compound.
When the alkylaluminum compound is added to the polymerization system before adding the catalyst composition, the amount used is preferably 5 to 500,000 moles, more preferably 50 to 50,000 moles of aluminum per mole of the transition metal compound.

At least a portion, preferably all, of the catalyst composition is preferably added continuously to the polymerization system containing norbornene monomer, or norbornene monomer and other monomers.
By continuously adding the catalyst composition, continuous production of the cyclic olefin resin composition becomes possible, and the production cost of the cyclic olefin resin composition can be reduced.

According to the method described above, the catalyst composition prepared by the method described above is used, so that the homopolymerization of the norbornene monomer or the copolymerization of the norbornene monomer and other monomers proceeds satisfactorily. , the cyclic olefin resin composition can be obtained with a high yield even if the amount of the catalyst composition used is small.

EXAMPLES 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 a transition metal compound with a concentration of 3.17 μmol/L was prepared. A compound having the following structure was used as the transition metal compound.

As the aluminoxane solution, a TMAO-211 toluene solution (a solution of methylaluminoxane, manufactured by Tosoh Finechem Co., Ltd.) having a concentration of 9.0% by mass (as the content of Al atoms), and 26 mol% trimethyl containing aluminum) was used.

A microreactor (product name: micro volume connector 1/16″ Y SUS 0.15 mm, VICI company), the molar ratio of Al/M is the value of "Al/M ratio (catalyst activation)" listed in Table 1, and the flow rates of the transition metal compound solution and the aluminoxane solution are 1 mL/ Minutes were delivered using a syringe pump (KD SCIENTIFIC, KDS100). The residence time in the microreactor was 3.18 milliseconds, and the discharged catalyst composition passed through a Teflon (registered trademark) tube having an inner diameter of 1 mm and a length of 50 cm in 11.8 seconds, and was then dropped continuously into the monomer solution. rice field.
Here, M means the central metal of the transition metal compound, and is Ti or Zr.
In addition, the microreactor has a Y-shaped channel in which three channels are connected. The included angle formed by two of the three channels that connect the inlet and the mixing field is 90°.
FIG. 4 schematically shows the shape of a microreactor having a Y-shaped channel. The microreactor shown in FIG. 4 is equipped with channels connected in a Y shape in the mixing field 3 inside a disk-shaped case 4 . A dotted line portion in FIG.

The solution containing the activated catalyst composition discharged from the outlet of the microreactor obtained under the above conditions was continuously supplied to the polymerization system over 1 minute at the start of the polymerization reaction. Thereafter, norbornene and 1-octene were copolymerized at the polymerization temperature shown in Table 1 for 5 hours.
In addition, in the polymerization system, the molar ratio of Al/M between the amount of transition metal compound and the amount of Al contained in methylaluminoxane is adjusted to the "Al/M ratio (polymerization tank)" described in Table 1. , the methylaminoxane was added prior to adding the catalyst composition to the polymerization system.
The types and concentrations of monomers contained in the polymerization system are shown in Table 2. The polymerization system contains toluene as a solvent.

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. Subsequently, 10 mol of hydrochloric acid was added to the resulting polymerization reaction solution relative to the transition metal compound and methylaluminoxane used in the polymerization reaction, and the mixture was stirred at room temperature for 1 hour. Then, ion-exchanged water of the same volume as the polymerization solution was added, and the mixture was further stirred at room temperature for 1 hour. The solution thus obtained was transferred to a separatory funnel and the organic and aqueous layers were separated. The obtained organic layer was washed with the same amount of deionized water three times. Next, the obtained organic layer was poured into a large amount of acetone to completely precipitate the polymer, filtered and washed with a large amount of acetone, dried under reduced pressure at 100°C for 1 day or more, and copolymerized. got a union. The mass of the obtained copolymer was measured, and the ratio of the obtained copolymer to the transition metal compound used was calculated ("g (copolymer)/g (transition metal compound)" in Table 3). .
Further, the number average molecular weight (Mn) of the obtained copolymer was determined, and the molecular weight distribution (weight average molecular weight Mw/number average molecular weight Mn) was determined from Mn and weight average molecular weight (Mw). A glass transition temperature (Tg) was measured by the DSC method. By NMR measurement, the proportion of norbornene-derived units contained in the copolymer was measured. Table 3 shows the measurement results of the ratio of units derived from Mn, Mw/Mn, Tg and norbornene.

(Measurement conditions for copolymer molecular weight (Mn and Mw))
Apparatus: Malvern Viscotek TDA302 detector + Pump autosampler apparatus Detector: RI
Solvent: toluene Column: TSKgel GMHHR-M manufactured by Tosoh Corporation (300 mm × 7.8 mm φ)
Flow rate: 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 Instruments)
Measurement atmosphere: Nitrogen Measurement mode: Modulated
Temperature rising conditions: 2°C/min

(Measurement conditions for the ratio of units derived from norbornene)
NMR equipment: Bruker AVANCE600
Measurement solvent: 1,1,2,2-tetrachloroethane _- d2
Measurement nuclide: ¹³ C
Measurement temperature: 381K
Sample concentration: 70 mg/mL
Sample tube diameter: 10mm
Measurement method: Power gate method _Decoupling : Complete decoupling Accumulation times: 18000 times , and 2-tetrachloroethane at 74.47 ppm.
Proportion of units derived from norbornene: A copolymer of norbornene and ethylene was prepared with reference to Non-Patent Document 1. Copolymers of norbornene and 1-octene, 1-hexene, or 1-decene were prepared with reference to Non-Patent Document 3.

[Example 2]
In addition to changing the microreactor with a Y-shaped channel to a microreactor with a T-shaped channel (product name: microvolume connector 1/16″ Tee SUS 0.15mm, manufactured by VICI), A copolymer was obtained in the same manner as in Example 1.
In addition, the transition metal compound solution and the aluminoxane solution were supplied so that their flows were perpendicular to each other in the microreactor having a T-shaped channel.
FIG. 3 schematically shows the shape of a microreactor having a T-shaped channel. The microreactor shown in FIG. 3 includes channels connected in a T-shape in the mixing field 3 inside a disk-shaped case 4 . In FIG. 3 , the dotted line portion is the outer edge of the flow path held inside the case 4 .

[Example 3]
A microreactor equipped with a Y-shaped channel is the same shape as the microreactor shown in FIG. 2 except for the number of mixing stages. A copolymer was obtained in the same manner as in Example 1, except that the number of mixing fields): 13, channel width: 200 μm, channel depth: 200 μm).

[Example 4]
A microreactor with a Y-shaped channel is replaced with a microreactor with a substantially T-shaped multi-stage mixing channel (the number of mixing stages ( A copolymer was obtained in the same manner as in Example 1, except that the number of mixing fields): 13, channel width: 200 μm, channel depth: 200 μm).

[Examples 5 to 7]
A copolymer was obtained in the same manner as in Example 1, except that the composition of the monomers was changed to that shown in Table 2.

[Examples 8 and 9]
A copolymer was obtained in the same manner as in Example 5, except that the reaction temperature was changed from 40° C. to the temperature shown in Table 1.

[Examples 10 and 11]
A toluene solution of a transition metal compound with a concentration of 0.215 μmol/L was prepared. As the transition metal compound, a compound (Ph ₂ C(Cpd)(Flu)ZrCl ₂ ) having the following structure was used.

The amount of transition metal compound supplied and the amount of methylaluminoxane supplied were changed according to the value of the "Al/M ratio (catalyst activation)" shown in Table 1, and the amount of methylaluminoxane added to the polymerization system was changed. , change according to the value of "Al / M ratio (polymerization tank)" listed in Table 1, change the composition of the monomers to the composition listed in Table 2, and change the polymerization temperature to 70 ° C. A copolymer was obtained in the same manner as in Example 1 except for this.

[Comparative Example 1]
A copolymer was produced in the same manner as in Example 1, except that the transition metal compound and aluminoxane used in the preparation of the catalyst composition in Example 1 were added in advance to the polymerization system without using a microreactor. Obtained.

[Comparative Example 2]
A copolymer was obtained in the same manner as in Example 1, except that an aluminoxane was added to the transition metal compound in a Schlenk tube to prepare a catalyst composition, and the resulting solution of the catalyst composition was added to the polymerization system. .

[Comparative Example 3]
A copolymer was produced in the same manner as in Example 10, except that the transition metal compound and aluminoxane used in the preparation of the catalyst composition in Example 10 were added in advance to the polymerization system without using a microreactor. Obtained.

[Comparative Example 4]
A copolymer was produced in the same manner as in Example 11, except that the transition metal compound and aluminoxane used in the preparation of the catalyst composition in Example 11 were added in advance to the polymerization system without using a microreactor. Obtained.

Table 1 below shows the activation method of the transition metal compound, the flow path shape of the microreactor, the Al/M ratio (polymerization tank), the Al/M ratio (catalyst activation), the polymerization temperature, and the polymerization time. and

Table 2 below shows the composition of the monomers used in the polymerization reaction.

Hereinafter, in Table 3, copolymer yield, g (copolymer) / g (transition metal compound), copolymer properties (number average molecular weight, molecular weight distribution, Tg, ratio of units derived from norbornene) write down

According to a comparison of Examples 1-7 with Comparative Examples 1 and 2, and a comparison of Examples 10 and 11 with Comparative Examples 3 and 4, by using a catalyst composition prepared using a microreactor , it can be seen that the ratio of the cyclic olefin resin composition obtained to the amount of the catalyst composition used is high. Therefore, it has become clear that the catalyst composition used for the production of the cyclic olefin resin composition is preferably produced in a microreactor.

1: Inlet 2: Outlet 3: Mixing field 3a to 3e: Mixing field 4: Case

Claims (4)

A method for producing a cyclic olefin resin composition, comprising homopolymerizing a norbornene monomer or copolymerizing a norbornene monomer with another monomer copolymerizable with the norbornene monomer ,
producing the catalyst composition for cyclic olefin polymerization;
performing the homopolymerization or the copolymerization in the presence of the catalyst composition;
The method for producing the catalyst composition includes mixing a transition metal compound (a), an aluminoxane (b1), and one or more selected from the group consisting of an ionic compound (b2) in a microreactor. including
The transition metal compound (a) is a transition metal complex containing a ligand containing a cyclopentadiene ring and a Group IV transition metal of the periodic table,
The ionic compound (b2) is a compound that produces a cationic transition metal compound by reaction with the transition metal compound (a),
A method, wherein the resulting cyclic olefin resin composition has a molecular weight distribution greater than 1.5 . Before adding the catalyst composition to the polymerization system containing the norbornene monomer or the norbornene monomer and the other monomer, one or more selected from aluminoxanes and alkylaluminum compounds are present. The method for producing a cyclic olefin resin composition according to claim 1 . 3. The method according to claim 1 or 2 , wherein at least part of the catalyst composition is continuously added to a polymerization system containing the norbornene monomer, or the norbornene monomer and the other monomer. A method for producing a cyclic olefin resin composition. Any one of claims 1 to 3 , 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. A method for producing the cyclic olefin resin composition according to the item.

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