JP5013402B2 - Polymerization catalyst composition containing metallocene complex and polymer produced using the same - Google Patents

Description

The present invention relates to a polymerization catalyst composition containing a metallocene complex, and particularly to a polymerization catalyst composition in which the central metal of the metallocene complex is a Group 3 metal or a lanthanoid metal.
The present invention also relates to a method for producing a polymer compound characterized by using the polymerization catalyst.
Furthermore, it is related with the copolymer of the high molecular compound which can be manufactured using this polymerization catalyst composition, especially an alpha olefin compound or a diene compound, and a cyclic olefin.

  Copolymers of norbornenes, which are one of cyclic olefins, and ethylene, which is an α-olefin, are known. Since the copolymers are excellent in transparency and heat resistance, they are expected to be developed into optical materials. (See Non-Patent Document 1). However, cyclic olefin compounds generally have low polymerization activity due to their bulky molecules, and effective polymerization catalyst systems are limited. As a catalyst for producing such a copolymer, the present inventors previously reported a polymerization catalyst containing the following complex, that is, a half metallocene complex (having a group 3 metal or a lanthanoid metal atom as a central metal). (See Patent Document 1).

(Where
M represents either a Group 3 metal atom or a lanthanoid metal atom;
Cp ^* represents a ligand comprising a substituted or unsubstituted cyclopentadienyl derivative;
Q ¹ and Q ² represent monoanionic ligands;
L represents a neutral Lewis base;
w represents an integer of 0 to 3. )

  A copolymer of an α-olefin and a cyclic olefin such as norbornene is produced by the polymerization catalyst. However, development of a method for producing a more active copolymer has been desired.

  As a polymerization catalyst for producing a copolymer of an α-olefin and a cyclic olefin, a complex composed of [methylene (bis (2,5-) dimethylcyclopentadienyl)] zirconium dichloride and methylaminoxan (MAO) The catalyst which consists of these combinations is reported, The copolymer of (alpha) -olefin and norbornene is reported (refer nonpatent literature 2).

  However, the above method has a problem that the reaction temperature needs to be set high (for example, 70 ° C.). It has also been desired to produce copolymers with higher α-olefin content.

On the other hand, dicyclopentadiene, which is one of norbornenes, has a C═C double bond derived from a norbornene structure and a C═C double bond derived from cyclopentene. Similar to norbornene, a copolymer with ethylene is an interesting compound, but recently it has been reported that it can be synthesized using a specific Zr complex as a polymerization catalyst (see Non-Patent Document 3). However, the copolymer of dicyclopentadiene and ethylene synthesized by the reported method has a limited molecular weight and dicyclopentadiene content.

  A copolymer of α-olefin and dicyclopentadiene is produced by the polymerization catalyst described in Patent Document 1, and a copolymer having an improved molecular weight and a content of dicyclopentadiene is obtained. However, it has been desired to develop a method for producing a more active α-olefin / dicyclopentadiene copolymer.

  Further, a copolymer of norbornene and a conjugated diene such as isoprene is known, and the copolymer has a high glass transition point, high transparency, low birefringence, low moisture absorption, and high efficiency light emitting diode. Because of this property, development to optical materials is expected. As a polymerization catalyst for producing such a copolymer, a complex comprising a nickel compound having an N- or O-donating ligand such as bis [1- (2,6-diisopropylphenylimino) ethyl] pyridine-nickel bromide, and A catalyst comprising a combination with modified methylaluminoxane (MMAO) has been reported (see Non-Patent Document 4).

  However, it has been desired to produce a diene / dicyclopentadiene copolymer having higher activity. It has also been desired to develop a method for producing a copolymer having a higher diene content.

  Dicyclopentadiene is industrially advantageous because the cost of the raw material is lower than that of norbornene. However, a method for producing a copolymer of dicyclopentadiene and a diene compound has not been known so far.

International Publication No. WO 06/004068 Pamphlet K. Nomura et al., Macromolecules, 36, 3797 (2003) Hye Young Jung et al., Polyhedron 24 (2005) 1269-1273 Adriane G. Simanke et al., Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 40, 471-485 (2002) Hirotaka Suzuki et al., Reactive & Functional Polymers 59 (2004) 253-266

  An object of the present invention is to provide a novel catalyst composition containing a metallocene complex. Furthermore, this invention makes it a subject to provide the method of manufacturing various high molecular compounds using the said catalyst composition. Preferably, an object of the present invention is to provide a method for producing a novel polymer compound using the catalyst composition.

As a result of intensive studies to solve the above problems, the present inventors have developed a complex that does not have a neutral Lewis base in the metallocene complex described in Patent Document 1. Since such a catalyst does not have a neutral Lewis base, it can be coordinated to the active center of the olefin monomer, so that the α-olefin can be efficiently compared to the metallocene complex described in Patent Document 1. It has been found that a copolymer of a compound and a cyclic olefin compound can be produced. Furthermore, it has been found that a copolymer of a diene compound and a cyclic olefin compound can be produced. The present invention has been completed based on these findings.

That is, the present invention is as follows.
1stly, this invention is invention of the manufacturing method of the polymer shown below.
(1) (a) a method for producing a copolymer of an α-olefin compound and a cyclic olefin compound, or (b) a diene compound and a cyclic olefin compound,
1) a metallocene complex represented by the general formula (I), and
2) an ionic compound comprising a non-coordinating anion and a cation,
A method for carrying out polymerization in the presence of a polymerization catalyst composition comprising:

(Where
M represents either a Group 3 metal atom or a lanthanoid metal atom;
Cp ^* represents a ligand comprising a substituted or unsubstituted cyclopentadienyl derivative;
Q ¹ and Q ² represent monoanionic ligands. )
(2) M in the general formula (I) is scandium (Sc), gadolinium (Gd), yttrium (Y), holmium (Ho), lutetium (Lu), erbium (Er), dysprosium (Dy), terbium (Tb) ) Or thulium (Tm). The production method according to (1).
(3) The production method according to (1) or (2), wherein Q ¹ and Q ² in formula (I) are each independently a substituted or unsubstituted hydrocarbyl group.
(4) Q ¹ and Q ² in the general formula (I) are each independently a general _{^{formula: η 3 -C 3 R 1 5}} ( In the formula, R ^1, each independently represent hydrogen or an alkyl group.) In The production method according to any one of (1) to (3), which is a group shown.
(5) Q ¹ and Q ² in the general formula (I) are each independently a general formula: CH ₂ C ₆ R ² ₄ ER ³ _n -o (wherein R ² independently represents a hydrogen atom or an alkyl group) E represents N, P, As, O, or S; R ³ each independently represents an alkyl group or an aryl group; n is 1 or 2). The production method according to any one of (1) to (3).
(6) general formula: E in _{^{CH 2 C 6 R 2 4 ER}} 3 n -o , characterized in that it is N, the production method according to (5).

Secondly, the present invention is an invention of the following complex and a polymerization catalyst composition containing the complex.
(7) A metallocene complex represented by the general formula (A).

(Where
M represents either a Group 3 metal atom or a lanthanoid metal atom;
Cp ^* represents a ligand comprising a substituted or unsubstituted cyclopentadienyl derivative;
R ¹ independently represents hydrogen or an alkyl group. )
(8) 1) The metallocene complex according to (7), and
2) an ionic compound comprising a non-coordinating anion and a cation,
A polymerization catalyst composition comprising:

3rdly, this invention is invention of the copolymer shown below.
(9) A copolymer of an α-olefin compound and a cyclic olefin compound obtained by the production method according to any one of (1) to (6).
(10) The copolymer according to (9), wherein the cyclic olefin compound is norbornene.
(11) The copolymer according to (10), wherein the norbornene is norbornene or dicyclopentadiene.
(12) A copolymer of a diene compound and a cyclic olefin compound obtained by the production method according to any one of (1) to (6).
(13) The copolymer according to (12), wherein the cyclic olefin compound is norbornene.
(14) The copolymer according to (13), wherein the norbornene is norbornene.
(15) A copolymer of a diene compound and dicyclopentadiene.
(16) The copolymer according to (15), wherein the diene compound is isoprene.

  By using the catalyst composition of the present invention, a new polymerization reaction is provided, and a new method for producing a polymer compound is provided.

  On the other hand, various cyclic olefin copolymers which are one of polymer compounds produced using the catalyst composition of the present invention are expected to be applied to a wide range of uses as optical materials, for example.

<Catalyst composition of the present invention>
The catalyst composition of the present invention includes a metallocene complex and an ionic compound. Moreover, the other arbitrary components may be included.

1. The metallocene complex contained in the catalyst composition of the present invention The metallocene complex contained in the catalyst composition of the present invention (hereinafter also referred to as “metallocene complex used in the present invention”) is a complex represented by the following general formula (I) It is. The complex is preferably a half metallocene complex.

In general formula (I), M is a central metal in a metallocene complex. The central metal M is a Group 3 metal or a lanthanoid metal, and is not particularly limited. Since the metallocene complex used in the present invention can be used as one component of the polymerization catalyst composition, the central metal M is appropriately selected depending on the type of monomer to be polymerized.
For example, when polymerizing isoprene and norbornene, any Group 3 metal or lanthanoid metal may be used. For example, scandium (Sc) can be selected.
In the case of polymerizing isoprene and dicyclopentadiene, any Group 3 metal or lanthanoid metal may be used. For example, scandium (Sc) can be selected.

In the general formula (I), Cp ^* is a ligand containing a cyclopentadienyl derivative and is π-bonded to the central metal M. The ligand is preferably a non-bridged ligand. Here, the non-bridged ligand means a ligand having a coordination atom or a coordination group other than the cyclopentadienyl derivative, wherein the cyclopentadienyl derivative is π-bonded to the central metal.
Examples of the cyclopentadienyl derivative contained in Cp ^* include a cyclopentadienyl ring, a condensed ring containing cyclopentadienyl (including but not limited to an indenyl ring and a fluorenyl ring), and the like. The most preferred cyclopentadienyl derivative is a cyclopentadienyl ring.

The cyclopentadienyl ring is represented by a composition formula C ₅ H _5-X R _X. Here, x represents an integer of 0 to 5. Each R is independently a hydrocarbyl group, a substituted hydrocarbyl group, or a metalloid group substituted with a hydrocarbyl group.

  The hydrocarbyl group is preferably a C 1-20 hydrocarbyl group, more preferably a C 1-20 (preferably C 1-10, more preferably C 1-6) alkyl group, phenyl group, benzyl group, and the like. And most preferably a methyl group.

  The hydrocarbyl group in the substituted hydrocarbyl group is the same as the hydrocarbyl group described above. The substituted hydrocarbyl group is a hydrocarbyl group in which at least one hydrogen atom of the hydrocarbyl group is substituted with a halogen atom, an amide group, a phosphide group, an alkoxy group, an aryloxy group, or the like.

  Examples of the metalloid in the metalloid group substituted with the hydrocarbyl group include germyl (Ge), stannyl (Sn), and silyl (Si). The hydrocarbyl group substituted with a metalloid group is the same as the hydrocarbyl group described above, and the number of substitutions is determined by the type of metalloid (for example, in the case of a silyl group, the number of substitutions of the hydrocarbyl group is 3).

  Preferably, at least one R of the cyclopentadienyl ring is a metalloid group (preferably a silyl group) substituted with a hydrocarbyl group, more preferably a trimethylsilyl group.

  Specific examples of preferred cyclopentadienyl rings include, but are not limited to, those represented by the following structural formulas.

The cyclopentadienyl derivative contained in the ligand Cp ^* has an indenyl ring (composition formula: C ₉ H
_7-x R _x ) or a tetrahydroindenyl ring (composition formula: C ₉ H _11-x R _x ). Here, R is the same as R in the above-described cyclopentadienyl ring, and X is an integer of 0 to 7 or 0 to 11.

The cyclopentadienyl derivative contained in the ligand Cp ^* is a fluorenyl ring (composition formula: C ₁₃ H _9-x R _x ) or octahydrofluorenyl ring (composition formula: C ₁₃ H _17-x R _x ). Etc. Here, R is the same as R in the above-described cyclopentadienyl ring, and X is an integer of 0-9 or 0-17.

In the complex represented by the general formula (I) used in the present invention, Q ¹ and Q ² are the same or different monoanionic ligands. The monoanionic ligand is preferably a substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, more preferably,
During _{^{1) η 3 -C 3 R 1}} 5 ( wherein, R ¹ each independently represent a hydrogen or an alkyl group.) A group represented by or,
2) CH ₂ C ₆ R ² ₄ ER ³ _n -o (wherein R ² independently represents hydrogen or an alkyl group; E represents N, P, As, O, or S; R ³ represents Each independently represents an alkyl group or an aryl group; n is 1 or 2.).

Alkyl group represented by R ¹ in the η _³ -C ³ R ¹ ₅ is preferably not an alkyl group having Cl -C 12 (preferably C1 to C8, more preferably C1 -C4), and most preferably a methyl group is there.
The alkyl group represented by R ² in the CH ₂ C ₆ R ² ₄ ER ³ _n -o is preferably a C1 to C10 (preferably C1 to 8, more preferably C1 to C4) alkyl group, most preferably. Is a methyl group. The alkyl group represented by R ³ is the same as the alkyl group represented by R ² . The aryl group represented by R ³ is a phenyl group, a naphthyl group, an anthracenyl group, or the like.
E in the CH ₂ C ₆ R ² ₄ ER ³ _n -o represents N, P, As, O, or S, preferably N.

Since the structure of the metallocene complex used in the present invention has been clarified in the present specification, it can be synthesized according to a known method, for example, a method described in International Publication No. WO 06/004068.
Moreover, since the specific example of the manufacturing method of these complexes is described also in the below-mentioned reference example, these can also be referred.

2. Ionic compound contained in catalyst composition of the present invention As described above, the catalyst composition of the present invention contains an ionic compound. Here, the ionic compound includes an ionic compound composed of a non-coordinating anion and a cation. The ionic compound is combined with the metallocene complex described above to cause the metallocene complex to exhibit activity as a polymerization catalyst. As the mechanism, it can be considered that the ionic compound reacts with the metallocene complex to generate a cationic complex (active species).

  As the non-coordinating anion which is a constituent component of the ionic compound, for example, a tetravalent boron anion is preferable, and tetra (phenyl) borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (tri Fluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) Examples thereof include borate, [tris (pentafluorophenyl), phenyl] borate, and tridecahydride-7,8-dicarbaoundecaborate.

  Of these non-coordinating anions, tetrakis (pentafluorophenyl) borate is preferred.

Examples of the cation that is a constituent component of the ionic compound include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal.
Specific examples of the carbonium cation include a tri-substituted carbonium cation such as a triphenylcarbonium cation and a tri-substituted phenylcarbonium cation. Specific examples of the tri-substituted phenyl carbonium cation include a tri (methylphenyl) carbonium cation and a tri (dimethylphenyl) carbonium cation.
Specific examples of ammonium cations include trialkylammonium cations, triethylammonium cations, tripropylammonium cations, tributylammonium cations, tri (n-butyl) ammonium cations, and the like, N, N-dimethylanilinium cations, N Dialkyl ammonium cations such as N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation, N, N-dialkylanilinium cation, di (isopropyl) ammonium cation, dicyclohexylammonium cation, etc. included.
Specific examples of the phosphonium cation include triarylphosphonium cations such as a triphenylphosphonium cation, a tri (methylphenyl) phosphonium cation, and a tri (dimethylphenyl) phosphonium cation.

  Among these cations, an anilinium cation or a carbonium cation is preferable, and an N, N-dimethylanilinium cation or a triphenylcarbonium cation is more preferable.

That is, the ionic compound contained in the catalyst composition of the present invention may be a combination of those selected from the above-mentioned non-coordinating anions and cations.
Preferably, triphenylcarbonium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocete Examples thereof include nium tetrakis (pentafluorophenyl) borate. One ionic compound may be used, or two or more ionic compounds may be used in combination.

  Among these ionic compounds, particularly preferred are N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and triphenylcarbonium tetrakis (pentafluorophenyl) borate.

In addition, B (C ₆ F ₅ ) ₃ , Al (C ₆ F ₅ ) _3, etc., which are Lewis acids that can react with transition metal compounds to form cationic transition metal compounds, are used as ionic compounds. These may be used in combination with the ionic compound.
Furthermore, an alkylaluminum compound (aluminoxane, preferably MAO or MMAO), or a combination of an alkylaluminum compound and a borate compound can also be used as an ionic compound, or may be used in combination with other ionic compounds. .

3. Other optional components contained in the catalyst composition of the present invention The catalyst composition of the present invention can contain optional components in addition to the metallocene complex and the ionic compound. Examples of the optional component include alkyl aluminum compounds, silane compounds, hydrogen and the like.
The alkylaluminum compound usually includes an organoaluminum compound called aluminoxane (alumoxane) used in a metallocene polymerization catalyst, in addition to a trialkylaluminum or a dialkylaluminum hydride. Examples thereof include methylaluminoxane (MAO) and triisobutylaluminum.
Examples of the silane compound include phenylsilane.

4). As described above, the catalyst composition of the present invention includes the metallocene complex and an ionic compound. In the catalyst composition of the present invention, the molar ratio of the ionic compound to the metallocene complex varies depending on the type of the complex and the ionic compound.
The molar ratio is, for example, that the ionic compound is composed of a carbonium cation or an anilinium cation and a boron anion (for example, [PhMe ₂ NH] [B (C ₆ F ₅ ) ₄ ], [Ph ₃ C] [B ( C ₆ F ₅ ) ₄ ]) is preferably 0.5 to 1, and in the case of MAO or the like, it is preferably about 10 to 4000.
Since the ionic compound is considered to be a catalytically active species by ionizing, that is, cationizing, the metallocene complex, it is considered that the metallocene complex cannot be sufficiently activated when the ratio is not more than the above-described ratio.
On the other hand, if an ionic compound composed of a carbonium cation and a boron anion is present in excess, there is a possibility that they may react with a monomer to be polymerized.

The catalyst composition of the present invention can be used as a polymerization catalyst composition (particularly an addition polymerization catalyst composition).
For example, 1) providing a composition containing each component (such as a metallocene complex and an ionic compound) in the polymerization reaction system, or 2) providing each component separately in the polymerization reaction system, By constituting the composition, it can be used as a polymerization catalyst composition.
In the above 1), “providing as a composition” includes providing a metallocene complex (active species) activated by reaction with an ionic compound.

As described above, the catalyst composition of the present invention can be used as a polymerization catalyst composition in polymerization reactions of various monomers. Examples of the polymerization reaction in which the catalyst composition of the present invention can act as a catalyst include polymerization reactions of arbitrary monomer compounds that are known to have addition polymerizability. For example, olefin monomers, epoxy monomers, and isocyanate monomers. Examples thereof include polymerization reactions of monomers, lactone monomers, lactide monomers, cyclic carbonate monomers, alkyne monomers, and the like. Preferably, a polymerization reaction of an olefin monomer, particularly preferably a polymerization reaction of α-olefin, styrene, ethylene, diene, cyclic olefin (including norbornenes such as 2-norbornene and dicyclopentadiene and cyclohexadiene), and the like. .
Examples of dienes that are olefinic monomers include 1,3-butadiene, 2-methyl-1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene, 1,4. -Hexadiene, 1,5-hexadiene, 2,4-dimethyl-1,3-pentadiene, 2-methyl-1,3-hexadiene, 2,4-hexadiene, cyclic dienes such as cyclohexadiene, and the like are included.

  The polymerization catalyst composition of the present invention can be used as a polymerization catalyst composition in homopolymerization and copolymerization reactions. The monomer to be copolymerized has only to have addition polymerizability, preferably two or more olefinic monomers, and particularly preferably two or more monomers selected from α-olefins, dienes, and cyclic olefins.

<Polymer compound of the present invention>
One embodiment of the polymer compound of the present invention is a copolymer of an α-olefin compound and a cyclic olefin compound (hereinafter, sometimes referred to as “α-olefin-cyclic olefin copolymer of the present invention”).
One embodiment of the polymer compound of the present invention is an α-olefin-norbornene copolymer.

One embodiment of the polymer compound of the present invention is a copolymer of a diene compound and a cyclic olefin compound. (Hereinafter, it may be referred to as “diene-cyclic olefin copolymer of the present invention”).
One embodiment of the polymer compound of the present invention is a diene-norbornene copolymer.

1. Copolymer of α-olefin and cyclic olefin produced by the production method of the present invention About the copolymer of α-olefin and cyclic olefin produced by the production method of the present invention, α-olefin-norbornene copolymer A combination (hereinafter, “olefin-norbornene copolymer in the present invention”) will be described as an example.
The copolymer of α-olefin and norbornene in the present invention is a polymer containing (preferably consisting of) an α-olefin structural unit and a norbornene structural unit. Here, the content of the α-olefin structural unit in the α-olefin-norbornene copolymer in the present invention can be arbitrarily selected, but is usually 20 to 100 mol%, preferably 30 mol% or more, and more. Preferably it is 50 mol%, More preferably, it is 70 mol% or more.
The content of the α-olefin structural unit in the α-olefin-norbornene copolymer in the present invention can be measured by analyzing a ¹³ C-NMR spectrum. Specifically, since each peak of the ¹³ C-NMR spectrum of the α-olefin-norbornene copolymer is attributed to each carbon of the copolymer, the ratio may be obtained based on the peak area.
Specifically, in the case of a 1-hexene-norbornene copolymer, for example, from a peak area P _{total of} a peak (polymer carbon) near 30-60 ppm on the basis of a peak area P _me of a peak (methyl carbon) near 14 ppm. The ratio of norbornene to 1-hexene can be determined. That is, it can be determined according to the following equation.
1-hexene content = P _me / [(P _total -4P _me ) / 7 + P _me ]
As will be described later, the content can be controlled between about 0% and 100% by adjusting the amount of norbornene in the monomer used as a raw material.

  As described above, the α-olefin-norbornene copolymer in the present invention includes an α-olefin structural unit and a norbornene structural unit, and both structural units may be arranged in an arbitrary order. That is, both of them may be arranged at random, or arranged with some regularity (for example, both structural units are arranged alternately, each of them is arranged to some extent continuously, or arranged in a fixed order. You may). Therefore, the α-olefin-norbornene copolymer in the present invention may be a random copolymer, an alternating copolymer, a block copolymer, or other ordered copolymer, but is preferably a random copolymer. A polymer or block copolymer, more preferably a random copolymer.

  As described above, the α-olefin-norbornene copolymer in the present invention includes a norbornene structural unit. Here, the norbornene means a compound having a 2-norbornene skeleton represented by the following formula.

In the above formula, R ^′ and R ^″ are arbitrary and are not particularly limited. For example, each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), Alternatively, R ^′ and R ^″ may be combined to form an alkylene chain or an alkenylene chain. More specifically, examples of the norbornene include 2-norbornene, dicyclopentadiene, tetracyclododecane (TCD), 1,4-methanotetrahydrofluorene (MTF), and the like.
The norbornene is more preferably 2-norbornene or dicyclopentadiene in which R ^′ and R ^″ are hydrogen atoms.

The norbornene structural unit in the α-olefin-norbornene copolymer in the present invention preferably has a high selectivity of the addition polymerization unit. That is, the structural units of polynorbornenes may be two addition polymerization units and ring-opening polymerization units shown below, but addition polymerization to all the structural units of norbornenes in the α-olefin-norbornene copolymer in the present invention. It is characterized by a high unit ratio. Specifically, the ratio of the addition polymerization unit in all structural units of norbornenes in the α-olefin-norbornene copolymer in the present invention is usually 95% or more, and preferably about 100%. The ratio between the addition polymerization unit and the ring-opening polymerization unit can be determined from a ¹ H-NMR spectrum.

  The molecular weight distribution of the α-olefin-norbornene copolymer in the present invention is not particularly limited, but its index Mw / Mn is usually 3 or less, preferably 2 or less. The molecular weight distribution means a value (Mw / Mn) measured by the GPC method (measured at 145 ° C. using polystyrene as a standard substance and 1,2-dichlorobenzene as an eluent). For example, a GPC measuring device (TOSOH HLC 8121 GPC / HT).

The molecular weight of the α-olefin-norbornene copolymer in the present invention is not particularly limited, but the number average molecular weight is usually 4 × 10 ³ or less, preferably 2 × 10 ³ or less. Although a minimum is not specifically limited, What is necessary is just 1000 or more. The molecular weight has little relation to the content of structural units derived from α-olefins. The molecular weight can be determined by the GPC method similar to the molecular weight distribution. Further, the molecular weight can be increased by raising the temperature of the polymerization reaction in the production of the α-olefin-norbornene copolymers.

The α-olefin-norbornene copolymers in the present invention usually have a glass transition point. It varies depending on the structure of the structural unit derived from α-olefin, the ratio of the structural unit derived from α-olefin and the structural unit derived from norbornene, and others. Usually, when the α-olefin content increases, the glass transition temperature decreases (see FIGS. 6 to 8). The glass transition temperature is measured by a differential scanning calorimetry (DSC) method.

2. 2. Copolymer of diene and cyclic olefin produced by the production method of the present invention 2-1. Copolymer of diene and norbornene produced by the production method of the present invention The copolymer of diene and cyclic olefin produced by the production method of the present invention is an isoprene-norbornene copolymer (hereinafter referred to as “isoprene in the present invention”). -Norbornene copolymer ") will be described as an example.
The isoprene-norbornene copolymer in the present invention has one or more types of structural units derived from norbornene represented by the following formula (B) and isoprene derived from formulas (C1) to (C4). It is a copolymer. The main unit of the structural unit derived from isoprene is the structural unit represented by (C1) (for example, 50% or more of all structural units derived from isoprene).

  In the isoprene-norbornene copolymer in the present invention, the structural units represented by the above formula (B) and formulas (C1) to (C4) may be arranged in an arbitrary order. That is, each structural unit may be arranged at random or may be arranged with some regularity. Therefore, the isoprene-norbornene copolymer in the present invention may be a random copolymer, an alternating copolymer, a block copolymer, or other ordered copolymer, preferably a random copolymer or A block copolymer, more preferably a random copolymer.

  The tacticity of the structural unit represented by the formulas (C1) to (C4) is not particularly limited, and is, for example, atactic.

As described above, the copolymer of isoprene and norbornene in the present invention is a polymer including (preferably consisting of) both an isoprene structural unit and a norbornene structural unit. Here, the content of the isoprene structural unit in the isoprene-norbornene copolymer in the present invention can be arbitrarily selected, but is usually 30 mol% or more, preferably 40 mol% or more, more preferably 50 mol% or more, still more preferably. Is 70 mol% or more.
The content of the norbornene structural unit in the isoprene-norbornene copolymer in the present invention can be measured by analyzing a ¹ H-NMR spectrum. Specifically, since each peak of the ¹ H-NMR spectrum of the isoprene-norbornene copolymer is attributed to each hydrogen of the copolymer, the ratio may be obtained based on the peak area.
Specifically, for example, a peak area P _3,4 of a peak near 4.7 ppm (3,4 vinyl hydrogen), a peak area P _1,4 , 0.8 of a peak near 5.1 ppm (1,4 hydrogen) It can be determined from the ratio of −2.2 ppm (hydrogen of norbornene and isoprene) P _total . That is, it can be determined according to the following equation.
NB content = 0.1 (P _total -7P _1,4 -3P _3,4 ) / [0.1 (P _total -7P _1,4 -3P _3,4 ) + P _1,4 + 0.5P _3,4 ]
As described later, the content can be controlled by adjusting the amount of norbornene in the monomer used as a raw material.

In the isoprene-norbornene copolymer of the present invention, the ratio of the addition polymerization unit in all the structural units of norbornene is usually 95% or more, preferably about 100%. The ratio between the addition polymerization unit and the ring-opening polymerization unit can be determined from a ¹ H-NMR spectrum.

  The molecular weight distribution of the isoprene-norbornene copolymer in the present invention is not particularly limited, but its index Mw / Mn is usually 3 or less, preferably 2 or less. The molecular weight distribution means a value (Mw / Mn) measured by the GPC method (measured at 145 ° C. using polystyrene as a standard substance and 1,2-dichlorobenzene as an eluent). For example, a GPC measuring device (TOSOH HLC 8121 GPC / HT).

The molecular weight of the isoprene-norbornene copolymer in the present invention is not particularly limited, but the number average molecular weight is usually 10 × 10 ⁴ or less, preferably 4 × 10 ⁴ or less. Although a minimum is not specifically limited, What is necessary is just 1000 or more. The molecular weight is related to the content of isoprene-derived structural units, and the higher the content, the higher the molecular weight. The molecular weight can be determined by the GPC method similar to the molecular weight distribution. Moreover, the molecular weight can be increased by increasing the temperature of the polymerization reaction in the production of the isoprene-norbornene copolymer.

  The isoprene-norbornene copolymer in the present invention usually has a glass transition point. The glass transition temperature varies depending on the structure of the structural unit derived from isoprene, the ratio of the structural unit derived from isoprene to the structural unit derived from norbornene, and the like. The glass transition temperature is usually 20 ° C. or higher (preferably 30 ° C. or higher). The glass transition temperature is measured by a differential scanning calorimetry (DSC) method.

2-2. Copolymer of diene and dicyclopentadiene of the present invention The copolymer of the diene and cyclic olefin of the present invention will be described by taking an isoprene-dicyclopentadiene copolymer as an example.
The main unit of the structural unit derived from isoprene in the isoprene-dicyclopentadiene copolymer of the present invention is a structural unit represented by the above formula (C1), and is, for example, 50% or more of all the structural units derived from isoprene. is there.

  In the isoprene-dicyclopentadiene copolymer of the present invention, the dicyclopentadiene and the structural units represented by the above formulas (C1) to (C4) may be arranged in an arbitrary order. That is, each structural unit may be arranged at random or may be arranged with some regularity. Therefore, the isoprene-dicyclopentadiene copolymer of the present invention may be a random copolymer, an alternating copolymer, a block copolymer, or other ordered copolymer, but is preferably a random copolymer. A polymer or block copolymer, more preferably a random copolymer.

  The tacticity of the structural unit represented by the formulas (C1) to (C4) is not particularly limited, and is, for example, atactic.

The content of isoprene structural units relative to all structural units contained in the isoprene-dicyclopentadiene copolymer of the present invention can be arbitrarily selected, but is usually 20 to 80 mol%, preferably 30 mol% or more, more preferably It is 50 mol% or more, more preferably 70 mol% or more.
The content can be measured by analyzing a ¹ H-NMR spectrum. Specifically, since each peak in the ¹ H-NMR spectrum of the isoprene-dicyclopentadiene copolymer is attributed to each hydrogen of the copolymer as shown in FIG. 14, the ratio of these peak areas Can be obtained from Specifically, for example, a peak area P _DCPD of a peak near 3.1 ppm (dicyclopentadiene hydrogen), a peak area P DC4 of a peak near 4.7 ppm (3,4 vinyl hydrogen), P _3, 4, near 5.1 ppm. It can be determined from the ratio of peak (1,4 vinyl hydrogen) P _1,4 . That is, it can be determined according to the following equation.
DCPD content = P _DCPD / (P _DCPD + P _1,4 + 0.5P _3,4 )
The content rate can be controlled by adjusting the amount (or concentration) of dicyclopentadiene in the raw material for producing the isoprene-dicyclopentadiene copolymer (described later).

Dicyclopentadiene has a C═C double bond derived from a norbornene structure and a C═C double bond derived from a cyclopentene structure. The ratio of the dicyclopentadiene structural unit based on the C═C double bond derived from the norbornene structure to the total structural unit of the dicyclopentadiene in the isoprene-dicyclopentadiene copolymer of the present invention is usually 80% or more, preferably Is 90% or more, more preferably 95% or more, and still more preferably 99% or more.
Similarly to the norbornene structural unit, the dicyclopentadiene structural unit based on the C═C double bond derived from the norbornene structure can be an addition polymerization unit and a ring-opening polymerization unit represented by the following formula. The ratio of the addition polymerization unit to the total structural unit of dicyclopentadiene in the dicyclopentadiene copolymer is usually 80% or more, preferably 90% or more, more preferably 95% or more, and further preferably 100% or more. .
The content can be determined from ¹ H-NMR spectrum data.

  The molecular weight distribution of the isoprene-dicyclopentadiene copolymer of the present invention is not particularly limited, but the index Mw / Mn is usually 3 or less, preferably 2 or less. The molecular weight distribution means a value (Mw / Mn) measured by the GPC method (measured at 145 ° C. using polystyrene as a standard substance and 1,2-dichlorobenzene as an eluent). For example, a GPC measuring device (TOSOH HLC 8121 GPC / HT).

The molecular weight of the isoprene-dicyclopentadiene copolymer of the present invention is not particularly limited, but the number average molecular weight is usually 1 × 10 ³ or more, preferably 3 × 10 ³ or more, more preferably 5 × 10. ³ or more, more preferably 9 × 10 ³ or more.
Although an upper limit is not specifically limited, A number average molecular weight should just be 50x10 < ³ > or less.
The molecular weight can be determined by the GPC method similar to the molecular weight distribution.

<Method for producing polymer compound of the present invention>
The method for producing a polymer compound of the present invention is characterized in that an arbitrary polymerizable monomer is polymerized (addition polymerization) using the above-described polymerization catalyst composition of the present invention.
The production method of the present invention may be the same as the conventional method of producing a polymer compound by an addition polymerization reaction using a coordination ion polymerization catalyst, except that the catalyst composition of the present invention is used as a polymerization catalyst. it can.

Specifically, for example, the following procedure can be used.
1. Polymerization is performed by supplying a polymerizable monomer into a system (preferably a liquid phase) containing the catalyst composition of the present invention. Here, if the monomer is liquid, it can be supplied by dropping, and if it is gas, it can be supplied through a gas pipe (for example, bubbling if it is a liquid phase reaction system).
2. Polymerization is carried out by adding the catalyst composition of the present invention or separately adding the components of the catalyst composition to a system (preferably a liquid phase) containing a polymerizable monomer. The catalyst composition to be added may be prepared in advance (preferably prepared in a liquid phase) and activated (in this case, it is preferable to add the catalyst composition so as not to touch outside air).

Here, the polymerizable monomer is a monomer having addition polymerization, for example, an olefin monomer, an epoxy monomer, an isocyanate monomer, a lactone monomer, a lactide polymer, a cyclic carbonate monomer, an alkyne monomer, and the like. A combination of these may also be used.
Of these, preferably one or more olefinic monomers, more preferably substituted and unsubstituted α-olefins (including 1-hexene), dienes, and cyclic olefins (including norbornenes and cyclohexadiene). Or one or more monomers selected from Here, as the diene which is an olefin monomer, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene, 1, 4-hexadiene, 1,5-hexadiene, 2,4-dimethyl-1,3-pentadiene, 2-methyl-1,3-hexadiene, 2,4-hexadiene, cyclic dienes such as cyclohexadiene, dicyclopentadiene, etc. Can be illustrated.

The production method may be any method such as a gas phase polymerization method, a solution polymerization method, a suspension polymerization method, a liquid phase bulk polymerization method, an emulsion polymerization method, a solid phase polymerization method. In the case of the solution polymerization method, the solvent to be used is not particularly limited as long as it is inert in the polymerization reaction and can dissolve the monomer and the catalyst. For example, saturated aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; saturated alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene and toluene; chlorobenzene, bromobenzene, chlorotoluene, and the like A halogenated hydrocarbon is mentioned.
Moreover, the solvent which does not have toxicity with respect to a biological body is preferable. Specifically, an aromatic hydrocarbon, particularly toluene is preferable. The solvent may be used alone or in combination of two or more.
The amount of the solvent used is arbitrary, but is preferably an amount that makes the concentration of the complex contained in the polymerization catalyst 0.1 to 0.0001 mol / l.

The polymerization temperature when the polymerization of the present invention is performed by solution polymerization can be performed at any temperature, for example, in the range of -90 to 100 ° C. Although it may be appropriately selected according to the type of monomer to be polymerized, etc., it can usually be performed at around room temperature, that is, at about 25 ° C.
The polymerization time is about several seconds to several tens of hours, and may be appropriately selected according to the type of monomer to be polymerized. For example, in the case of copolymerization of an α-olefin and a cyclic olefin, it is usually 24 hours or less, and in some cases, 12 hours or less. In the case of copolymerization of a diene and a cyclic olefin, it is usually 1 hour or less, and in some cases 15 minutes or less.
However, these reaction conditions can be appropriately selected according to the polymerization reaction temperature, the type and molar amount of the monomer, the type and amount of the catalyst composition, etc., and should be limited to the ranges exemplified above. There is no.

For the production of the copolymer,
1) If it is a random copolymer or an alternating copolymer, it can be produced by polymerizing a mixture of two or more monomers in the presence of a catalyst composition,
2) If it is a block copolymer, it can manufacture by supplying each monomer in order in the reaction system containing a catalyst composition.

Specific examples of the polymer compound produced by the production method of the present invention include the following, but are not limited thereto.
1) Copolymer of α-olefin and cyclic olefin.
2) A copolymer of a diene and a cyclic olefin.
The method for producing the copolymer will be described in more detail below by taking several copolymers as examples. A person skilled in the art can produce various (co) polymers based on the following specific description, examples and ordinary organic chemical techniques.

1. Method for Producing α-Olefin-Norbornene Copolymer An α-olefin-norbornene copolymer can be produced by polymerizing an α-olefin and norbornene using the catalyst composition of the present invention.
As the complex in the catalyst composition, a complex in which the central metal is scandium (Sc), yttrium (Y), gadolinium (Gd), lutetium (Lu), more preferably scandium (Sc) is preferably used. On the other hand, the ionic compound in the catalyst composition is preferably a compound composed of a tetravalent boron anion and a carbonium cation such as [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ]. The molar ratio of the complex (in terms of central metal) and the ionic compound is preferably about 1: 1.

As a specific procedure, for example, the complex of the present invention is dissolved in a solvent (preferably toluene), and a solvent in which an α-olefin and norbornenes are dissolved is added thereto. The active compound is generated by supplying the active compound to form the catalyst composition, and the reaction is performed. The reaction temperature is preferably adjusted to about 25 ° C.
In addition, in the conventional catalyst composition, reaction was possible at high temperature, but according to the manufacturing method of this invention, reaction is possible at normal temperature.
By changing the monomer charge ratio, the α-olefin content can be adjusted to approximately 0% to 100%. There is no significant trend between the α-olefin ratio and the molecular weight of the resulting copolymer.
The amount of the solvent used in the polymerization reaction is preferably about 5 ml with respect to 20 mmol of total monomers, but is not particularly limited thereto.
The amount of the monomer to be provided is preferably 100 to 1000 times in molar ratio with respect to the complex (in terms of central metal).
The polymerization reaction is often completed in about several minutes to several tens of hours. When the reaction is completed, the viscosity of the reaction system increases and stirring may not be possible.

After completion of the reaction, the produced polymer can be precipitated by placing the reaction mixture in methanol or the like. The α-olefin-norbornene copolymer can be obtained by filtering the precipitated polymer and drying it. The yield of the resulting α-olefin-norbornene copolymer varies depending on the type of complex used. For example, in the 1-hexene-norbornene copolymer, the conversion rate of each monomer can be about 100% for 1-hexene and about 80% for norbornene.
According to such a production method, an α-olefin-norbornene copolymer having a high α-olefin content can be produced.

2. Method for producing isoprene-norbornene copolymer The isoprene-norbornene copolymer can be produced by polymerizing isoprene and norbornene using the catalyst composition of the present invention.
As the complex in the catalyst composition, a complex in which the central metal is scandium (Sc), yttrium (Y), gadolinium (Gd), lutetium (Lu), more preferably scandium (Sc) is preferably used. On the other hand, examples of the ionic compound in the catalyst composition include a compound comprising a tetravalent boron anion and a carbonium cation such as [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] and [PhNMe ₂ H] [B A compound composed of a tetravalent boron anion and an anilinium cation such as (C ₆ F ₅ ) ₄ ] is preferred. The molar ratio of the complex (in terms of central metal) and the ionic compound is preferably about 1: 1.

As a specific procedure, for example, the complex of the present invention, isoprene, and norbornene are dissolved in a solvent (preferably toluene), and while stirring this, an ionic compound is further supplied to form a catalyst composition to be active. Generate seeds and react. The reaction temperature is preferably adjusted to about 25 ° C.
In addition, according to the manufacturing method of this invention, reaction is possible with high efficiency.
By changing the monomer charge ratio, the isoprene content can be adjusted. When the proportion of isoprene is increased, the molecular weight of the resulting copolymer tends to increase, and the isoprene content tends to increase.
The amount of the solvent used in the polymerization reaction is preferably about 5 ml with respect to 10 to 20 mmol of total monomers, but is not particularly limited thereto.
The amount of the monomer to be provided is preferably 100 to 2000 times in molar ratio with respect to the complex (in terms of central metal).
The polymerization reaction is often completed in about several seconds to 1 hour. When the reaction is completed, the viscosity of the reaction system increases and stirring may not be possible.

After completion of the reaction, the produced polymer can be precipitated by placing the reaction mixture in methanol or the like. The precipitated polymer is collected by filtration and dried to obtain an isoprene-norbornene copolymer. The yield of the resulting isoprene-norbornene copolymer varies depending on the type of complex used. For example, in the isoprene-norbornene copolymer, the conversion rate of each monomer can be about 100% for isoprene and about 80% for norbornene.
According to such a production method, a diene-norbornene copolymer having a high diene content can be produced.

3. Production Method of Isoprene-Dicyclopentadiene Copolymer An isoprene-dicyclopentadiene copolymer can be produced by polymerizing isoprene and dicyclopentadiene using the catalyst composition of the present invention.
As the complex in the catalyst composition, a complex in which the central metal is scandium (Sc), yttrium (Y), gadolinium (Gd), lutetium (Lu), more preferably scandium (Sc) is preferably used. On the other hand, the ionic compound in the catalyst composition is preferably a compound composed of a tetravalent boron anion and a carbonium cation such as [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ]. It is preferable that the complex and the ionic compound have a molar ratio of about 1: 1.

As a specific procedure, for example, the complex of the present invention is dissolved in a solvent (preferably toluene), and a solvent in which isoprene and dicyclopentadiene is dissolved is added thereto. A compound is supplied to form a catalyst composition to generate active species, and a reaction is performed. The reaction temperature is preferably adjusted to about 25 ° C.
The amount of the solvent used in the polymerization reaction is preferably about 5 ml with respect to 20 mmol of total monomers, but is not particularly limited thereto.
The amount of the monomer to be provided is preferably 100 to 2000 times in molar ratio with respect to the complex (in terms of central metal).
The polymerization reaction is often completed in about several seconds to 1 hour. When the reaction is completed, the viscosity of the reaction system increases and stirring may not be possible.

  After completion of the reaction, the produced polymer can be precipitated by placing the reaction mixture in methanol or the like. The precipitated polymer is collected by filtration and dried to obtain an isoprene and dicyclopentadiene copolymer. The yield of the resulting isoprene and dicyclopentadiene copolymer varies depending on the type of complex used. For example, in the isoprene-dicyclopentadiene copolymer, the conversion rate of each monomer can be about 100% for isoprene and about 20% for dicyclopentadiene.

Hereinafter, the present invention will be described in more detail with reference to Examples and Reference Examples, but the scope of the present invention is not limited by these. ¹³ C-NMR was measured at a frequency of 75.5 MHz.

<Reference example>
<Synthesis of metallocene complexes>
The compounds were synthesized according to the methods described in the following documents (1) and (2).
(1) Tardif, O .; Nishiura, M .; Hou, ZM Organometallics 22, 1171, (2003).
(2) Hultzsch, KC; Spaniol, TP; Okuda, J. Angew. Chem. Int. Ed, 38, 227,
(1999).

1. Synthesis of (η ⁵ -C ₅ Me ₄ SiMe ₃ ) Sc (η ³ -C ₃ H ₅ ) ₂
C ₅ Me ₄ SiMe ₃ Li (1 mmol, in 10 ml THF) prepared in situ was added to a suspension of ScCl ₃ (151 mg, 1 mmol) in 20 ml THF. The mixture was stirred for 30 minutes until a clear solution was obtained indicating that the ScCl ₃ was completely consumed. (Allyl) MgCl (1 ml, 2 mmol, in 2.0 M THF) was added dropwise and the resulting pale yellow solution was left overnight. Removal of volatiles yielded a yellow residue that was extracted with hexane. Evaporation of the solvent gave the product as yellow solid crystals (291 mg, 91%).

The physical property data of (η ⁵ -C ₅ Me ₄ SiMe ₃ ) Sc (η ³ -C ₃ H ₅ ) ₂ are shown below.
¹ H NMR (C ₆ D _6, 25 ° C): (7.11 (quintet, 2H, J = 12.3 Hz, CH ₂ C H CH ₂ ), 3.76 (br s,
4H, syn-C H ₂ CHC H ₂ ), 2.92 (br s, 4H, anti-C H ₂ CHC H ₂ ), 2.22 (s, 6H, C ₅ Me ₄ ), 1.73 (s, 6H, C ₅ Me ₄ ), 0.17 (s, 9H, C ₅ Me ₄ S iMe ₃ ).
¹³ C NMR (C ₆ D ₆ , 25 ° C): (157.9 (CH ₂ C HCH ₂ ), 130.7 ( C ₅ Me ₄ SiMe ₃ ), 125.8 ( C ₅ Me ₄ SiMe ₃ ), 119.1 (C _ipso of C ₅ Me ₄ SiMe ₃ ), 79.3 ( C H ₂ CH C H ₂ ), 16.0 (C ₅ Me ₄ SiMe ₃ ), 12.2 (C ₅ Me ₄ SiMe ₃ ), 2.2 (C ₅ Me ₄ SiMe ₃ ).
Anal. Calcd for C ₁₈ H ₃₁ ScSi: C, 67.46; H, 9.75. Found: C, 67.40; H, 9.22.

2. Synthesis of (η ⁵ -C ₅ Me ₅ ) Sc (η ³ -C ₃ H ₅ ) ₂
C ₅ Me ₅ Li (1 mmol, in 10 ml THF) prepared in situ was added to a suspension of ScCl ₃ (151 mg, 1 mmol) in 20 ml THF. The mixture was stirred for 4 hours until a clear solution was obtained indicating that the ScCl ₃ was completely consumed. After (Allyl) MgCl (1 ml, 2 mmol, 2.0 M in THF) was added dropwise, the resulting pale yellow solution was allowed to stand overnight at room temperature. Removal of volatiles yielded a yellow residue that was extracted with hexane. Evaporation of the solvent gave the product as a yellow solid (187 mg, 71%).

The physical property data of (η ⁵ -C ₅ Me ₅ ) Sc (η ³ -C ₃ H ₅ ) ₂ are shown below.
¹ H NMR (C ₆ D ₆ ): (6.91-6.72 (m, 2H, CH ₂ C H CH ₂ ), 3.03 (br s, 8H, C H ₂ CHC H ₂ ), 1.61 (s, 15H, C ₅ Me ₅ ).
¹³ C NMR (C ₆ D ₆ ): (158.05 (CH ₂ C HCH ₂ ), 120.72 ( C ₅ Me ₅ ), 78.44 ( C H ₂ CH C H ₂ ), 11.81 (C ₅ Me ₅ ).
Anal. Calcd for C ₁₆ H ₂₅ Sc: C, 73.26; H, 9.61. Found: C, 72.79; H, 9.76.

3. Synthesis of (η ⁵ -C ₅ Me ₅ ) Sc (η ³ -2-Me-C ₃ H ₄ ) ₂
C ₅ Me ₅ Li (1 mmol, in 10 ml THF) prepared in situ was added to a suspension of ScCl ₃ (151 mg, 1 mmol) in 20 ml THF. The mixture was stirred for 4 hours until a clear solution was obtained indicating that the ScCl ₃ was completely consumed. (2-Me-Allyl) MgCl (4 ml, 2 mmol, in 0.5 M THF) was added dropwise, and the resulting pale yellow solution was allowed to stand at room temperature overnight. Removal of volatiles yielded a yellow residue that was extracted with hexane. Evaporation of the solvent gave the product as a brown solid (275 mg, 95%).

The physical property data of (η ⁵ -C ₅ Me ₅ ) Sc (η ³ -2-Me-C ₃ H ₄ ) ₂ are shown below.
¹ H NMR (C ₆ D ₆ ): (2.87 (br s, 8H, C H ₂ CMeC H ₂ ), 1.81 (s, 6H, CH ₂ C Me CH ₂ ), 1.71 (s,
15H, C ₅ Me ₅ ).
¹³ C NMR (C ₆ D ₆ ): (167.58 (CH ₂ C MeCH ₂ ), 120.57 ( C ₅ Me ₅ ), 74.91 ( C H ₂ CMe C H ₂ ), 27.87
(CH ₂ C Me CH ₂ ), 12.02 (C ₅ Me ₅ ).
Anal. Calcd for C ₁₈ H ₂₉ Sc: C, 74.45; H, 10.07. Found: C, 73.72; H, 9.85.

4). ^{_{(η 5 -C 5 Me 4 SiMe}} 3) Sc (η 3 -C 3 H 5) 2 / [PhNMe 2 H] [B (C 6 F 5) 4] Synthesis of toluene (10ml), (η ⁵ - A mixture of C ₅ Me ₄ SiMe ₃ ) Sc (η ³ -C ₃ H ₅ ) ₂ (64 mg, 0.20 mmol) and [PhNMe ₂ H] [B (C ₆ F ₅ ) ₄ ] (162 mg, 0.20 mmol) Added to. The resulting red suspension was stirred at 25 ° C. for 30 minutes, and the solvent was removed by concentration under reduced pressure. The obtained dark red residue was washed with hexane (5 ml × 3) until a fine brick-colored powder (200 mg, 93%) was obtained.

The physical property data of (η ⁵ -C ₅ Me ₄ SiMe ₃ ) Sc (η ³ -C ₃ H ₅ ) ₂ / [PhNMe ₂ H] [B (C ₆ F ₅ ) ₄ ] are shown below.
¹ H NMR (C ₄ D ₈ O, 25 (C): (7.06 (t, 2H, J = 7.8 Hz, m-Ph), 6.91-6.75 (m, 1H, CH ₂ C H CH ₂ ), 6.64 ( d, 2H, J = 4.2 Hz, o-Ph), 6.42 (t, 1H, J = 6.6Hz, p-Ph), 3.14 (s, 2H, syn-C H ₂ CHC H ₂ ), 3.10 (s, 2H, anti-C H ₂ CHC H ₂ ), 2.85 (s, 6H, N Me ₂ ), 2.21 (s, 6H,
C ₅ Me ₄ ), 1.98 (s, 6H, C ₅ Me ₄ ), 0.26 (s, 9H, C ₅ Me ₄ S iMe ₃ ).

¹ H NMR (C ₆ D ₅ Cl, 25 (C): (7.21-7.17 (m, 2H, m-Ph), 7.03-6.95 (m, 2H, o-Ph), 6.66-6.63 (m, 1H, p-Ph), 2.61 (s, 6H, N Me ₂ ), 2.05 (s, 6H, C ₅ Me ₄ ), 1.61 (s, 6H, C ₅ Me ₄ ), 0.09 (s, 9H, C ₅ Me ₄ S iMe ₃ ). Proton resonance of allyl ligand was not detected.

¹³ C NMR (C ₄ D ₈ O, 25 (C, C ₆ F ₅ resonances not reported): (155.2 (CH ₂ C HCH ₂ ), 151.6 (C _ipso of Ph NMe ₂ ), 134.6 ( C ₅ Me ₄ SiMe ₃ ), 129.4 ( Ph NMe ₂ ), 128.4 ( C ₅ Me ₄ SiMe ₃ ), 122.9 (C _ipso of C ₅ Me ₄ SiMe ₃ ), 117.0 ( Ph NMe ₂ ), 113.2 ( Ph NMe ₂ ), 82.1 ( C H ₂ CH C H ₂ ), 40.4
(PhN Me ₂ ), 15.4 (C ₅ Me ₄ SiMe ₃ ), 11.8 (C ₅ Me ₄ SiMe ₃ ), 1.8 (C ₅ Me ₄ SiMe ₃ ).

¹⁹ F NMR (C ₄ D ₈ O, 25 (C): (-131.8 (s, oF), -164.0 (t, J _FF = 19.5 Hz, pF), -167.5 (t, J _FF = 16.2 Hz, mF ).
¹¹ B NMR (C ₄ D ₈ O, 25 (C): (-16.3.

¹⁹ F NMR (C ₆ D ₅ Cl, 25 (C): (-132.3 (s, oF), -162.6 (t, J _FF = 19.5 Hz, pF), -166.6 (t, J _FF = 17.3 Hz, mF ).
¹¹ B NMR (C ₆ D ₅ Cl, 25 (C): (-16.6.
Anal. Calcd for C ₄₇ H ₃₈ BF ₂₀ NScSi: C, 52.29; H, 3.45; N, 1.30. Found: C, 52.15; H, 3.62; N, 1.49.

<Production Example 1> Production of isoprene polymer In a glove box, in a 100 ml glass flask, (η ⁵ -C ₅ Me ₄ SiMe ₃ ) Sc (η ³ -C ₃ H ₅ ) ₂ (8 mg, 25 μmol , Sc conversion) and isoprene (682 mg, 10 mmol). Toluene (8 ml) was added and stirred well for 1 minute. A toluene solution (2 ml) of [PhNMe ₂ H] [B (C ₆ F ₅ ) ₄ ] (20 mg, 25 μmol) was quickly added, and the mixture was stirred at room temperature (25 ° C.) for 15 minutes. The polymerization was stopped with methanol. The obtained mixture was poured into a large amount of methanol to precipitate the polymer. It was washed with methanol and dried under reduced pressure at 60 ° C. until a constant weight was obtained.
The results are shown in Table 1.

<Production Example 2> Production of norbornene polymer Polymerization was carried out in the same manner as in Reference Example 1 except that isoprene was changed to norbornene (942 mg, 10 mmol) and the reaction time was changed to 12 hours.
The results are shown in Table 1.

In Table 1, Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were determined by GPC method against polystyrene standards.
2. The structure of polyisoprene was determined by ¹ H NMR.
3. The glass transition point (Tg) was determined by the DSC method.

  As shown in Table 1, isoprene polymer and norbornene polymer can be produced by the complex 1 of the present invention.

<Example 1> Production of isoprene-norbornene random copolymer In a 100 ml glass flask, (η ⁵ -C ₅ Me ₄ SiMe ₃ ) Sc (η ³ -C ₃ H ₅ ) ₂ (8 mg, 25 μmol, converted to Sc), isoprene (341 mg, 5 mmol), and norbornene (471 mg, 5 mmol) were charged. Toluene (3 ml) was added and stirred well for 1 minute. A toluene solution (2 ml) of [PhNMe ₂ H] [B (C ₆ F ₅ ) ₄ ] (20 mg, 25 μmol) was quickly added, and the mixture was stirred at room temperature (25 ° C.) for 15 minutes. The polymerization was stopped with methanol. The obtained mixture was poured into a large amount of methanol to precipitate the polymer. It was washed with methanol and dried under reduced pressure at 60 ° C. until a constant weight was obtained.
The results are shown in Table 2.

<Example 2>
Polymerization was carried out in the same manner as in Example 1 except that the norbornene / isoprene (NB / IP) ratio was 5.
The results are shown in Table 2.

<Example 3>
Polymerization was carried out in the same manner as in Example 1 except that the NB / IP ratio was 7.
The results are shown in Table 2.

<Example 4>
Polymerization was carried out in the same manner as in Example 1 except that the NB / IP ratio was 10.
The results are shown in Table 2.

In Table 2, Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were determined by GPC method against polystyrene standards.
2. The NB content and polyisoprene structure were determined by ¹ H NMR.
3. The glass transition point (Tg) was determined by the DSC method.

As shown in Table 2, an isoprene-norbornene copolymer can be produced by the production method of the present invention.
It was found that adjusting the monomer charge ratio can adjust the isoprene content in the resulting polymer. When the ratio of isoprene in the charging ratio increases, the isoprene content in the resulting polymer increases and the molecular weight increases.

Example 5 Effect of Temperature on Production of Isoprene-Norbornene Copolymer In a glove box, a glass flask with a 100 ml J. Young bulb was placed in a (η ⁵ -C ₅ Me ₄ SiMe ₃ ) Sc (η ³ -C ₃ H ₅ ) ₂ (8 mg, 25 μmol, converted to Sc), isoprene (681 mg, 10 mmol), and norbornene (942 mg, 10 mmol) were charged. Toluene (3 ml) was added and stirred well for 1 minute. The reaction vessel was taken out and placed in a cold bath set at -20 ° C. A toluene solution (2 ml) of [PhNMe ₂ H] [B (C ₆ F ₅ ) ₄ ] (20 mg, 25 μmol) was quickly added, and the mixture was stirred at −20 ° C. for 5 minutes. The polymerization was stopped with methanol. The obtained mixture was poured into a large amount of methanol to precipitate the polymer. It was washed with methanol and dried under reduced pressure at 60 ° C. until a constant weight was obtained.
The results are shown in Table 3.

<Example 6>
Polymerization was carried out in the same manner as in Example 5 except that the reaction temperature was 25 ° C.
The results are shown in Table 3.

<Example 7>
Polymerization was carried out in the same manner as in Example 5 except that the reaction temperature was 50 ° C.
The results are shown in Table 3.

In Table 3,
1. The activity is expressed as the number of kg of polymer produced when the reaction is carried out for 1 hour using 1 mol of the complex (in terms of Sc).
2. Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were determined by GPC method against polystyrene standards.
3. The NB content and polyisoprene structure were determined by ¹ H NMR.

  Increasing the polymerization temperature increases the norbornene content.

Example 8 Production of 1-hexene-norbornene random copolymer (η ⁵ -C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ C ₆ H ₄ NMe at 25 ° C. in a 20 ml flask in a glove box. Norbornene (0.94 g, 10 mmol) and 1-hexene (0.84 g, 10 mmol) were added to a toluene solution (2 ml) of ₂ -o) ₂ (20 mg, 40 μmol). The mixture was stirred well at room temperature for several minutes, and a solution of [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] (37 mg, 40 μmol) in toluene (3 ml) was added with vigorous stirring. After 12 hours, the flask was taken out of the glove box and methanol was added to stop the polymerization. The resulting mixture was poured into methanol (200 ml) to precipitate the polymer. The white polymer powder was collected by filtration and dried under reduced pressure at 60 ° C. until a constant weight was obtained (1.54 g, 3.2 kg copolymer / mol-Sc · h). The resulting product was soluble in THF at room temperature and had a number average molecular weight of 1500 and a molecular weight distribution of 1.77. The glass transition point of the polymer is about 61 ° C. The resulting amorphous polymer is a random copolymer having a 1-hexene content of about 53 mol% as determined by ¹³ C NMR.
The results are shown in Table 4.

<Example 9>
Example 8 except that the catalyst system was changed to (η ⁵ -C ₅ Me ₅ ) Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ / [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] Polymerization was carried out in the same manner as described above. A 1-hexene-norbornene random copolymer was obtained.
The results are shown in Table 4.

<Example 10>
Except for changing the catalyst system to (η ⁵ -C ₅ Me ₄ SiMe ₃ ) Sc (η ³ -C ₃ H ₅ ) ₂ / [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ], Polymerization was carried out in the same manner. A 1-hexene-norbornene random copolymer was obtained.
The results are shown in Table 4.

<Example 11>
Except for changing the catalyst system to (η ⁵ -C ₅ Me ₅ ) Sc (η ³ -C ₃ H ₅ ) ₂ / [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ], the same procedure as in Example 8 was performed. Polymerization was performed. A 1-hexene-norbornene random copolymer was obtained.
The results are shown in Table 4.

<Example 12>
Example 8 except that the catalyst system is changed to (η ⁵ -C ₅ Me ₅ ) Sc (η ³ -C ₃ H ₄ Me) ₂ / [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] Polymerization was carried out. A 1-hexene-norbornene random copolymer was obtained.
The results are shown in Table 4.

<Example 13>
Polymerization was carried out in the same manner as in Example 8 except that the reaction temperature was changed from 25 ° C to 0 ° C. A 1-hexene-norbornene random copolymer was obtained.
The results are shown in Table 4.

<Example 14>
Polymerization was carried out in the same manner as in Example 8 except that the reaction temperature was changed from 25 ° C to 50 ° C. A 1-hexene-norbornene random copolymer was obtained.
The results are shown in Table 4.

<Example 15>
Polymerization was carried out in the same manner as in Example 8 except that the comonomer supply ratio (1-hexene / norbornene molar ratio) was changed from 1/1 to 2/1. A 1-hexene-norbornene random copolymer was obtained.
The results are shown in Table 4.

<Example 16>
Polymerization was carried out in the same manner as in Example 8 except that the comonomer supply ratio (1-hexene / norbornene molar ratio) was changed from 1/1 to 4/3. A 1-hexene-norbornene random copolymer was obtained.
The results are shown in Table 4.

<Example 17>
Polymerization was carried out in the same manner as in Example 8 except that the comonomer supply ratio (1-hexene / norbornene molar ratio) was changed from 1/1 to 3/4. A 1-hexene-norbornene random copolymer was obtained.
The results are shown in Table 4.

<Example 18>
Polymerization was carried out in the same manner as in Example 8 except that the comonomer supply ratio (1-hexene / norbornene molar ratio) was changed from 1/1 to 1/2. A 1-hexene-norbornene random copolymer was obtained.
The results are shown in Table 4.

<Example 19>
Polymerization was carried out in the same manner as in Example 8 except that the comonomer supply ratio (1-hexene / norbornene molar ratio) was changed from 1/1 to 1/3. A 1-hexene-norbornene random copolymer was obtained.
The results are shown in Table 4.

In Table 4, Complex 1 represents (η ⁵ -C ₅ Me ₄ SiMe ₃ ) Sc (η ³ -C ₃ H ₅ ) ₂ , 2 represents (η ⁵ -C ₅ Me ₅ ) Sc (η ³ -C ₃ H ₅ ) ₂ 3 represents (η ⁵ -C ₅ Me ₅ ) Sc (η ³ -C ₃ H ₄ Me) ₂ and 4 represents (η ⁵ -C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ and 5 indicates (η ⁵ -C ₅ Me ₅ ) Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ .
2. The activity is expressed as the number of kg of polymer produced when the reaction is carried out for 1 hour using 1 mol of the complex (in terms of Sc).
3.1-Hex content was determined by ¹³ C NMR.
4). Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were determined by GPC method against polystyrene standards.
5. The glass transition point (Tg) was determined by the DSC method.

As shown in Table 4, a 1-hexene-norbornene copolymer can be produced from the complexes 1 to 4 of the present invention.
It was found that the 1-hexene content in the resulting polymer can be adjusted by adjusting the monomer charge ratio. As the ratio of 1-hexene in the charging ratio increases, the 1-hexene content in the resulting polymer increases. As the 1-hexene content increases, the glass transition temperature decreases.
The polymerization temperature is best at room temperature, and the polymerization activity and the 1-hexene content decrease at low and high temperature conditions.

Example 20 Production of 1-octene-norbornene random copolymer (η ⁵ -C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ C ₆ H ₄ NMe at 25 ° C. in a 20 ml flask in a glove box. Norbornene (0.94 g, 10 mmol) and 1-octene (1.12 g, 10 mmol) were added to a toluene solution (2 ml) of ₂ -o) ₂ (20 mg, 40 μmol). The mixture was stirred well at room temperature for several minutes, and a solution of [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] (37 mg, 40 μmol) in toluene (3 ml) was added with vigorous stirring. After 12 hours, the flask was taken out of the glove box and methanol was added to stop the polymerization. The resulting mixture was poured into methanol (200 ml) to precipitate the polymer. The white polymer powder was collected by filtration and dried under reduced pressure at 60 ° C. until a constant weight was obtained (1.12 g, 2.3 kg copolymer / mol-Sc · h). The resulting product was soluble in THF at room temperature and had a number average molecular weight of 1400 and a molecular weight distribution of 1.50. The glass transition point of the polymer is about 73 ° C. The resulting amorphous polymer is a random copolymer having a 1-octene content of about 48.7 mol% as determined by ¹³ C NMR.
The results are shown in Table 4.

<Example 21>
Example 20 except that the catalyst system is changed to (η ⁵ -C ₅ Me ₅ ) Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ / [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] Polymerization was carried out in the same manner as described above. A 1-octene-norbornene random copolymer was obtained.
The results are shown in Table 5.

<Example 22>
Example 20 except that the catalyst system is changed to (η ⁵ -C ₅ Me ₄ SiMe ₃ ) Sc (η ³ -C ₃ H ₅ ) ₂ / [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] Polymerization was carried out in the same manner. A 1-octene-norbornene random copolymer was obtained.
The results are shown in Table 5.

<Example 23>
Example 20 was repeated except that the catalyst system was changed to (η ⁵ -C ₅ Me ₅ ) Sc (η ³ -C ₃ H ₅ ) ₂ / [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ]. Polymerization was performed. A 1-octene-norbornene random copolymer was obtained.
The results are shown in Table 5.

<Example 24>
Example 20 except that the catalyst system is changed to (η ⁵ -C ₅ Me ₅ ) Sc (η ³ -C ₃ H ₄ Me) ₂ / [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] Polymerization was carried out. A 1-octene-norbornene random copolymer was obtained.
The results are shown in Table 5.

<Example 25>
Polymerization was carried out in the same manner as in Example 20 except that the comonomer supply ratio (1-octene / norbornene molar ratio) was changed from 1/1 to 2/1. A 1-octene-norbornene random copolymer was obtained.
The results are shown in Table 5.

<Example 26>
Polymerization was carried out in the same manner as in Example 20 except that the comonomer supply ratio (1-octene / norbornene molar ratio) was changed from 1/1 to 4/3. A 1-octene-norbornene random copolymer was obtained.
The results are shown in Table 5.

<Example 27>
Polymerization was carried out in the same manner as in Example 20 except that the comonomer supply ratio (1-octene / norbornene molar ratio) was changed from 1/1 to 7/6. A 1-octene-norbornene random copolymer was obtained.
The results are shown in Table 5.

<Example 28>
Polymerization was carried out in the same manner as in Example 20 except that the comonomer supply ratio (1-octene / norbornene molar ratio) was changed from 1/1 to 1/2. A 1-octene-norbornene random copolymer was obtained.
The results are shown in Table 5.

In Table 5, Complex 1 represents (η ⁵ -C ₅ Me ₄ SiMe ₃ ) Sc (η ³ -C ₃ H ₅ ) ₂ , 2 represents (η ⁵ -C ₅ Me ₅ ) Sc (η ³ -C ₃ H ₅ ) ₂ 3 represents (η ⁵ -C ₅ Me ₅ ) Sc (η ³ -C ₃ H ₄ Me) ₂ and 4 represents (η ⁵ -C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ and 5 indicates (η ⁵ -C ₅ Me ₅ ) Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ .
2. The activity is expressed as the number of kg of polymer produced when the reaction is carried out for 1 hour using 1 mol of the complex (in terms of Sc).
3.1-Oct content was determined by ¹³ C NMR.
4). Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were determined by GPC method against polystyrene standards.
5. The glass transition point (Tg) was determined by the DSC method.

As shown in Table 5, a 1-octene-norbornene copolymer can be produced from the complexes 1 to 5 of the present invention.
It was found that by adjusting the monomer charge ratio, the 1-octene content in the resulting polymer can be adjusted. Increasing the 1-octene ratio in the feed ratio increases the 1-octene content in the resulting polymer. As the 1-octene content increases, the glass transition temperature decreases.

Example 29 Production of 4-methyl-1-pentene-norbornene random copolymer (η ⁵ -C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ C) at 25 ° C. in a 20 ml flask in a glove box. ₆ H ₄ NMe ₂ -o) ₂ (20 mg, 40 μmol) in toluene solution (2 ml) added norbornene (0.94 g, 10 mmol) and 4-methyl-1-pentene (0.84 g, 10 mmol) did. The mixture was stirred well at room temperature for several minutes, and a solution of [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] (37 mg, 40 μmol) in toluene (3 ml) was added with vigorous stirring. After 12 hours, the flask was taken out of the glove box and methanol was added to stop the polymerization. The resulting mixture was poured into methanol (200 ml) to precipitate the polymer. The white polymer powder was collected by filtration and dried under reduced pressure at 60 ° C. until a constant weight was obtained (0.67 g, 1.4 kg copolymer / mol-Sc · h). The resulting product was soluble in THF at room temperature and had a number average molecular weight of 1900 and a molecular weight distribution of 1.58. The glass transition point of the polymer is about 196 ° C. The resulting amorphous polymer is a random copolymer having a 4-methyl-1-pentene content determined by ¹³ C NMR of about 23.0 mol%.
The results are shown in Table 6.

<Example 30>
Example 29 except that the catalyst system is changed to (η ⁵ -C ₅ Me ₅ ) Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ / [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] Polymerization was carried out in the same manner as described above. A 4-methyl-1-pentene-norbornene random copolymer was obtained.
The results are shown in Table 6.

<Example 31>
Example 29 with the exception that the catalyst system was changed to (η ⁵ -C ₅ Me ₄ SiMe ₃ ) Sc (η ³ -C ₃ H ₅ ) ₂ / [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] Polymerization was carried out in the same manner. A 4-methyl-1-pentene-norbornene random copolymer was obtained.
The results are shown in Table 6.

<Example 32>
Except for changing the catalyst system to (η ⁵ -C ₅ Me ₅ ) Sc (η ³ -C ₃ H ₅ ) ₂ / [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ], the same as in Example 29 Polymerization was performed. A 4-methyl-1-pentene-norbornene random copolymer was obtained.
The results are shown in Table 6.

<Example 33>
Example 29 except that the catalyst system is changed to (η ⁵ -C ₅ Me ₅ ) Sc (η ³ -C ₃ H ₄ Me) ₂ / [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] Polymerization was carried out. A 4-methyl-1-pentene-norbornene random copolymer was obtained.
The results are shown in Table 6.

<Example 34>
Polymerization was carried out in the same manner as in Example 29 except that the comonomer supply ratio (4-methyl-1-pentene / norbornene molar ratio) was changed from 1/1 to 2/1. A 4-methyl-1-pentene-norbornene random copolymer was obtained.
The results are shown in Table 6.

<Example 35>
Polymerization was carried out in the same manner as in Example 29 except that the comonomer supply ratio (4-methyl-1-pentene / norbornene molar ratio) was changed from 1/1 to 4/3. A 4-methyl-1-pentene-norbornene random copolymer was obtained.
The results are shown in Table 6.

<Example 36>
Polymerization was carried out in the same manner as in Example 29 except that the comonomer supply ratio (4-methyl-1-pentene / norbornene molar ratio) was changed from 1/1 to 1/2. A 4-methyl-1-pentene-norbornene random copolymer was obtained.
The results are shown in Table 6.

In Table 6, Complex 1 represents (η ⁵ -C ₅ Me ₄ SiMe ₃ ) Sc (η ³ -C ₃ H ₅ ) ₂ , 2 represents (η ⁵ -C ₅ Me ₅ ) Sc (η ³ -C ₃ H ₅ ) ₂ 3 represents (η ⁵ -C ₅ Me ₅ ) Sc (η ³ -C ₃ H ₄ Me) ₂ and 4 represents (η ⁵ -C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ and 5 indicates (η ⁵ -C ₅ Me ₅ ) Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ .
2. The activity is expressed as the number of kg of polymer produced when the reaction is carried out for 1 hour using 1 mol of the complex (in terms of Sc).
The 3.4M1P content was determined by ¹³ C NMR.
4). Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were determined by GPC method against polystyrene standards.
5. The glass transition point (Tg) was determined by the DSC method.

As shown in Table 6, 4-methyl 1-pentene-norbornene copolymer can be produced from the complexes 1 to 5 of the present invention.
It turned out that the 4-methyl 1-pentene content rate in the obtained polymer can be adjusted by adjusting the charging ratio of the monomers. That is, when the ratio of 4-methyl 1-pentene in the charging ratio increases, the content of 4-methyl 1-pentene in the obtained polymer increases. As the 4-methyl 1-pentene content increases, the glass transition temperature tends to decrease.

Example 37 Production of 1-hexene dicyclopentadiene (DCPD) random copolymer (η ⁵ -C ₅ Me ₄ SiMe ₃ ) Sc (CH _{2 in a} glove box in a 20 ml flask at 25 ° C. Dicyclopentadiene (1.32 g, 10 mmol) and 1-hexene (0.84 g, 10 mmol) were added to a toluene solution (2 ml) of C ₆ H ₄ NMe ₂ -o) ₂ (20 mg, 40 μmol) . The mixture was stirred well at room temperature for several minutes, and a solution of [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] (37 mg, 40 μmol) in toluene (3 ml) was added with vigorous stirring. After 12 hours, the flask was taken out of the glove box and methanol was added to stop the polymerization. The resulting mixture was poured into methanol (200 ml) to precipitate the polymer. The white polymer powder was collected by filtration and dried under reduced pressure at 60 ° C. until a constant weight was obtained (1.80 g, 3.8 kg copolymer / mol-Sc · h). The resulting product was soluble in THF at room temperature and had a number average molecular weight of 1400 and a molecular weight distribution of 1.60. The glass transition point of the polymer is about 93 ° C. The resulting amorphous polymer is a random copolymer having a 1-hexene content of about 50.9 mol% as determined by ¹³ C NMR.
The results are shown in Table 7.

<Example 38>
Example 37, except that the catalyst system is changed to (η ⁵ -C ₅ Me ₅ ) Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ / [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] Polymerization was carried out in the same manner as described above. A 1-hexene / dicyclopentadiene random copolymer was obtained.
The results are shown in Table 7.

In Table 7, Complex 4 represents (η ⁵ -C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ , and 5 represents (η ⁵ -C ₅ Me ₅ ) Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂
2. The activity is expressed as the number of kg of polymer produced when the reaction is carried out for 1 hour using 1 mol of the complex (in terms of Sc).
The 3.1-hexene content was determined by ¹³ C NMR.
4). Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were determined by GPC method against polystyrene standards.
5. The glass transition point (Tg) was determined by the DSC method.

  As shown in Table 7, 1-hexene-dicyclopentadiene copolymer can be produced by the complexes 4 and 5 of the present invention.

Example 39 Preparation of 1-octene-dicyclopentadiene random copolymer (η ⁵ -C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ C ₆ H) at 25 ° C. in a 20 ml flask in a glove box. ₄ NMe ₂ -o) ₂ (20 mg, 40 μmol) in toluene (2 ml) was added to dicyclopentadiene (1.50 g, 11.4 g
mmol) and 1-octene (0.96 g, 8.6 mmol) were added. The mixture was stirred well at room temperature for several minutes, and a solution of [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] (37 mg, 40 μmol) in toluene (3 ml) was added with vigorous stirring. After 12 hours, the flask was taken out of the glove box and methanol was added to stop the polymerization. The resulting mixture was poured into methanol (200 ml) to precipitate the polymer. The white polymer powder was collected by filtration and dried under reduced pressure at 60 ° C. until a constant weight was obtained (1.91 g, 4.0 kg copolymer / mol-Sc · h). The resulting product was soluble in THF at room temperature and had a number average molecular weight of 1700 and a molecular weight distribution of 1.57. The glass transition point of the polymer is about 112 ° C. The resulting amorphous polymer is a random copolymer having a 1-hexene content of about 47.4 mol% as determined by ¹³ C NMR.
The results are shown in Table 8.

<Example 40>
Example 39, except that the catalyst system was changed to (η ⁵ -C ₅ Me ₅ ) Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ / [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] Polymerization was carried out in the same manner as described above. A 1-octene-dicyclopentadiene random copolymer was obtained.
The results are shown in Table 8.

In Table 8, Complex 4 represents (η ⁵ -C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ , and 5 represents (η ⁵ -C ₅ Me ₅ ) Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂
2. The activity is expressed as the number of kg of polymer produced when the reaction is carried out for 1 hour using 1 mol of the complex (in terms of Sc).
The 3.1-octene content was determined by ¹³ C NMR.
4). Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were determined by GPC method against polystyrene standards.
5. The glass transition point (Tg) was determined by the DSC method.

  As shown in Table 8, a 1-octene-dicyclopentadiene copolymer can be produced from the complexes 1 and 4 of the present invention.

<Example 41> Production of isoprene-dicyclopentadiene random copolymer (η ⁵ -C ₅ Me ₄ SiMe ₃ ) Sc (η ³ -C ₃ H ₅ ) in a 20 ml flask in a glove box ) to ₂ (8 mg, 25 _μmol toluene solution (2 ml) of), dicyclopentadiene (1.32 g, 10.0 mmol) and isoprene (0.68 g, was added 10.0 mmol). The mixture was stirred well at room temperature for several minutes, and a toluene solution (3 ml) of [PhNHMe ₂ ] [B (C ₆ F ₅ ) ₄ ] (20 mg, 25 μmol) was added with vigorous stirring. After 15 minutes, the flask was taken out of the glove box and methanol was added to stop the polymerization. The resulting mixture was poured into methanol (200 ml) to precipitate the polymer. The white polymer powder was collected by filtration and dried under reduced pressure at 60 ° C. until a constant weight was obtained (0.68 g, 1.1 × 10 ⁵ g copolymer / mol-Sc · h). The resulting product was soluble in THF at room temperature with a number average molecular weight of 29800 and a molecular weight distribution of 1.54. The glass transition point of the polymer is about 112 ° C. The resulting amorphous polymer is a random copolymer having a DCPD content of about 8.2 mol% as determined by ¹³ C NMR.
The results are shown in Table 9.

<Example 42>
Example except that the catalyst system is changed to (η ⁵ -C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ / [PhNHMe ₂ ] [B (C ₆ F ₅ ) ₄ ] Polymerization was carried out in the same manner as in 41. An isoprene / dicyclopentadiene random copolymer was obtained.
The results are shown in Table 9.

In Table 9, Complex 1 represents (η ⁵ -C ₅ Me ₄ SiMe ₃ ) Sc (η ³ -C ₃ H ₅ ) ₂ and 4 represents (η ⁵ -C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂
2. The activity is expressed as the number of grams of polymer produced when the reaction is carried out for 1 hour using 1 mol of the complex (in terms of Sc).
3. The DCPD content was determined by ¹³ C NMR.
4). Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were determined by GPC method against polystyrene standards.
5. The glass transition point (Tg) was determined by the DSC method.

  As shown in Table 9, isoprene-dicyclopentadiene copolymers can be produced from the complexes 1 and 4 of the present invention.

  By using the polymerization catalyst composition of the present invention, new methods for producing various polymer compounds are provided, and new polymer compounds are further provided.

4 is a GPC profile of a copolymer of isoprene and norbornene obtained in Example 2. 2 is a DSC curve of a copolymer of isoprene and norbornene obtained in Example 2. 3 is a ¹³ C-NMR spectrum chart of the isoprene polymer obtained in Reference Example 1 and the copolymer of isoprene and norbornene obtained in Example 2. FIG. 3 is an enlarged view (δ0-60 ppm) of a ¹³ C-NMR spectrum chart of the isoprene polymer obtained in Reference Example 1 and the copolymer of isoprene and norbornene obtained in Example 2. FIG. 2 is a ¹ H-NMR spectrum chart of a copolymer of isoprene and norbornene obtained in Example 2. FIG. It is the graph which plotted the 1-hexene content in the copolymer of 1-hexene and norbornene obtained in Example 8, 14-19, and the glass transition point of a copolymer. It is the graph which plotted the 1-octene content in the copolymer of 1-octene obtained in Example 20, 25-28, and the glass transition point of a copolymer. It is the graph which plotted the 4-methyl-1-pentene content in the copolymer of 4-methyl-1-pentene and norbornene obtained in Examples 29 and 34-36 and the glass transition point of the copolymer. It is a ¹³ C-NMR spectrum chart of the copolymer of 1-octene and norbornene obtained in Examples 20 and 25-28. It is a ¹³ C-NMR spectrum chart of the copolymer of 1-hexene and norbornene obtained in Examples 8 and 15-19. It is a ¹³ C-NMR spectrum chart of a copolymer of 4-methyl-1-pentene and norbornene obtained in Examples 29 and 34-36. 6 is a ¹³ C-NMR spectrum chart of a copolymer of 1-hexene and dicyclopentadiene obtained in Example 37. FIG. 4 is a ¹³ C-NMR spectrum chart of a copolymer of 1-octene and dicyclopentadiene obtained in Example 40. FIG. 4 is a ¹ H-NMR spectrum chart of a copolymer of isoprene and dicyclopentadiene obtained in Example 42. FIG. 4 is a ¹³ C-NMR spectrum chart of a copolymer of isoprene and dicyclopentadiene obtained in Example 42. FIG.

Claims (6)

(A) a method for producing a copolymer of an α-olefin compound and a cyclic olefin compound, or (b) a diene compound and a cyclic olefin compound,
1) a metallocene complex represented by the general formula (I), and
2) an ionic compound comprising a non-coordinating anion and a cation,
A method for carrying out polymerization in the presence of a polymerization catalyst composition comprising:

(Where
M represents scandium ;
Cp ^* represents a ligand comprising a substituted or unsubstituted cyclopentadienyl derivative;
Q ¹ and Q ² each independently represent a substituted or unsubstituted hydrocarbyl group . ) Formula Q ¹ and Q ² in (I) is the general formula each independently: (. In the formula, R ^1, each independently represent hydrogen or an alkyl group) η _³ -C ³ R ¹ ₅ is shown in group The manufacturing method according to claim 1 , wherein: Q ¹ and Q ² in the general formula (I) are each independently a general formula: CH ₂ C ₆ R ² ₄ ER ³ _n -o (wherein R ² independently represents a hydrogen atom or an alkyl group; E Represents N, P, As, O, or S; each R ³ independently represents an alkyl group or an aryl group; and n is 1 or 2. The manufacturing method according to claim 1. The production method according to claim 3 , wherein E in the general formula: CH ₂ C ₆ R ² ₄ ER ³ _n -o is N. A metallocene complex represented by the general formula (A).

(Where
M represents scandium ;
Cp ^* represents a ligand comprising a substituted or unsubstituted cyclopentadienyl derivative;
R ¹ independently represents hydrogen or an alkyl group. ) 1) The metallocene complex according to claim 5 , and
2) an ionic compound comprising a non-coordinating anion and a cation,
A polymerization catalyst composition comprising:

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