JP2003252963A - Catalyst for ring-opening metathesis polymerization and method for producing norbornene-based ring-opened polymer using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst for ring-opening metathesis polymerization that gives a norbornene-based ring-opened polymer having a narrow molecular weight distribution and a method for producing a norbornene-based ring-opened polymer using the catalyst. <P>SOLUTION: The catalyst for ring-opening metathesis polymerization of a norbornene-based monomer comprises (A) a transition metal compound represented by formula (1) (wherein M denotes a molybdenum atom or a tungsten atom; R<SP>1</SP>-R<SP>4</SP>denote each independently a hydrogen atom, a halogen atom, a 1-12C alkyl group, an aryl group or the like; X denotes a halogen atom, an oxygen atom or the like; m denotes 1, 2 or 3; and n is a number satisfying a valence number of M) and (B) an organometallic reducing agent. The method for producing a norbornene-based ring-opened polymer comprises polymerizing the norbornene-based monomer in the presence of the catalyst for the ring- opening metathesis polymerization. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a catalyst for ring-opening metathesis polymerization of a norbornene-based monomer, and a method for producing a norbornene-based ring-opening polymer using this catalyst.

[0002]

2. Description of the Related Art Conventionally, for example, WCl ₆ or MoCl
₅ , a polymerization catalyst obtained from a halide such as ₅ and an organic tin such as tetraphenyltin or tetra (n-butyl) tin, an oxyhalide such as WOCl ₄ or MoOCl ₄ and triethylaluminum, diethylaluminum chloride, ethylaluminum dichloride Ziegler type polymerization catalysts such as those obtained from organoaluminum are widely known as catalysts for ring-opening metathesis polymerization of norbornene monomers. ('Olefin
Metathesis and Metathesis
Polymerization'K. J. Ivan,
J. C. Mol, 1997, ACADEMIC P
RESS, TOKYO, etc. ).

However, although the above-mentioned polymerization catalyst exhibits high polymerization activity, there is a problem that a norbornene-based ring-opening polymer having a wide molecular weight distribution is likely to be formed and the use of the polymer is restricted.

In recent years, a norbornene ring-opening polymer having more excellent physical properties (heat resistance, etc.) has been demanded, and development of a method for producing a norbornene ring-opening polymer having a narrow molecular weight distribution has been desired. It was

[0005]

SUMMARY OF THE INVENTION The present invention has been made under the above circumstances, and a ring-opening metathesis polymerization catalyst that gives a norbornene-based ring-opening polymer having a narrow molecular weight distribution, and a norbornene-based opening catalyst using this catalyst. An object is to provide a method for producing a ring polymer.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a polymerization catalyst obtained from a (substituted) catecholate complex of molybdenum and tungsten and an organometallic reducing agent. It was found that a norbornene-based ring-opening polymer having a molecular weight distribution (Mw / Mn) of 2 or less can be obtained by polymerizing a norbornene-based monomer by using, and the present invention has been completed.

Thus, according to the first aspect of the present invention, (A)
Formula (1)

[0008]

[Chemical 2]

(In the formula, M represents a molybdenum atom or a tungsten atom. R ^{1 to} R ⁴ are each independently,
It represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group, a haloalkyl group having 1 to 12 carbon atoms, or a cyano group. R ¹ and R ² , R ² and R ³ , or R ³ and R ⁴ may be bonded to each other to form a ring structure. X represents a halogen atom, an oxygen atom, an alkoxy group or an aryloxy group. m represents 1, 2 or 3,
n is a number that satisfies the valence of M. The present invention provides a catalyst for ring-opening metathesis polymerization of a norbornene-based monomer, which comprises a transition metal compound represented by (4) and (B) an organometallic reducing agent.

According to the second aspect of the present invention, a norbornene-based ring-opening polymer is produced by polymerizing a norbornene-based monomer in the presence of the ring-opening metathesis polymerization catalyst of the present invention. Will be provided.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, preferred embodiments of the present invention will be divided into 1) a catalyst for ring-opening metathesis polymerization of a norbornene-based monomer, and 2) a method for producing a norbornene-based ring-opening polymer. The details will be described.

1) Catalyst for Ring-Opening Metathesis Polymerization of Norbornene Monomer The polymerization catalyst of the present invention comprises (A) a transition metal compound represented by the above formula (1), and (B) an organometallic reducing agent. Consists of.
The transition metal compound represented by the formula (1), which is the component (A), is a molybdenum compound or a tungsten compound having a (substituted) catecholate as a ligand.

In the above formula (1), R ^{1 to} R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, an alkoxy group having 1 to 12 carbon atoms, or aryl. It represents an oxy group, a haloalkyl group having 1 to 12 carbon atoms or a cyano group.

Specific examples of R ^{1 to} R ⁴ include a hydrogen atom;
Halogen atom such as fluorine, chlorine, bromine; methyl group, ethyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group and the like having 1 to 12 carbon atoms Alkyl group of phenyl group, 2-isopropylphenyl group, 2,6-dimethylphenyl group, mesityl group, tetrafluorophenyl group,
2,4,6-trichlorophenyl group, 1-naphthyl group,
Aryl group such as 2-naphthyl group; C1-C12 alkoxy group such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, tert-butoxy group; phenoxy group, 2,6 -Aryloxy groups such as dimethylphenyloxy group, 2,4,6-trimethylphenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group; chloromethyl group, trifluoromethyl group, 2-chloroethyl group, 2, A haloalkyl group having 1 to 12 carbon atoms such as a 2,2-trifluoroethyl group; a cyano group; and the like.

Of these, R ^{1 to} R ⁴ are each independently preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms or an aryl group.

M represents 1, 2 or 3. That is,
One to three (substituted) catecholates can be bonded to one molybdenum atom or one tungsten atom.

X represents a halogen atom, an oxygen atom, an alkoxy group or an aryloxy group. Examples of the halogen atom include fluorine, chlorine and bromine, examples of the alkoxy group include a methoxy group, ethoxy group and isopropoxy group, and examples of the aryloxy group include a phenoxy group and a 4-methylphenyloxy group. be able to. Among these, X is preferably a halogen atom or an oxygen atom in order to achieve the object of the present invention.

The number n, that is, the number of bonds of X to the molybdenum atom or the tungsten atom, is a number satisfying the valences of molybdenum and tungsten as the central metal M.

A transition metal compound represented by the above formula (1)
Are known methods, for example, (i) Inorg. Che
m. ，25, 1962 (1986),
(ii) (Substituted) catechol and molybdenum halide
(Hereinafter referred to as “Mo halide”) or tongue
Stain halide (hereinafter referred to as "W halide"
U ) And in a solution, (iii) Chemi
story Letters. , 691 (1996)
Bis (trimethylsiloxy) benzene described in
And Mo halides and W halides in solution
It can be synthesized by a reaction method or the like. here
As Mo halide or W halide used in
Is, for example, MoCl₅, MoOCl_Four, WCl₆, W
OCl_Four, WO _TwoCl_TwoAnd so on.

Further, in the above formula (1), the compound in which X is an alkoxy group or an aryloxy group includes a compound represented by the above formula (1) in which X is a halogen atom and a metal alkoxide or a metal phenoxide. It can also be obtained by reacting.

The transition metal compound represented by the above formula (1) can be isolated by adding a reaction solution to an insoluble organic solvent, for example, saturated hydrocarbon such as n-pentane or n-hexane to cause precipitation. You can Further, the residue or reaction solution obtained by distilling off the solvent used in the reaction can be used as it is for the preparation of the polymerization catalyst of the present invention.

The transition metal compound represented by the formula (1) which is the component (A) becomes a highly active polymerization catalyst when combined with the organometallic reducing agent which is the component (B). As the organometallic reducing agent, for example, an organometallic compound of Groups 1, 2, 12, 13, and 14 of the periodic table having a hydrocarbon group having 1 to 20 carbon atoms can be used. Among them, organolithium, organomagnesium, organozinc, organoaluminum,
The use of organotin is preferred, and the use of organolithium, organoaluminum, organotin is particularly preferred.

Examples of the organolithium include n-butyllithium, methyllithium, phenyllithium, neopentyllithium, neophylllithium and the like. Examples of the organomagnesium include butylethylmagnesium, butyloctylmagnesium, dihexylmagnesium, ethylmagnesium bromide, n-butylmagnesium chloride, allylmagnesium bromide, neopentylmagnesium chloride and neophyllmagnesium chloride. Examples of the organic zinc include dimethyl zinc, diethyl zinc, diphenyl zinc and the like.

Examples of the organic aluminum include alkyl aluminum such as trimethyl aluminum, triethyl aluminum and triisobutyl aluminum; alkyl aluminum halides such as diethyl aluminum chloride, ethyl aluminum sesquichloride and ethyl aluminum dichloride; and the like. Examples of the organic tin include tetramethyl tin and tetra (n-).
Butyl) tin, tetraphenyl tin, and the like.

Further, in the present invention, a conventionally known aluminoxane obtained by the reaction of the above organoaluminum and water can be used as the organometallic reducing agent. Examples of the aluminoxane include methylaluminoxane, modified methylaluminoxane, dry methylaluminoxane, butylaluminoxane, and the like.

The amount of the organometallic reducing agent added varies depending on the organometallic reducing agent used, but the molar ratio of the metal (in the polymerization catalyst (A) component: the organometallic reducing agent) is 1: 0.1-1.
10,000 is preferable, 1: 0.2 to 5,000 is more preferable, and 1: 0.5 to 2,000 is particularly preferable. If the amount added is too small, the polymerization activity may be insufficient. On the other hand, if the addition amount is too large, the polymerization activity is saturated, but side reactions are likely to occur.

The catalyst is usually prepared by mixing the above components in an organic solvent. The organic solvent used is not particularly limited as long as it can dissolve or disperse each component and is not affected by the reaction, but an industrially used solvent is preferable.

Specific examples of such an organic solvent include aliphatic hydrocarbons such as pentane, hexane and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, Alicyclic hydrocarbons such as decahydronaphthalene, bicycloheptane, tricyclodecane, hexahydroindene, cyclooctane; benzene, toluene,
Aromatic hydrocarbons such as xylene; Halogen-based aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; Halogen-containing aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; Nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile System solvent;
Aliphatic ether solvents such as diethyl ether and tetrahydrofuran; aromatic ether solvents such as anisole and phenetole can be used. Among these, readily available aromatic hydrocarbon-based solvents and aliphatic hydrocarbon-based solvents, alicyclic hydrocarbon-based solvents, aliphatic ether-based solvents, aromatic ether-based solvents are preferable, and use of aromatic ether-based solvents Is particularly preferable. The prepared solution or dispersion of the catalyst can be used as it is for the polymerization reaction.

2) Method for producing norbornene ring-opening polymer The second aspect of the present invention is a method for producing a norbornene ring-opening polymer, which comprises using the polymerization catalyst of the present invention.
Examples of the norbornene-based monomer used for ring-opening metathesis polymerization in the production method of the present invention include norbornenes, dicyclopentadiene, tetracyclododecene, and the like. These may be substituted with a hydrocarbon group such as an alkyl group, an alkenyl group, an alkylidene group or an aryl group, or a polar group. In addition to the double bond of the norbornene ring, it may further have a double bond.

Specific examples of the norbornene-based monomer include:
Dicyclopentadiene, methyl-dicyclopentadiene
Dihydrodicyclopentadiene (tricyclo [4.
3.1 ^2,5． 0] -deca-3-ene) etc.
Interdiene;

Tetracyclododecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 8
-Cyclohexyltetracyclododecene, 8-cyclopentyltetracyclododecene, 8-methylidenetetracyclododecene, 8-ethylidenetetracyclododecene,
8-vinyltetracyclododecene, 8-propenyltetracyclododecene, 8-cyclohexenyltetracyclododecene, 8-cyclopentenyltetracyclododecene, 8-phenyltetracyclododecene, 8-methoxycarbonyltetracyclododecene , 8-methyl-8-methoxycarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, 8-carboxytetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid, tetracyclododecene-8, Tetracyclodo such as 9-dicarboxylic acid anhydride, 8-cyanotetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid imide, 8-chlorotetracyclododecene and 8-trimethoxysilyltetracyclododecene Decenes;

Norbornene, 5-methylnorbornene,
5-ethyl norbornene, 5-butyl norbornene, 5
-Hexyl norbornene, 5-decyl norbornene, 5
-Cyclohexyl norbornene, 5-cyclopentylno
Lebornene, 5-ethylidene norbornene, 5-vinyl
Norbornene, 5-propenyl norbornene, 5-shik
Rohexenyl norbornene, 5-cyclopentenyl nor
Bornene, 5-phenylnorbornene, tetracyclo
[6.5.1^2,5． 0^1,6． 0^{8, 13}] Trideca
-3,8,10,12-tetraene (1,4-methano-
Also known as 1,4,4a, 9a-tetrahydrofluorene
U), tetracyclo [6.6.1]^2,5． 0 ^1,6． 0
^{8, 13}] Tetradeca-3,8,10,12-tetrae
(1,4-methano-1,4,4a, 5,10,10a
-Hexahydroanthracene), 5-methoxy
Carbonyl norbornene, 5-ethoxycarbonyl nor
Borne, 5-methyl-5-methoxycarbonyl norbo
Lunene, 5-methyl-5-ethoxycarbonyl norbol
Nene, norbornenyl-2-methylpropionate, no
Lebornenyl-2-methyl octanate, norbornene
-5,6-dicarboxylic anhydride, 5-hydroxymethyl
Norbornene, 5,6-di (hydroxymethyl) norbo
Lunene, 5,5-di (hydroxymethyl) norborne
5-hydroxy-i-propylnorbornene, 5,
6-dicarboxynorbornene, 5-methoxycarboni
Norbornenes such as le-6-carboxynorbornene;

Oxanorbornene, 5-methyloxanorbornene, 5-ethyloxanorbornene, 5-butyloxanorbornene, 5-hexyloxanorbornene, 5-decyloxanorbornene, 5-cyclohexyloxanorbornene, 5-cyclopentyloxanorbornene, 5- Phenyloxanorbornene, 5-ethylideneoxanorbornene, 5-vinyloxanorbornene, 5-propenyloxanorbornene, 5-cyclohexenyloxanorbornene, 5-cyclopentenyloxanorbornene, 5-methoxycarbonyloxanorbornene, 5-ethoxycarbonyloxanorbornene, 5-methyl-5-methoxycarbonyloxanorbornene, 5-methyl-5-ethoxycarbonyloxanorbornene, oki Norbornenyl-2-methylpropionitrile Nate, oxa norbornenyl-2-methyl oct Nate, oxanorbornene 5,6-dicarboxylic anhydride, 5-hydroxymethyl-oxa-norbornene, 5,6
-Di (hydroxymethyl) oxanorbornene, 5,5
-Di (hydroxymethyl) oxanorbornene, 5-hydroxy-i-propyloxanorbornene, 5,6-
Oxanorbornenes such as dicarboxyoxanorbornene, 5-methoxycarbonyl-6-carboxyoxanorbornene, 5-cyanooxanorbornene, oxanorbornene-5,6-dicarboxylic acid imide;

Hexacycloheptadecene, 12-methylhexacycloheptadecene, 12-ethylhexacycloheptadecene, 12-butylhexacycloheptadecene, 12-hexylhexacycloheptadecene, 12-
Decylhexacycloheptadecene, 12-cyclohexylhexacycloheptadecene, 12-cyclopentylhexacycloheptadecene, 12-ethylidenehexacycloheptadecene, 12-vinylhexacycloheptadecene, 12-propenylhexacycloheptadecene, 12
-Cyclohexenyl hexacycloheptadecene, 12-
Hexacycloheptadecenes such as cyclopentenyl hexacycloheptadecene; and the like. These norbornene-based monomers can be used alone or in combination of two or more.

(Solvent) The polymerization reaction of the norbornene-based monomer is usually carried out in an organic solvent. As the organic solvent used,
The norbornene-based monomer and the norbornene-based ring-opening polymer are not particularly limited as long as they dissolve or disperse under predetermined conditions and do not affect the polymerization, and the same solvents as those used for preparing the above-mentioned catalyst can be mentioned. You can

(Polymerization Method) In the method of the present invention, the ratio of the polymerization catalyst to the monomer is (Mo in the polymerization catalyst is
Alternatively, the molar ratio of W: monomer) is usually 1:50 to 1:
2,000,000, preferably 1: 100 to 1.00
10,000, more preferably 1: 100 to 1: 500,
It is 000. If the amount of the catalyst used is too large, it becomes difficult to remove the catalyst, and if it is too small, sufficient polymerization activity cannot be obtained.

When the ring-opening metathesis polymerization is carried out in a solvent, the concentration of the norbornene-based monomer in the solution is preferably 1 to 50% by weight, more preferably 2 to 45% by weight, and 3 to 3% by weight.
40% by weight is particularly preferred. If the concentration of the monomer is 1% by weight or less, the productivity will be poor. On the contrary, when it is 50% by weight or more, the viscosity of the solution after polymerization is too high and the subsequent hydrogenation reaction becomes difficult.

The polymerization reaction is started by mixing the monomer and the polymerization catalyst. The polymerization temperature is not particularly limited, but is generally -30 to + 200 ° C, preferably 0 to +18.
It is 0 ° C. The polymerization time is not particularly limited, but is usually 1
Minutes to 100 hours.

In the present invention, the molecular weight of the obtained ring-opening polymer can be controlled more precisely by adding an appropriate amount of a vinyl compound or a diene compound to the reaction solution during the polymerization of the norbornene-based monomer. be able to.

The vinyl compound used is not particularly limited as long as it is an organic compound having a vinyl group. Specifically, α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; styrenes such as styrene and vinyltoluene; vinyl ethers such as ethyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; Examples thereof include halogen-containing vinyl compounds such as allyl chloride; oxygen-containing vinyl compounds such as allyl acetate, allyl alcohol, and glycidyl methacrylate; nitrogen-containing vinyl compounds such as acrylamide.

As the diene compound, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene,
Non-conjugated dienes such as 1,6-heptadiene, 2-methyl-1,4-pentadiene and 2,5-dimethyl-1,5-hexadiene; 1,3-butadiene, 2-methyl-1,
Examples thereof include conjugated dienes such as 3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene.

The addition amount of the vinyl compound or the diene compound varies depending on the intended molecular weight, but usually, it can be arbitrarily selected from 0.1 to 10 mol% based on the monomer.

After completion of the polymerization, a reaction terminator such as methanol is added to the reaction solution to stop the polymerization reaction, and the obtained reaction solution is poured into a large amount of insoluble solvent (methanol or the like) to remove the polymer. The polymer can be isolated by aggregating as an insoluble matter, and centrifuging or filtering. The molecular weight of the isolated polymer is, for example, gel permeation
It can be measured by a chromatography (GPC) method or the like.

[0044]

EXAMPLES The present invention will be described more specifically below with reference to Examples and Comparative Examples. The present invention is not limited to the examples below. (1) The molecular weight and dispersion ratio (Mw / Mn) of the norbornene ring-opening polymer are gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.
It was measured as a polystyrene conversion value according to. (2) The ratio of cis bonds (cis content) in all double bonds of the norbornene ring-opening polymer was determined by ¹ H-NMR measurement.

Reference Example 1 Monocatecholate tungsten
Synthesis of tetrachloride In a glass reactor equipped with a stirrer, which was replaced with high-purity argon,
Catechol 12.0 g (109 mmol) and tetrahydrofuran 100 ml were added. A solution of 13.9 g (218 mmol) of n-butyllithium in n-hexane was added thereto, and the resulting mixture was stirred at room temperature for 1.5 hours. Then, add chlorotrimethylsilane 3 to the reaction solution.
5.5 g (327 mmol) was added dropwise. The reaction proceeded rapidly and insoluble matter was produced. A solution was obtained by removing the precipitated insoluble matter by centrifugation. The solvent was distilled off under reduced pressure from the solution, and the resulting residue was dried at 56 ° C. and 0.1 kPa.
A colorless transparent oil was obtained by vacuum distillation at. This is designated as compound a.

The ¹ H-NMR spectrum of the compound a was as follows. ¹ H-NMR (CDCl ₃ , δppm); 6.84
(S, 4H), 0.26 (s, 18H). From the above, the compound a is 1,2-C ₆ H ₄ (OSiM
e ₃ ) ₂ was identified. The yield was 77%.

Then, 2.12 g of tungsten hexachloride was placed in a glass reactor equipped with a stirrer, which was replaced with high-purity argon.
(5.3 mmol) and 60 ml of toluene were added, and the mixture was cooled to -78 ° C while stirring. Where 1,2-C ₆
H ₄ (OSiMe ₃ ) 1.57 ml (5.5 mmo
1) was added, the resulting mixture was gradually warmed to room temperature with stirring, and the reaction was carried out for 1 hour. Further, the reaction was carried out for 2 hours under reflux conditions. After completion of the reaction, the solvent was distilled off under reduced pressure to dissolve the fine crystals remaining in the glass reactor in toluene / n-hexane, and the resulting solution was recrystallized at -20 ° C to give a dark solution. A green powdery compound b was obtained.

The ¹ H-NMR spectrum of the compound b was as follows. ¹ H-NMR (C ₆ D ₆ , δppm); 5.37
(M, 2H), 4.44 (m, 2H). From this, the compound b was identified as monocatecholate tungsten tetrachloride ((C6H4O2) WCl4). The yield was 68%.

Reference Example 2 Bis (3,5-di-tert-)
Butyl) catecholate Tungsten dichloride synthesis In a glass reactor equipped with a stirrer, which was replaced with high-purity argon,
1.74 g (4.40 mmol) of tungsten hexachloride and 45 ml of benzene were added and stirred. Where 3,
1.96 g of 5-di-tert-butylcatechol (8.
A solution of 80 mmol) dissolved in 45 ml of benzene was added while stirring in the glass reactor. The resulting mixture was stirred and reacted at room temperature for 24 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the pressure was further reduced at 90 ° C. to completely remove volatile components, whereby a dark green powdery compound c was obtained.

The ¹ H-NMR spectrum of the compound c was as follows. ¹ H-NMR (C ₆ D ₆ , δppm); 7.08 (b
rs, 1H), 6.62 (brs, 1H), 1.34
(Brs, 9H), 1.11 (brs, 9H).

The result of elemental analysis of this compound c is carbon:
It was 48.2 (wt%) and hydrogen: 5.8 (wt%). The elemental analysis results are calculated values of bis (3,5-di-tert-butyl) catecholate tungsten dichloride (carbon: 48.4 (wt%), hydrogen: 5.8 (wt).
%)). From the above, the compound c was identified as bis (3,5-di-tert-butyl) catecholate tungsten dichloride. The yield is 82%
Met.

Example 1 Monocatecholate tungsten
A catalyst composed of tetrachloride and triethylaluminum
Preparation of medium and polymerization of norbornene In a glass reactor equipped with a stirrer, 8.68 mg (0.02 mmol, monocatecholate tungsten tetrachloride) was added.
10 mmol / L equivalent) and toluene 1.0
A uniform solution was prepared by adding ml and stirring.
The solution was cooled to −78 ° C. with stirring, and 2.28 mg (0.02 mmol, triethylaluminum) was added thereto.
Solution of 0.1 mmol / L) in toluene.
The catalyst was prepared by adding 5 ml and stirring for 10 minutes.

The glass reactor containing the resulting mixture was warmed to room temperature, whereupon 188 mg norbornene (2 m
(0.5 mol / L, 1.0 mol / L equivalent) was added to 0.5 ml of a solution of toluene to start the polymerization reaction. After reacting for 10 minutes at room temperature, methanol was added to the reaction solution to stop the polymerization reaction. The product was aggregated with a large amount of methanol, and the insoluble portion was recovered by centrifugation. The yield was 69%, and the number average molecular weight (Mn) was 1,37.
50,000, the dispersion ratio (Mw / Mn) was 1.7, and the cis content was 42%.

Examples 2 to 4 A catalyst comprising monocatecholate tungsten tetrachloride and another organometallic reducing agent was prepared, and norbornene was polymerized in the same manner as in Example 1. Type of organometallic reducing agent used, reaction molar ratio, reaction temperature, yield, number average molecular weight (Mn) of the obtained norbornene ring-opening polymer, M
The value of w / Mn and the cis content are shown in Table 1 including the case of Example 1.

[0055]

[Table 1]

Example 5 Bis (3,5-di-tert-)
Butyl) catecholate tungsten dichloride and Trier
Preparation and catalyst of chill aluminum catalyst
Polymerization of bis (3,5-di-ter) in a glass reactor equipped with a stirrer.
t-Butyl) catecholate tungsten dichloride 1
3.9 mg (0.02 mmol, 10 mmol / L equivalent) was added, 1.0 ml of toluene was further added, and the mixture was stirred to form a uniform solution. This solution was cooled to −78 ° C. with stirring, and 0.5 ml of a solution in which 2.28 mg (0.02 mmol, 10 mmol / L equivalent) of triethylaluminum was dissolved in toluene was added thereto, and the mixture was stirred for another 10 minutes to prepare a catalyst. Was prepared.

The glass reactor containing the resulting mixture was warmed to room temperature, where 188 mg norbornene (2 m
mol, 1.0 mol / L) was added to 0.5 ml of a solution of toluene to start the polymerization reaction. After reacting for 10 minutes at room temperature, the polymerization reaction was stopped with methanol. The product was aggregated with a large amount of methanol, and the insoluble portion was recovered by centrifugation. Yield 49%,
The number average molecular weight (Mn) is 688,000, and the dispersion ratio is 1.
9. The cis content was 86%.

Examples 6 to 8 Bis (3,5-di-tert-butyl) catecholate A catalyst comprising tungsten dichloride and another organometallic reducing agent was prepared and the norbornene polymerization reaction was carried out in the same manner as in Example 5. I did. The type of the organometallic reducing agent used, the reaction molar ratio, the reaction temperature, the yield, the number average molecular weight (Mn) of the obtained norbornene ring-opening polymer, the value of Mw / Mn, and the cis content of Example 5 were measured. The cases are shown in Table 2.

[0059]

[Table 2]

Comparative Example 1 Norbornene was polymerized in the same manner as in Example 1 except that tungsten hexachloride was used instead of monocatecholate tungsten tetrachloride, and the polymerization was instantaneously completed. The yield of polynorbornene is 100%,
The number average molecular weight (Mn) is 468,000, and the dispersion ratio is 8.
It was 6.

[0061]

The present invention provides a catalyst for ring-opening metathesis polymerization which gives a norbornene-based ring-opening polymer having a narrow molecular weight distribution, and a method for producing a norbornene-based ring-opening polymer using this catalyst.

Claims (2)

[Claims] 1. A formula (1): (In the formula, M represents a molybdenum atom or a tungsten atom. R ^{1 to} R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, or 1 to 12 carbon atoms. It represents an alkoxy group, an aryloxy group, a haloalkyl group having 1 to 12 carbon atoms, or a cyano group, and R ¹ and R ² , R ² and R ³ , or R ³ and R.
⁴ may combine with each other to form a ring structure. X represents a halogen atom, an oxygen atom, an alkoxy group or an aryloxy group. m represents 1, 2 or 3, and n is a number satisfying the valence of M. ) A transition metal compound represented by
(B) A catalyst for ring-opening metathesis polymerization of a norbornene-based monomer comprising an organometallic reducing agent. 2. A method for producing a norbornene ring-opening polymer, which comprises polymerizing a norbornene monomer in the presence of the catalyst for ring-opening metathesis polymerization according to claim 1.