JPH10130311A - Catalyst for polymerizing cyclic olefins and production of cyclic olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cyclic olefin polymerization catalyst capable of realizing a high cyclic olefin conversion in an extremely small amount, and to provided a method for producing a high mol.wt. cyclic olefin polymer. SOLUTION: This catalyst for polymerizing a cyclic olefin comprises (A) a transition metal compound, (B) a compound capable of reacting with the transition metal compound to form an ionic complex, and (C) water or an acid. A method for producing the cyclic olefinic polymer comprises polymerizing a cyclic olefin in the presence of the catalyst. This method for producing the cyclic olefinic polymer comprises polymerizing the cyclic olefin in the presence of a catalyst comprising (A) the transition metal compound and (B) the compound capable of reacting with the transition metal component to form the ionic complex in water as a dispersing medium.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a catalyst for polymerization of cyclic olefins and a method for producing a cyclic olefin polymer.

[0002]

2. Description of the Related Art It is known that cyclic olefins represented by norbornene are polymerized by various polymerization methods to give a cyclic olefin polymer mainly composed of an addition structure. Such a cyclic olefin polymer generally has a higher glass transition temperature than an acyclic olefin polymer, and is expected to be used as a film or various molded products as a high heat-resistant resin. I have.

[0003] Various methods are known for producing such cyclic olefin polymers. For example, for norbornene-based polymers, US Pat. No. 3,330,815 has proposed a method using Pd (C ₆ H ₅ CN) ₂ Cl ₂ as a catalyst, and Japanese Unexamined Patent Publication No. 4-63807 discloses a transition metal. A method using a catalyst comprising a compound component and an aluminoxane component has been proposed. However, the former has a problem of low catalytic activity, and the latter requires the use of a large amount of aluminoxane, so that a large amount of metal remains in the polymer, causing deterioration and coloring of the polymer. There was a problem.

JP-A-5-262821 discloses a catalyst comprising a transition metal compound component and a compound component which reacts with the transition metal compound to form an ionic complex.
A method for producing a cyclic olefin-based polymer including a copolymer has been proposed. This method is an excellent method in that a relatively high catalytic efficiency can be achieved without using a large amount of a cocatalyst such as aluminoxane, but the conversion of cyclic olefins is low, and in many cases, as a cocatalyst, It is not yet sufficient in that it requires the use of organoaluminum compounds that are difficult to handle.

As a method for solving such a problem, Japanese Patent Application Laid-Open No. 7-304834 discloses a cyclic method using a catalyst containing as a main component a compound which reacts with a palladium compound and a transition metal compound to form an ionic complex. A method for producing an olefin polymer has been proposed. Although this method is excellent as a method capable of polymerizing cyclic olefins at a high conversion, industrially, it has been desired to further increase the catalytic activity and improve the molecular weight of the obtained polymer.

On the other hand, studies have been made on adding water to a polymerization system of cyclic olefins using a transition metal compound. For example, Macromol. Symp. 89,433 (1995)
In the polymerization of norbornene using [Pd (CH ₃ CH ₂ CN) ₄ ] [BF ₄ ] ₂ as a catalyst, it has been proved that a polymer can be obtained even when water is added. The molecular weight of the union is lower than that of the non-added system.
As described above, it is a fact that a commercially satisfactory method has not yet been found for a cyclic olefin polymer.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances. That is, an object of the present invention is to provide a catalyst for polymerizing a cyclic olefin which realizes a high conversion of a cyclic olefin with a very small amount of a catalyst, and a method for producing a high molecular weight cyclic olefin-based polymer.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found a catalyst obtained by further adding water or an acid as a component to a specific catalyst system, and completed the present invention. Reached. That is, the present invention provides (A) a transition metal compound, (B) a compound which reacts with a transition metal compound to form an ionic complex, and (C) a catalyst for polymerizing cyclic olefins containing water or an acid; The present invention relates to a method for producing a cyclic olefin polymer in which a cyclic olefin is polymerized using a catalyst. Further, the present invention provides a method for polymerizing a cyclic olefin using water as a dispersion solvent, using a catalyst containing (A) a transition metal compound and (B) a compound which reacts with the transition metal compound to form an ionic complex. The present invention relates to a method for producing a cyclic olefin polymer.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (1) Cyclic olefins The cyclic olefins used in the present invention are those having four or more carbon atoms which may have various substituents form a ring, and one carbon-carbon atom in the ring. A compound containing a double bond. Examples of such cyclic olefins include monocyclic olefins such as cyclobutene, cyclopentene and cyclohexene; substituted monocyclic olefins such as 3-methylcyclopentene and 3-methylcyclohexene; polycyclic olefins such as norbornene and 1,2-dihydrodicyclopentadiene. A substituted polycyclic olefin such as 1-methylnorbornene and 5-methylnorbornene.

Preferred among these are cyclic olefins
Is a compound represented by the following general formula [I].(Where R¹~ R¹²Are each independently a hydrogen atom, halogen
Atom, hydroxyl group, amino group and 1-20 carbon atoms
A substituent selected from the group consisting of organic groups; ^Five, R⁶
And R⁷, R⁸May form a ring. n is an integer of 0 or more
Show. )

Here, the substituent has 1 to 1 carbon atoms.
Specific examples of the organic group of 20 include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group and a dodecyl group; an aryl group such as a phenyl group, a tolyl group and a naphthyl group; Aralkyl groups such as phenethyl group; alkylidene groups such as methylidene group and ethylidene group; alkenyl groups such as vinyl group and allyl group; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; An alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group; an acyloxy group such as an acetyloxy group; a (substituted) silyl group such as a trimethylsilyl group; an alkylamino group such as a dimethylamino group or a diethylamino group; a carboxyl group; And the above alkyl group, aryl group and aralkyl Groups in which some of the hydrogen atoms of the above are substituted with halogen atoms, hydroxyl groups, amino groups, acyl groups, carboxyl groups, alkoxy groups, alkoxycarbonyl groups, acyloxy groups, (substituted) silyl groups, alkylamino groups or cyano groups. be able to.

Preferred substituents are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and 1 carbon atom.
-20 alkylidene group, alkenyl group having 2-20 carbon atoms, acyl group having 1-20 carbon atoms, 1 carbon atom
-20 alkoxycarbonyl groups, 1-20 carbon atoms
And a (substituted) silyl group having 1 to 20 carbon atoms.

Specific examples of preferred cyclic olefins represented by the general formula [I] include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, and tetrabenzylnorbornene. Cyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, ethylidene norbornene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 5-acetylnorbornene, 5-acetyloxy Norbornene, 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5
-Methyl-5-methoxycarbonylnorbornene, 5-
Cyanonorbornene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-methoxycarbonyltetracyclododecene, 8-cyanotetracyclododecene and the like can be mentioned.

In the polymerization, these cyclic olefins are used alone or in combination. Further, in a range not impairing the excellent properties of the cyclic olefin-based polymer, that is, in a range in which the proportion of the cyclic olefins in all the monomers is generally not less than 10% by weight, preferably in a range not less than 50% by weight. Other monomers copolymerizable with the cyclic olefin may be used together with the cyclic olefin. Examples of such other monomers are ethylene,
Propylene, 1-butene, 4-methylpentene-1, 1,
Α-olefins such as hexene and 1-octene; alkenyl aromatic hydrocarbons such as styrene; alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; unsaturated halogenated hydrocarbons such as vinyl chloride; methyl acrylate, ethyl acrylate, methyl methacrylate Α, β-unsaturated carboxylic acid esters; unsaturated nitriles such as acrylonitrile; vinyl carboxylate such as vinyl acetate.

(2) Transition metal compound (A) The component (A) in the catalyst of the present invention is a transition metal compound. Here, the transition metal compound refers to the periodic table (IUPA).
C inorganic chemical nomenclature revised edition, 1989)
A compound having a Group 1 element. Specific examples of the Group 6 to Group 11 elements include chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, and the like. The transition metal compound is not particularly limited as long as it is a compound having these elements. Preferred transition metal compounds are Group 10 transition metal compounds, such as nickel, palladium, and platinum.

Specific examples thereof include inorganic salts of nickel such as nickel chloride, nickel sulfate and nickel perchlorate;
Organic acid salts of nickel such as nickel acetate and nickel oxalate;
Nickel complexes such as nickel acetylacetonate and nickel phthalocyanine; inorganic salts of palladium such as palladium chloride, palladium bromide, palladium iodide, palladium sulfate and palladium nitrate; palladium such as palladium acetate, palladium trifluoroacetate and palladium cyanide Organic acid salt of palladium acetylacetonate, bis (allyl) palladium, dichloro (1,5-cyclooctadiene) palladium, dichlorobis (acetonitrile) palladium, dichlorobis (benzonitrile) palladium, carbonyltris (triphenylphosphine)
Palladium, dichlorobis (triethylphosphine) palladium, diacetbis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, dichloro [1,2-bis (diphenylphosphino) ethane] palladium, bis [1,2-bis (diphenyl) Phosphino) ethane] palladium, tetraamine palladium nitrate, tetrakis (acetonitrile) palladium tetrafluoroborate, etc .; inorganic salts of platinum such as platinum chloride and platinum iodide; platinum complexes such as platinum acetylacetonate; Can be mentioned. Of these, preferred Group 10 transition metal compounds are palladium compounds and nickel compounds, and more preferred Group 10 transition metal compounds are palladium compounds. Particularly preferred transition metal compounds (A) are palladium chloride, palladium bromide, palladium iodide, palladium sulfate, palladium nitrate, palladium acetate, dichlorobis (acetonitrile) palladium, dichlorobis (benzonitrile) palladium, and palladium acetylacetonate. .

(3) Compound which forms an ionic complex by reacting with a transition metal compound (B) The component (B) in the catalyst of the present invention is a compound which forms an ionic complex by reacting with a transition metal compound. It is. As the compound (B) which reacts with a transition metal compound to form an ionic complex, any compound can be used as long as it can react with a transition metal compound to form an ionic complex. Preferably, compound (B) is a compound that produces a non-coordinating anion by reaction with a transition metal compound.

Preferably, (B1) a Lewis acid capable of converting a transition metal compound into a cation to form a corresponding non-coordinating anion, and (B2) a general formula G ⁺ A ⁻ (where G ⁺ is an oxide of the transition metal, Or a cation capable of extracting a ligand from a transition metal compound, wherein A ⁻ is a non-coordinating anion. ) general formula ^{(L-H) + a -} ( where, L is a neutral Lewis base, (L-H) ⁺ is a Bronsted acid, a transition metal can be cationic, and a ^- is Which is a non-coordinating anion).

More preferably, (B1), (B2),
(B3) is a boron compound.

The Lewis acid (B1) is more preferably a boron compound represented by the general formula BQ ¹ Q ² Q ³ . Wherein B is a trivalent boron atom, Q ^{1 to} Q ³ are a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, and a halogenated carbon atom containing 1 to 20 carbon atoms. A hydrogen group, a substituted silyl group containing 1 to 20 carbon atoms, an alkoxy group containing 1 to 20 carbon atoms or a disubstituted amino group containing 2 to 40 carbon atoms, which are the same, May also be different.

Specific examples of the Lewis acid (B1) include tris (pentafluorophenyl) borane, tris (2,
3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) borane,
Tris (3,4,5-trifluorophenyl) borane,
Tris (2,3,4-trifluorophenyl) borane,
Phenylbis (pentafluorophenyl) borane and the like can be mentioned, and most preferred is tris (pentafluorophenyl) borane.

[0022] the general formula G ⁺ A ^- in the compound represented by (B2) is more preferably represented by the general formula G ⁺ (BQ ¹ Q
² Q ³ Q ^{4) -} is a boron compound represented by the. However,
B is a boron atom in a trivalent valence state, and Q ^{1 to} Q ⁴
Is the same as Q ^{1 to} Q ³ in the above Lewis acid (B1).

Specific examples of the compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^— include a cationic oxidizing agent, G ⁺ , a ferrocenium cation and an alkyl-substituted ferrocenium. Cations, silver cations and the like,
G ⁺ , which is a cation capable of extracting a ligand from a transition metal compound, includes a triphenylmethyl cation. A non-coordinating anion (BQ ¹ Q ² Q
³ Q ^{4) -,} the tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,
5-tetrafluorophenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate
And tetrakis (3,5-bistrifluoromethylphenyl) borate.

Specific examples of these combinations include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1'-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, Phenylmethyltetrakis (pentafluorophenyl) borate,
Triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate and the like can be mentioned, and most preferred is triphenylmethyltetrakis (pentafluorophenyl) borate.

Further, the above-mentioned general formula (L-H) ⁺ A ^- in the compound represented by (B3) is, more preferably, the general formula ^{(L-H) + (BQ} 1 Q 2 Q 3 Q 4) - It is a boron compound represented by these. However, B is a boron atom in the trivalent valence state, Q ¹ to Q ⁴ are the same as Q ¹ to Q ³ in the above Lewis acid (B1).

General formula (LH)⁺ (BQ¹ Q^Two Q^Three Q
^Four )^- Specific examples of the compound represented by
Acid (LH)⁺ Has a trialkyl-substituted an
Monium, N, N-dialkylanilinium, dialky
Luammonium, triarylphosphonium, etc.
Is a non-coordinating anion (BQ¹ Q^Two Q^Three Q^Four )
^- Are the same as described above.

Specific examples of these combinations include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (normal butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (normal) Butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N- 2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3,5
-Bistrifluoromethylphenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl)
Examples thereof include borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, and tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate. Most preferably, tri (normal butyl) ammonium tetrakis (pentane) Fluorophenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

(4) Water or Acid (C) The component (C) in the catalyst of the present invention is water or an acid. The acid is preferably a Bronsted acid. Here, the Bronsted acid is a compound having a property of giving a proton, and is not particularly limited as long as it is a compound having such a property. Specific examples of the acid include hydrochloric acid, sulfuric acid, nitric acid, hypochlorous acid, perchloric acid, boric acid, phosphoric acid, permanganic acid, dichromic acid, hydrogen peroxide,
Inorganic acids such as hydrofluoric acid; heteropolyacids such as tungstophosphoric acid and molybdophosphoric acid or hydrates thereof; formic acid;
Acetic acid, propionic acid, trifluoroacetic acid, monochloroacetic acid, dichloroacetic acid, butyric acid, benzoic acid, methylbenzoic acid,
Carboxylic acids such as chlorobenzoic acid, methoxybenzoic acid, fumaric acid, maleic acid, salicylic acid, and naphthalene carboxylic acid; phenol, cresol, fluorophenol, chlorophenol, hydroquinone, bromophenol, methoxyphenol, cyanophenol, aminophenol, nitro Phenols such as phenol and pentafluorophenol; and solid acids such as silica and alumina.

Preferred Bronsted acids are hydrochloric acid, perchloric acid, boric acid, aqueous hydrogen peroxide, tungstophosphoric acid, hydrofluoric acid, formic acid, acetic acid, propionic acid, trifluoroacetic acid, benzoic acid, fumaric acid, maleic acid , Glyoxal, phenol, pentafluorophenol, 4-methoxyphenol, cresol and hydroquinone. These compounds can be used alone or in combination.

(5) Cyclic Olefin Polymerization Catalyst The cyclic olefin polymerization catalyst of the present invention is a catalyst containing the above components (A), (B) and (C). These components may be used, for example, as a solution in which the component (A), the component (B) and the component (C) are mixed in a suitable solvent in advance, or the components (A) and (B) may be added to the polymerization system. And the components (C) or a solution in which they are dissolved in a monomer or an appropriate solvent may be supplied simultaneously or separately to bring them into contact in the polymerization system.

Although the preferred amount of the component (A) varies depending on the type of the cyclic olefin selected and other polymerization conditions, the range cannot be determined without limitation.
Usually 0.00001 to 1 based on the monomers used
Mol%, preferably 0.0001 to 0.1 mol%. The amount of the component (B) is not particularly limited, either, but is usually 0.1 to 100 mol, preferably 0.5 to 10 mol, per 1 mol of the component (A). The use amount of the component (C) is not limited, but is usually 0.001 mol or more per 1 mol of the component (A). Preferably it is about 0.1 to 100000 mol per 1 mol of the component (A), but it can be used in a large amount and used as a polymerization solvent.

(6) Production of Cyclic Olefin Polymer In the present invention, the polymerization method is not particularly limited. For example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane and octane, benzene, Aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene dichloride and ethylene dichloride, alcohols such as methanol, ethanol, propanol and butanol, ethers such as diethyl ether and tetrahydrofuran, acetone, methyl ethyl ketone and methyl isobutyl ketone In addition to ketones, solvent polymerization using aqueous solution of acetic acid, hydrochloric acid, perchloric acid, etc. and water alone or as a mixture of plural solvents, slurry polymerization, gas phase polymerization in gaseous monomer and high pressure ion Polymerization is possible, and continuous polymerization And batch polymerization.

In the solvent polymerization or slurry polymerization, the polymerization temperature can usually range from -50 to 200 ° C.
The temperature is preferably in the range of −20 to 100 ° C., and the polymerization pressure is preferably normal pressure to 60 kg / cm ² G. In the gas phase polymerization, the polymerization temperature is 60 to 120 ° C and the polymerization pressure is 1 to 30 k
g / cm ² G is preferred. In the high pressure ionic polymerization, the polymerization temperature is 150 to 300 ° C., and the polymerization pressure is 300 to 2500 k.
g / cm ² G is preferred. In general, the polymerization time is appropriately determined depending on the kind of the intended polymer and the reaction apparatus, but can usually be in the range of 1 minute to 20 hours.
In the present invention, a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the copolymer.

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to the Examples. [Η] in the examples is
It is an intrinsic viscosity measured at 135 ° C. using tetralin as a solvent.

Example 1 Dichlorobis (benzonitrile) palladium 0.001 was placed in a 300 ml round-bottom separable flask purged with nitrogen.
Millimol, 100 ml of dehydrated toluene, 10 ml of a toluene solution of norbornene at a concentration of 5 mol / liter (50 mmol as norbornene), and 1 mmol of water were charged and heated to obtain a homogeneous solution at 50 ° C. To this, 0.001 mmol of triphenylmethyltetrakis (pentafluorophenyl) borate was added, and stirring was continued at 50 ° C. for 15 minutes. Thereafter, the reaction solution was poured into 100 ml of methanol, and the precipitated white solid was collected by filtration. The solid was washed with methanol and dried under reduced pressure to give a polymer, 288 mg.
(The conversion of norbornene was 6.1%, and the catalytic activity was 1150 kg / mol-Pd). No absorption based on a carbon-carbon double bond was observed in the infrared absorption spectrum of the polymer, confirming that the polymer was polynorbornene having a saturated structure. [Η] of the polymer
Was 0.63 dl / g.

Example 2 The water in Example 1 was replaced with a 40% aqueous glyoxal solution 14
The same operation as in Example 1 was carried out except that the amount was changed to 5 μl, to obtain 1.44 g of polynorbornene. The yield was 31% as a conversion of norbornene and 5760 kg / as a catalytic activity.
It corresponds to mol-Pd. The reaction system was in the form of a slurry in which the produced polymer was suspended in toluene.

Example 3 The water in Example 1 was replaced with 1.0 mol / l of hydrochloric acid 18
The same operation as in Example 1 was carried out except for changing to μl, to obtain 305 mg of polynorbornene. The yield was 6.5% as the conversion of norbornene and 1220 kg / as the catalytic activity.
It corresponds to mol-Pd. [Η] of the polymer is 0.1.
It was 28 dl / g.

Example 4 The water in Example 1 was replaced with 160 μl of a 60% aqueous solution of perchloric acid.
The operation was carried out in the same manner as in Example 1 except that 1.84 g of polynorbornene was obtained. The yield was 39% as the conversion of norbornene and 7350 kg / mol as the catalytic activity.
-Pd. The reaction system was in the form of a slurry in which the produced polymer was suspended in toluene.

Example 5 The same operation as in Example 1 was carried out except that the water in Example 1 was changed to 18% of 31% aqueous hydrogen peroxide, to obtain 338 mg of polynorbornene. The yield was 7.2% as a conversion of norbornene and 1350 kg / mol- as a catalytic activity.
It corresponds to Pd. [Η] of the polymer is 1.23 d.
1 / g.

Example 6 The water in Example 1 was replaced with a 42% aqueous hydrofluoric acid solution 2
The same operation as in Example 1 was carried out except that the amount was changed to 09 µl, to obtain 1.447 g of polynorbornene. The yield was 31% as a conversion of norbornene and 5790 k as a catalytic activity.
g / mol-Pd. The reaction system was in the form of a slurry in which the produced polymer was suspended in toluene.

Example 7 The procedure of Example 1 was repeated, except that water was changed to boric acid, to obtain 585 mg of polynorbornene. This yield corresponds to a conversion of norbornene of 12% and a catalytic activity of 2320 kg / mol-Pd. [Η] of the polymer was 2.38 dl / g.

Example 8 The procedure of Example 1 was repeated except that 1 mmol of water in Example 1 was changed to 0.1 mmol of Tungsto IV phosphoric acid hydrate to obtain 1.24 g of polynorbornene. This yield corresponds to a conversion of norbornene of 26% and a catalytic activity of 4950 kg / mol-Pd. The reaction system was in the form of a slurry in which the produced polymer was suspended in toluene.

Example 9 The procedure of Example 1 was repeated, except that 1 mmol of water in Example 1 was changed to 0.1 mmol of Tangst IV phosphoric acid hydrate and 1 mmol of water, to obtain 1.83 g of polynorbornene.
I got This yield is a conversion of norbornene of 39.
%, Which corresponds to 7320 kg / mol-Pd as the catalytic activity. The reaction system was in the form of a slurry in which the produced polymer was suspended in toluene.

Example 10 The water in Example 1 was replaced with 1.0 mol / liter of acetic acid 18
The same operation as in Example 1 was carried out except for changing to μl, to obtain 1.25 g of polynorbornene. The yield was 27% as a conversion of norbornene and 4990 kg / m as a catalytic activity.
ol-Pd. [Η] of the polymer is 2.
It was 33 dl / g.

Example 11 The water in Example 1 was replaced with 1.0 mol / l of formic acid 18
The same operation as in Example 1 was carried out except for changing to μl, to obtain 0.398 g of polynorbornene. The yield was 8.5% as the conversion of norbornene and 1590 kg as the catalytic activity.
/ Mol-Pd. [Η] of the polymer was 2.62 dl / g.

Example 12 1 mmol of water in Example 1 was replaced with 1 m of trifluoroacetic acid.
The same operation as in Example 1 was carried out except that the mol and the water were changed to 1 mmol, to obtain 307 mg of polynorbornene. This yield corresponds to a conversion of norbornene of 6.6% and a catalytic activity of 1240 kg / mol-Pd. [Η] of the polymer was 0.37 dl / g.

Example 13 The same operation as in Example 1 was carried out except that water was changed to phenol, to obtain 276 mg of polynorbornene. This yield was 5.9% as a conversion of norbornene,
This corresponds to a catalytic activity of 1100 kg / mol-Pd. [Η] of the polymer was 0.36 dl / g.

Example 14 The procedure of Example 1 was repeated, except that water was changed to pentafluorophenol.
5 mg were obtained. This yield corresponds to a conversion of norbornene of 3.7% and a catalytic activity of 700 kg / mol-Pd.

Example 15 The procedure of Example 1 was repeated, except that water was changed to 4-methoxyphenol.
0 mg was obtained. The yield was 5.7% as the conversion of norbornene and 1080 kg / mol-Pd as the catalytic activity.
Is equivalent to [Η] of the polymer is 0.57 dl /
g.

Example 16 The procedure of Example 1 was repeated, except that water was changed to hydroquinone, to obtain 436 mg of polynorbornene. This yield was 9.3% as a conversion of norbornene,
The catalytic activity corresponds to 1740 kg / mol-Pd.

Comparative Example 1 The same operation as in Example 1 was carried out except that 1 mmol of water was not added.
0 mg was obtained. This yield corresponds to a conversion of norbornene of 3.2% and a catalytic activity of 600 kg / mol-Pd. [Η] of the polymer is 0.20 dl / g.
Met.

Example 17 The same operation as in Example 1 was carried out except that 1 mmol of water in Example 1 was changed to 10 mmol of water, and polynorbornene 8 was used.
92 mg were obtained. This yield corresponds to% as the conversion of norbornene and 3570 kg / mol-Pd as the catalytic activity. [Η] of the polymer was 1.92 dl / g.

Example 18 The procedure of Example 1 was repeated except that 1 mmol of water was changed to 50 mmol of water to obtain 1.31 g of polynorbornene. The yield was 28% as a conversion of norbornene and 5220 kg / mol-P as a catalytic activity.
d. [Η] of the polymer is 2.74 dl.
/ G.

Example 19 The procedure of Example 1 was repeated, except that 1 mmol of water was changed to 100 mmol of water, to obtain 1.28 g of polynorbornene. The yield was 27% as the conversion of norbornene and 5130 kg / mol-P as the catalytic activity.
d. The reaction system was in the form of a slurry in which the produced polymer was suspended in toluene. [Η] of the 135 ° C. tetralin soluble portion of the polymer was dl / g.

Example 20 100 ml of dehydrated toluene in Comparative Example 1 was replaced with 100 m of water.
The same operation as in Comparative Example 1 was carried out except that the amount was changed to 1, to obtain 818 mg of polynorbornene. The yield was 17% as the conversion of norbornene and 3270 kg / mo as the catalytic activity.
It corresponds to 1-Pd. The reaction system was in the form of a slurry in which the produced polymer was suspended in water. The polymer was also insoluble in toluene.

Example 21 18 μm of 1.0 mol / l acetic acid in Example 10
The procedure of Example 10 was repeated, except that 1 was changed to 18 μl of acetic acid of 0.01 mol / l.
2 mg were obtained. This yield corresponds to a conversion of norbornene of 15% and a catalytic activity of 2850 kg / mol-Pd. [Η] of the polymer is 1.81 dl / g.
Met.

Example 22 1.0 μm / liter acetic acid of 18 μm in Example 10
The same operation as in Example 10 was carried out except that 1 was changed to 18 μl of acetic acid of 0.1 mol / l, and polynorbornene 1.3 was used.
82 g were obtained. This yield corresponds to a conversion of norbornene of 29% and a catalytic activity of 5530 kg / mol-Pd. [Η] of the polymer is 2.79 dl / g.
Met.

Example 23 18 μl of 1.0 mol / l acetic acid in Example 10
The same operation as in Example 10 was carried out except that 1 was changed to 18 μl of 10 mol / l acetic acid.
g was obtained. This yield is 19% as the conversion of norbornene.
%, Which corresponds to a catalytic activity of 3610 kg / mol-Pd. [Η] of the polymer was 1.87 dl / g.

Example 24 The same operation as in Example 1 was carried out except that the stirring time in Example 1 was changed from 15 minutes to 60 minutes, to obtain 844 m of polynorbornene.
g was obtained. This yield is 18% as the conversion of norbornene.
%, Corresponding to a catalyst activity of 844 kg / mol-Pd. [Η] of the polymer was 0.89 dl / g.

Comparative Example 2 The same operation as in Comparative Example 1 was carried out except that the stirring time in Comparative Example 1 was changed from 15 minutes to 60 minutes.
g was obtained. This yield is calculated as a conversion of norbornene of 7.
5%, corresponding to a catalytic activity of 350 kg / mol-Pd. [Η] of the polymer was 0.55 dl / g.

Example 25 A 300 ml round bottom separable flask purged with nitrogen was charged with 0.002 mmol of palladium acetylacetonate.
27 ml of dehydrated toluene, 3 ml of a toluene solution of norbornene at a concentration of 5 mol / liter (30 ml as norbornene)
Mmol) and 20 mmol of water, and heated to 50 ° C.
Was obtained as a homogeneous solution. Here, triphenylmethyltetrakis (pentafluorophenyl) borate 0.002
Mmol was added and stirring was continued at 50 ° C. for 5 minutes. The reaction solution was poured into 100 ml of methanol, and the precipitated white solid was collected by filtration. The solid was washed with methanol and then dried under reduced pressure to obtain a polymer (yield: 790 mg) (conversion of norbornene: 56%, catalytic activity: 4740 kg / mol-).
Pd). No absorption based on a carbon-carbon double bond was observed in the infrared absorption spectrum of the polymer, confirming that the polymer was polynorbornene having a saturated structure. [Η] of the polymer was 3.25 dl / g.

Comparative Example 3 The same operation as in Example 25 was carried out except that 20 mmol of water was not added, and polynorbornene 177 was used.
mg was obtained. The yield is 1 as the conversion of norbornene.
3%, corresponding to a catalytic activity of 1060 kg / mol-Pd.

[0062]

As described above in detail, according to the method of the present invention, a useful cyclic olefin polymer can be efficiently produced using an extremely small amount of catalyst, and its industrial value is extremely large. is there.

[Brief description of the drawings]

FIG. 1 is a flowchart for helping the understanding of the present invention. The flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this.

Claims (13)

[Claims] 1. A catalyst for polymerization of cyclic olefins, comprising (A) a transition metal compound, (B) a compound which reacts with a transition metal compound to form an ionic complex, and (C) water. . 2. A catalyst for polymerization of cyclic olefins, comprising (A) a transition metal compound, (B) a compound which reacts with the transition metal compound to form an ionic complex, and (C) an acid. . 3. The catalyst according to claim 2, wherein the acid (C) is a Bronsted acid. 4. The catalyst according to claim 3, wherein the Bronsted acid is an inorganic acid. 5. The catalyst according to claim 3, wherein the Bronsted acid is a heteropoly acid or a hydrate thereof. 6. The catalyst for polymerizing cyclic olefins according to claim 3, wherein the Bronsted acid is a carboxylic acid compound. 7. The catalyst according to claim 3, wherein the Bronsted acid is phenol or phenols. 8. The catalyst for polymerization of cyclic olefins according to claim 1, wherein the transition metal compound (A) is a Group 10 transition metal compound. 9. The catalyst for polymerization of cyclic olefins according to claim 1, wherein the transition metal compound (A) is a palladium compound. 10. The compound (B), which reacts with a transition metal compound to form an ionic complex, is a compound which produces a non-coordinating anion by reacting with the transition metal compound. Item 10. The cyclic olefin polymerization catalyst according to any one of Items 1 to 9. 11. The compound (B) which reacts with a transition metal compound to form an ionic complex is represented by the following (B1) to (B3)
The catalyst for polymerization of cyclic olefins according to any one of claims 1 to 9, wherein (B1) Boron compound represented by general formula BQ ¹ Q ² Q ³ (B2) Boron compound represented by general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- (B3) General formula (LH) ) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^-
Wherein B is a boron atom in a trivalent valence state,
^{1 to} Q ⁴ are a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, a halogenated hydrocarbon group containing 1 to 20 carbon atoms, a substituted silyl group containing 1 to 20 carbon atoms,
An alkoxy group containing 1 to 20 carbon atoms or 2 to 4
Disubstituted amino groups containing zero carbon atoms, which may be the same or different. G ⁺ is a cationic oxidizing agent capable of oxidizing a transition metal to a cation or a cation capable of extracting a ligand from a transition metal compound. L is a neutral Lewis base,
(LH) ⁺ is a Bronsted acid. ) 12. A process for producing a cyclic olefin polymer, comprising polymerizing a cyclic olefin using the catalyst according to any one of claims 1 to 11. 13. A cyclic olefin is polymerized using a catalyst containing (A) a transition metal compound and (B) a compound which reacts with the transition metal compound to form an ionic complex, using water as a dispersion solvent. A method for producing a cyclic olefin polymer.