JP2002363264A - Method for producing norbornene resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a norbornene resin by polymerizing a norbornene monomer using a ruthenium-based metathesis catalyst in combination with a reaction retarding agent, enabling the operation of polymerization preparation step in an easily handleable state while keeping the characteristic extremely high activity of the catalyst and rapidly proceeding the reaction in the polymerization reaction stage. SOLUTION: The method for the production of a norbornene resin comprises the polymerization of a norbornene monomer using a ruthenium-based metathesis catalyst in combination with at least one kind of reaction retarding agent composed of a compound having the skeleton of the formula A or B in the molecule: X=X-Y-Y-Z=Z (A) and X=X-Y=Y-Z=Z (B) (X, Y and Z are each a carbon atom provided that X and Z are not in the different rings when the compound having the skeleton of A or B is a polycyclic compound having >=2 rings).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a norbornene resin by polymerizing a norbornene monomer. More specifically, production of a norbornene-based resin in which a norbornene-based monomer is polymerized by using a ruthenium complex catalyst to which a heteroatom-containing carbene compound is bonded in combination with a compound having a reaction delay effect (hereinafter, referred to as a “reaction retardant”). About the method.

[0002]

2. Description of the Related Art Conventionally, various norbornene-based resin molded articles have been produced by polymerizing norbornene-based monomers such as dicyclopentadiene and tricyclopentadiene in the presence of a tungsten-based or molybdenum-based catalyst. At this time, it is necessary to adjust the pot life of the reaction solution according to the size and shape of the target molded product or the molding method to be employed, and various reaction control methods have been proposed.

[0003] For example, Japanese Patent Application Laid-Open No. 3-146516 discloses a method in which a molybdenum-based metathesis polymerization catalyst and 5-alkenyl-2-norbornene are used in combination to delay the pot life (pot life) of a reaction solution. Has been described.
In this method, it is considered that 5-alkenyl-2-norbornene acts as a chain transfer agent and suppresses the growth of the polymer chain generated immediately after the start of the reaction, thereby suppressing an increase in the viscosity of the reaction solution. However, since it has no effect of slowing down the reaction rate itself, there is a problem that the time until the polymerization reaction is completed cannot be extended (reaction delay effect).

In recent years, it has been reported that ruthenium or osmium complexes are useful as a polymerization catalyst for norbornene monomers (US Pat. No. 5,710,029).
8 and 5849851). In recent years, WO99 / 51344 and WO00
/ 58322 and WO00 / 71554 also have developed a ruthenium complex to which a heteroatom-containing carbene compound is bonded. These ruthenium complexes have extremely high activity and are expected to reduce costs by increasing the efficiency of the molding process and reducing the amount of catalyst.

[0005] Even when such a ruthenium complex or the like is used as a catalyst, it is necessary to control the polymerization reaction, and there has been reported a method in which the use of a reaction retarder temporarily suppresses the catalytic activity and causes the reaction to proceed slowly. Have been. For example, JP-T-2000-500506 discloses that
The following formula (a) or (b)

[0006]

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Wherein Me represents ruthenium or osmium, T ₁ and T ₂ independently of one another represent a tertiary phosphine, or T ₁ and T ₂ together form a ditertiary diphosphine; T ₃ is a hydrogen atom;
An alkyl group; a cycloalkyl group having 3 to 8 carbon atoms which may contain 1 or 2 O atoms, S atoms or N atoms; T ₄ represents an alkyl group having 1 to 4 carbon atoms; X ₁ and X ₂ represent a halogen atom. The use of a ruthenium or osmium complex catalyst represented by the formula (1) in combination with an acetylene compound or a diene compound suppresses the catalytic activity and extends the process time.

In this document, open-chain or cyclic dienes can be used as the diene compound, butadiene, norbornadiene, cyclopentadiene, cyclohexa-1,3
-Diene, cyclohepta-1,3-diene, cycloocta-1,3- and 1,5-diene and the like are specifically exemplified, and it is also described that the use of 1,3-dienes or cyclic dienes is preferred. .

However, this document includes the above general formula
In (a), T₁And / or T ₂Is imidazolidine
Hetero atom-containing carbene compounds such as carbene compounds
No ruthenium complex catalyst is described.

In general, the reactivity of a ruthenium complex catalyst varies greatly depending on the type of ligand bound to ruthenium. Therefore, in a ruthenium complex catalyst having different ligands, what kind of compound exerts a reaction delay effect is considered. It is difficult to predict. In fact, according to our findings,
Even if an attempt is made to control the activity of a ruthenium complex catalyst to which an imidazolidine carbene compound is bound by using a cyclic or chain 1,3-diene compound as described in JP-T-2000-500506, the reaction is delayed. No effect was observed.

[0011]

The above-mentioned WO 99/513
No. 44 and WO00 / 58322, WO00 / 58322
Since the ruthenium complex catalyst to which a heteroatom-containing carbene compound as disclosed in JP-A-71554 is extremely active, poor mixing with a monomer, gelation before molding, and the like are liable to occur. The need for high reaction retarders is increasing. Therefore, it is strongly desired to develop a method for efficiently producing norbornene-based resin molded products on an industrial scale by using a ruthenium complex catalyst to which a heteroatom-containing carbene compound is bonded in combination with a reaction retarder.

According to the present invention, when a norbornene-based monomer is polymerized using a ruthenium complex catalyst, a reaction retarder is used in combination to suppress the extremely high activity inherent in the catalyst while preparing the polymerization in an easy-to-handle state. It is an object of the present invention to provide a method for producing a norbornene-based resin that can be operated and that allows the reaction to proceed quickly in the polymerization reaction stage.

[0013]

Means for Solving the Problems In order to achieve the above object, the present inventors have made intensive studies on a reaction retarder used in combination with a ruthenium catalyst system to which a heteroatom carbene compound is bonded, and as a result, a specific It has been found that an olefin compound having a structure has an excellent effect. It has also been found that this reaction delay effect is unique to the ruthenium catalyst system which is different from the action of the molybdenum catalyst system as a chain transfer agent of the reaction retarder already reported. Furthermore, by using such a reaction retarder and a ruthenium catalyst system in combination, it is possible to carry out a polymerization preparation operation in an easy-to-handle state. The present inventors have found that a norbornene-based resin can be obtained, and have completed the present invention.

That is, the present invention firstly provides the following general formula (1) or (2)

[0015]

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(In the formula, R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or a C ₁ -C which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom. Represents a hydrocarbon group of _20. X ¹ ,
X ² independently represents any anionic ligand. L ¹ represents a hetero atom-containing carbene compounds, ^{L 2}
Represents a heteroatom-containing carbene compound or a neutral electron-donating compound. Also, R ¹ , R ² , X ¹ , X ² , L ¹ and L ² may combine with each other in any combination to form a polydentate chelating ligand. )) And at least one kind of reaction delay between a compound having a 1,5-diene skeleton (A) or a 1,3,5-triene skeleton (B) represented by the following formula in a molecule: Provided is a method for producing a norbornene-based resin, which comprises polymerizing a norbornene-based monomer in combination with an agent.

[0017]

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(Wherein X, Y and Z each represent a carbon atom. However, when the compound having a skeleton represented by A or B is a polycyclic compound having two or more rings, X = X moiety And Z
Excludes those where the Z moiety is in a different ring. )

In the first aspect of the present invention, 5-isopropenyl-2-norbornene and / or
Alternatively, it is preferable to use 5- (1-propenyl) -2-norbornene, and to use a monomer mixture containing 50% by weight or more of dicyclopentadiene as the norbornene-based monomer. In the first aspect of the present invention, it is preferable to control the pot life of the reaction solution by adjusting the amount of the reaction retarder.

The present invention secondly provides 5-isopropenyl-2.
-Norbornene and / or 5- (1-propenyl) -2
A method for producing a norbornene-based resin in which a norbornene-based monomer mixture containing 50% by weight or more of dicyclopentadiene containing norbornene as an impurity is polymerized using a ruthenium complex catalyst represented by the general formula (1) or (2). And controlling the content of 5-isopropenyl-2-norbornene and / or 5- (1-propenyl) -2-norbornene contained in the dicyclopentadiene used in the monomer mixture, to thereby control the reaction solution. Provided is a method for producing a norbornene-based resin, characterized in that the use time is controlled.

In the second aspect of the present invention, the mixing ratio of two or more dicyclopentadiene having different contents of 5-isopropenyl-2-norbornene and / or 5- (1-propenyl) -2-norbornene is adjusted. By doing
5-isopropenyl-2-norbornene and / or 5-
The content of (1-propenyl) -2-norbornene in the monomer mixture is preferably set to a predetermined value.

[0022]

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a ruthenium complex catalyst having a heteroatom-containing carbene compound bonded thereto,
A norbornene-based resin is obtained by subjecting a norbornene-based monomer mixture to ring-opening metathesis polymerization in combination with at least one kind of reaction retarder of a compound having a 5-diene skeleton (A) or a 1,3,5-triene skeleton (B). It is a manufacturing method. Hereinafter, the production method of the present invention will be described in detail by dividing into a ruthenium complex catalyst, a reaction retarder, a norbornene-based monomer, and a polymerization method.

(Ruthenium complex catalyst) The ruthenium complex catalyst used in the present invention is a ruthenium carbene complex represented by the following general formula (1) or (2).

[0024]

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In the formulas (1) and (2), R ¹ and R ²
Each independently represents a hydrogen atom, a halogen atom, or a C _{1 to} C ₂₀ hydrocarbon group which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom. X ¹ and X ² each independently represent an arbitrary anionic ligand. L ¹ represents a carbene compound containing a hetero atom, and L ² represents a carbene compound containing a hetero atom or a neutral electron donating compound. Also, R ¹ , R ² , X
¹ , X ² , L ¹ and L ² may combine with each other in any combination to form a polydentate chelating ligand.

In the present invention, the term “hetero atom” means an atom belonging to Group 15 or 16 of the periodic table.
Examples thereof include N, O, P, S, As, and Se atoms. Among these, from the viewpoint of obtaining a stable carbene compound, N, O, P, S atoms and the like are preferable, and N atoms are particularly preferable.

The hetero atom-containing carbene compound preferably has a hetero atom bonded to both sides of the carbene carbon, and further comprises a hetero ring containing the carbene carbon atom and the hetero atoms on both sides thereof. Is more preferred. Further, the hetero atom adjacent to the carbene carbon preferably has a bulky substituent.

Examples of the hetero atom-containing carbene compound include a compound represented by the following formula (3) or (4).

[0029]

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(Wherein, R ^{3 to} R ⁶ each independently represent a hydrogen atom, a halogen atom, or a C ₁ -C which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom) Represents a hydrocarbon group of ₂₀ .
R ^{3 to} R ⁶ may combine with each other in any combination to form a ring. )

Specific examples of the compounds represented by the above formulas (3) and (4) include 1,3-dimesitylimidazolidine-2-ylidene and 1,3-di (1-adamantyl) imidazolidin- 2-ylidene, 1-cyclohexyl-3-
Mesitylimidazolidin-2-ylidene, 1,3-dimesityloctahydrobenzimidazole-2-ylidene, 1,3-diisopropyl-4-imidazoline-2-
Ilidene, 1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene, 1,3-dimesityl-2,
3-dihydrobenzimidazole-2-ylidene and the like.

In addition to the compounds represented by the formulas (3) and (4), 1,3,4-triphenyl-2,
3,4,5-tetrahydro-1H-1,2,4-triazol-5-ylidene, 1,3-dicyclohexylhexahydropyrimidine-2-ylidene, N, N, N ',
N'-tetraisopropylformamidinylidene, 1,
3,4-triphenyl-4,5-dihydro-1H-1,
2,4-triazole-5-ylidene, 3- (2,6-
Heteroatom-containing carbene compounds such as (diisopropylphenyl) -2,3-dihydrothiazole-2-ylidene may also be used.

In the above formulas (1) and (2),
On (anionic) ligand X¹, X ²Is from the central metal
Ligand that has a negative charge when separated, such as
For example, halogen atoms such as F, Cl, Br and I, diketone
Group, substituted cyclopentadienyl group, alkoxy group,
Examples include a reeloxy group and a carboxyl group.
You. Of these, a halogen atom is preferable, and a chlorine atom
Is more preferred.

The neutral electron donating compound may be any ligand as long as it has a neutral charge when separated from the central metal. Specific examples thereof include carbonyl, amines, pyridines, ethers, nitriles, esters, phosphines, thioethers, aromatic compounds, olefins, isocyanides, thiocyanates, and the like. Among these, phosphines and pyridines are preferred, and trialkylphosphines are more preferred.

Examples of the complex compound represented by the general formula (1) include benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride and (1,3-dimesium). Tylimidazolidine-2-ylidene) (3-methyl-2
-Butene-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-
Dimesityl-octahydrobenzimidazole-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene [1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-2,3-dihydrobenzimidazole-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4,5 -Tetrahydro-1H-1,2,2
4-triazole-5-ylidene) ruthenium dichloride, (1,3-diisopropylhexahydropyrimidine-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesitylimidazolidine-2) A ruthenium complex compound in which a heteroatom-containing carbene compound such as -ylidene) pyridineruthenium dichloride and a neutral electron-donating compound are bonded;

Benzylidenebis (1,3-dicyclohexylimidazolidin-2-ylidene) ruthenium dichloride, benzylidenebis (1,3-diisopropyl-4)
A ruthenium complex compound in which two heteroatom-containing carbene compounds such as -imidazoline-2-ylidene) ruthenium dichloride are combined;

The complex compound represented by the general formula (2) includes, for example, (1,3-dimesitylimidazolidine-2-ylidene) (phenylvinylidene) (tricyclohexylphosphine) ruthenium dichloride,
(T-butylvinylidene) (1,3-diisopropyl-
4-imidazoline-2-ylidene) (tricyclopentylphosphine) ruthenium dichloride, bis (1,3-
Dicyclohexyl-4-imidazoline-2-ylidene)
And phenylvinylidene ruthenium dichloride.

These ruthenium complex catalysts include, for example,
Org. Lett. , 1999, vol. 1, p. 953,
Tetrahedron. Lett. , 1999, Vol. 40, p. 2247.

The amount of the ruthenium complex catalyst used is usually from 1: 2,000 to 1: 2,000,000 as a molar ratio of (metal ruthenium: norbornene monomer) in the catalyst.
0, preferably 1: 5,000 to 1: 1,000,000
0, more preferably 1: 10,000 to 1: 500,0
00 range.

The catalyst can be used by dissolving it in a small amount of an inert solvent, if necessary. Such solvents include:
For example, chain aliphatic hydrocarbons such as pentane, hexane and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, dicycloheptane,
Alicyclic hydrocarbons such as tricyclodecane, hexahydroindenecyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; nitromethane;
Nitrogen-containing hydrocarbons such as nitrobenzene and acetonitrile;
Solvents such as oxygen-containing hydrocarbons such as diethyl ether and tetrahydrofuran can be used. Among these, industrially used aromatic hydrocarbons and aliphatic hydrocarbons,
The use of alicyclic hydrocarbons is preferred.

(Reaction Delaying Agent) In the production method of the present invention, a compound having a 1,5-diene skeleton (A) represented by the following formula or 1,3 in the molecule is used as a reaction delaying agent together with the ruthenium complex catalyst. , 5-triene skeleton (B).

[0042]

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In the above formulas (A) and (B), X, Y and Z each represent a carbon atom. The compound having a 1,5-diene skeleton (A) or a 1,3,5-triene skeleton (B) has a 1,5-diene skeleton (A) or 1,1 in a molecule.
If the compound has a 3,5-triene skeleton (B),
It may be a compound having any structure such as a chain compound, a monocyclic compound, and a bicyclic or higher polycyclic compound.

Examples of the reaction retarder having a 1,5-diene skeleton (A) in the molecule include 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene, ci
s, cis-2,6-octadiene, cis, tran
s-2,6-octadiene, trans, trans-
Chain 1,5-diene compounds such as 2,6-octadiene;
1,5-cyclooctadiene, 1,5-dimethyl-1,
5-cyclooctadiene, cis, trans, tra
Monocyclic compounds such as ns-1,5,9-cyclododecatriene, 4-vinylcyclohexene, dipentene; 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5- (1-propenyl)- Polycyclic 1,5-diene compounds such as 2-norbornene; and the like.

Specific examples of the reaction retarder having a 1,3,5-triene skeleton (B) include trans-1,
3,5-hexatriene, cis-1,3,5-hexatriene, trans-2,5-dimethyl-1,3,5
-Hexatriene, cis-2,5-dimethyl-1,
Chain and cyclic compounds such as 3,5-hexatriene and 1,3,5-cycloheptatriene are exemplified.

However, 1,5-diene skeleton (A) or 1,5-diene skeleton (A)
Even when the compound has a 3,5-triene skeleton (B), when the compound is a bicyclic or higher polycyclic compound, the X = X portion and the Z = Z portion in (A) or (B) Are in different rings are excluded from the reaction retarders of the present invention. Examples of such compounds include bicyclo [4.3.0] nona-3,7-diene, 2-methylbicyclo [4.3.0] nona-3,7-diene, 3-methylbicyclo [4 .3.0] nona-3,7-diene, dicyclopentadiene, bicyclo [4.3.0] nona-3,
5,7-triene and the like. These compounds do not have a reaction delay effect. It is considered that these compounds have a structure in which two double bonds are relatively fixed, and the two double bonds are not at positions where they simultaneously act on ruthenium.

Particularly preferred compounds for the reaction retarder used in the present invention include cyclic isocyclics such as 5-isopropenyl-2-norbornene, 5- (1-propenyl) -2-norbornene and 1,5-cyclooctadiene. , 5-diene compounds. These compounds not only act as a reaction retarder, but also copolymerize with the norbornene-based monomer, and thus also play a role in reducing the deterioration in physical properties due to the reaction retarder remaining in the polymer.

The addition ratio of the reaction retarder is in the range of 0.01 to 5% by weight, preferably 0.02 to 2% by weight, based on the norbornene monomer mixture. If the addition ratio of the reaction retarder is less than 0.01% by weight, the reaction retarding effect is not exhibited. On the other hand, when the content exceeds 5% by weight, there is a possibility that the physical properties may be reduced by the reaction retarder remaining in the polymer or the polymerization reaction may not proceed sufficiently.

(Norbornene-Based Monomer) In the present invention, among the compounds having a norbornene ring structure, those which do not correspond to the above-mentioned reaction retarders are used as norbornene-based monomers. Examples of the norbornene-based monomer include, for example, norbornene, norbornadiene, methyl norbornene, dimethyl norbornene, ethyl norbornene, chlorinated norbornene, ethylidene norbornene, chloromethyl norbornene, trimethylsilyl norbornene, phenyl norbornene, cyano norbornene, dicyanorbornene, methoxycarbonyl norbornene, and pyridyl norbornene. And bicyclic norbornenes such as carboxylic acid anhydrides and carboxylic acid imides;

Tricyclic norbornenes such as alkyl, alkylidene and aryl-substituted dicyclopentadiene and dicyclopentadiene; dimethanohexahydronaphthalene, dimethanooctahydronaphthalene and their alkyl, alkenyl, alkylidene and aryl-substituted products Tetracyclic norbornenes; pentacyclic norbornenes such as tricyclopentadiene, and hexacyclic norbornenes such as hexacycloheptadecene; dinorbornene, compounds in which two norbornene rings are bonded by a hydrocarbon chain or an ester group, and alkyls thereof And a compound containing a norbornene ring such as an aryl-substituted product. Among these, the use of substituted and unsubstituted bicyclic or tricyclic or higher polycyclic norbornene compounds is preferred.

In the present invention, it is also possible to use a copolymer of the above norbornene-based monomer with a monocyclic cycloolefin such as cyclobutene, cyclopentene, cyclooctene, cyclododecene or a derivative thereof having a substituent.

The norbornene-based monomer may be used alone or
More than one kind may be used, but two or more kinds are preferably used. When two or more kinds are used, the thermoplastic resin becomes 1
Resins having various physical properties can be obtained by appropriately combining a monomer having two double bonds and a monomer having a plurality of double bonds to be a thermosetting resin. When two or more monomers are used in combination, there is an advantage that a monomer having a high freezing point temperature can be handled as a liquid due to a freezing point drop.

Among these, in the present invention, it is particularly preferable to use a monomer mixture containing 50% by weight or more of dicyclopentadiene as the norbornene-based monomer.

When dicyclopentadiene is used for ring-opening metathesis polymerization, it is common to use high-purity dicyclopentadiene having a purity of 98 to 99.9%.
This usually contains 5-isopropenyl-2-norbornene and 5- (1-propenyl) -2-norbornene as impurities. Conventionally, this dicyclopentadiene has been used. However, when a molybdenum-based or tungsten-based catalyst is used, 5-isopropenyl-2-norbornene and 5- (1-propenyl) are used.
Since -2-norbornene does not exhibit a reaction delay effect,
Even if these contents were adjusted, the catalytic activity could not be controlled. However, when the ruthenium complex catalyst of the present invention is used, 5-isopropenyl-2-norbornene and 5- (1-propenyl) -2-norbornene exhibit a reaction delay effect, and thus are included in dicyclopentadiene. By adjusting the content of 5-isopropenyl-2-norbornene and 5- (1-propenyl) -2-norbornene, it became possible to freely control the catalytic activity.

5-Isopropenyl-2-norbornene and 5- (1-propenyl)-in dicyclopentadiene
As a method of adjusting the content of 2-norbornene, for example, by a known purification method such as a distillation method and a decomposition dimerization method,
5-isopropenyl-2-norbornene and 5- (1-
A method for obtaining dicyclopentadiene containing a predetermined amount of (propenyl) -2-norbornene is exemplified. Also, 5-
By mixing two or more dicyclopentadienes having different contents of isopropenyl-2-norbornene and 5- (1-propenyl) -2-norbornene at an arbitrary ratio, 5-isopropenyl-2-norbornene and Dicyclopentadiene containing a predetermined amount of 5- (1-propenyl) -2-norbornene can be obtained. According to the latter method, the desired amounts of 5-isopropenyl-2-norbornene and 5- (1-propenyl-
Dicyclopentadiene containing 2-norbornene can be obtained.

In the present invention, 5-isopropenyl-2-norbornene and / or dicyclopentadiene are used.
Alternatively, the content of 5- (1-propenyl) -2-norbornene is 0.01 to 5% by weight in total, preferably 0.0 to 5% by weight.
It is in the range of 2 to 2% by weight. 5-isopropenyl-2-
Norbornene and / or 5- (1-propenyl) -2-
If the total content of norbornene is less than 0.01% by weight, no reaction delay effect is exhibited. On the contrary, when it exceeds 5% by weight, the polymerization reaction may not proceed sufficiently.

Dicyclopentadiene having a controlled content of 5-isopropenyl-2-norbornene and 5- (1-propenyl) -2-norbornene can be used alone, but may be used in combination with other norbornene monomers. Can also be used. When used in combination with other norbornene-based monomers, handling is facilitated due to freezing point depression. Again, 5-isopropenyl-2-norbornene and 5- (1-propenyl)-in the monomer mixture.
By adjusting the 2-norbornene content, the polymerization reactivity of the monomer can be controlled.

(Production of norbornene-based resin) A reaction solution containing the norbornene-based monomer, the ruthenium complex catalyst and the reaction retarder is prepared, and the reaction solution is heated to a predetermined temperature to carry out ring-opening metathesis polymerization. A norbornene-based resin can be produced.

The method of preparing the reaction solution is not particularly limited. For example, (i) a solution in which a predetermined amount of a norbornene-based monomer and a predetermined amount of a reaction retarder are dissolved or dispersed, and a predetermined amount of a powder or ruthenium complex of a ruthenium complex catalyst A method in which a solution in which a predetermined amount of a catalyst is dissolved or dispersed in an appropriate solvent is separately prepared, and mixed and prepared immediately before the reaction, (ii) a norbornene-based monomer (no solvent or solution), and a ruthenium complex catalyst And separately preparing a solution in which the reaction retarder is dispersed or dissolved, and mixing and preparing the mixture immediately before the reaction, (iii)
Examples thereof include a method of dissolving or dispersing a norbornene-based monomer, a reaction retarder, and a ruthenium complex catalyst in an appropriate solvent to prepare the same. In the present invention, it is preferable to use the method (i) or (ii).

The reaction solution may contain, as necessary, a Lewis acid and various additives such as an antioxidant, an ultraviolet absorber,
Contains elastomers, polymer modifiers, fillers, coloring agents, flame retardants, cross-linking agents, sliding agents, odorants, fillers for reducing weight, foaming agents, whiskers for surface smoothing, etc. Can be done. These Lewis acids and additives can be dissolved or dispersed in advance in a solution of a norbornene-based monomer or a solution of a ruthenium complex catalyst.

The Lewis acid is added to improve the polymerization reaction rate and the like. Such Lewis acids include, for example, trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, trialkylaluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride, dialkylaluminum chloride, trialkoxyscandium, tetraalkoxytitanium , Tetraalkoxytin, tetraalkoxyzirconium and the like.

Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group and an n-octyloxy group. In addition to these alkoxy groups, the use of a halogen-containing alkoxy group in which a halogen atom is bonded to the β-position not only improves the reaction rate, but also increases the reaction rate without impairing the miscibility of the monomer and the catalyst. It is suitable. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a sec-butyl group.

The amount of the Lewis acid to be used is usually a molar ratio of (metal ruthenium in the ruthenium catalyst: Lewis acid), usually 1: 1:
0.05 to 1: 100, preferably 1: 0.2 to 1: 2
0, more preferably 1: 0.5 to 1:10.

Examples of the elastomer include natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), and styrene-isoprene-styrene copolymer (SIS). ), Ethylene-propylene-diene terpolymer (EPDM), ethylene-vinyl acetate copolymer (EVA), and hydrides thereof. When these elastomers are added to the reaction solution, not only the resulting polymer is given impact resistance, but also the viscosity of the reaction solution can be adjusted.

Examples of the antioxidant include various antioxidants for plastics and rubbers such as hindered phenols, phosphorus and amines. These antioxidants may be used alone, but it is preferable to use two or more kinds in combination. Further, an antioxidant that can be copolymerized with the monomer can also be used. As a specific example,
Examples include norbornenylphenol compounds such as 5- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-norbornene (JP-A-57-8352).
No. 2).

Examples of the filler include glass powder, carbon black, talc, calcium carbonate, mica, and inorganic fillers such as aluminum hydroxide. In addition, a filler that has been surface-treated with a silane coupling agent or the like can also be used. As the cross-linking agent, sulfur or peroxide is used, and the heat resistance can be improved.

As the coloring agent, dyes, pigments and the like are used. Dyes are preferred because they can impart vivid dye colors to molded articles. There are various types of dyes, and known dyes may be appropriately selected and used. For example, nitro dye, nitroso dye, azo dye, ketoimine dye, triphenylmethane dye, xanthene dye, acridine dye, quinoline dye, methine dye, thiazole dye, indamine dye, azine dye, oxazine dye, thiazine dye, sulfur dye,
Examples include aminoketone dyes, anthraquinone dyes, indigoid dyes, and phthalocyanine dyes. Examples of the pigment include carbon black, graphite, graphite, iron oxide yellow, titanium dioxide, zinc oxide, trilead tetroxide, lead tin, chromium oxide, navy blue, and titanium black.

In the present invention, the ring-opening metathesis polymerization reaction may be a solution polymerization carried out in a solvent, or may be a bulk polymerization.
Polymerization may be used, but bulk polymerization in which a reaction solution containing a predetermined amount of a norbornene-based monomer, a reaction retarder, and a ruthenium complex catalyst is poured into a mold and cured is preferable. According to the bulk polymerization, a desired norbornene-based resin molded article can be produced at a stroke without performing post-curing (post-treatment).

In the case of solution polymerization, a reaction solution is prepared by dissolving or dispersing one or more of norbornene-based monomers, a reaction retarder and a ruthenium complex catalyst in an appropriate solvent, and stirring the mixture under stirring to obtain a reaction solution. By heating to a temperature, the intended norbornene-based resin can be produced. The polymerization temperature of the solution polymerization is generally -30 ° C to 2 ° C.
00 ° C, preferably 0 ° C to 180 ° C. The polymerization time is usually from 1 minute to 100 hours.

In the case of solution polymerization, the concentration of the norbornene-based monomer is preferably 1 to 50% by weight,
% By weight, more preferably 5 to 40% by weight. If the concentration of the norbornene-based monomer is too low, the productivity will be poor, while if it is too high, the viscosity after polymerization will be too high, making post-treatment difficult.

As a solvent used for preparing a reaction solution for solution polymerization, a solvent that dissolves the produced polymer and does not inhibit polymerization is used. For example, pentane, hexane,
Aliphatic hydrocarbons such as heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene,
Alicyclic hydrocarbons such as bicycloheptane, tricyclodecane, hexahydroindenecyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile; diethyl ether; Ethers such as tetrahydrofuran; esters such as ethyl acetate and isobutyl acetate; halogen-containing hydrocarbons such as chloroform, dichloromethane, chlorobenzene and dichlorobenzene; and the like. Among these solvents, the use of industrially versatile aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents and ethers is preferable, and they are inert during the polymerization reaction. ,
From the viewpoint of excellent polymer solubility, toluene,
It is more preferable to use an aromatic or alicyclic hydrocarbon solvent such as cyclohexane.

In the case of bulk polymerization, examples of the molding method that can be used include molding methods such as injection, injection, casting, rotation, centrifugation, extrusion, drawing, injection compression, and hand lay-up. This is a molding method using a mold. In particular, a method in which a norbornene-based monomer is polymerized in a lump in a mold by a resin transfer molding (RTM) method or a reaction injection molding (RIM) method is recommended. In this polymerization method, a known RTM machine or RIM is used to mix a reaction solution or a catalyst solution containing a monomer or a catalyst.
A molding machine such as a molding machine can be used.

The RTM machine generally comprises a monomer mixture tank, a catalyst mixture tank, a metering pump, a mixer and the like. By a metering pump, the monomer compounding solution and the catalyst compounding solution are fed into a mixer at a volume ratio of 1,000: 1 to 10: 1 to be mixed, and then injected into a mold heated to a predetermined temperature, where they are immediately lumped. A molded article can be obtained by polymerization.

In a preferred molding method using an RTM machine, a monomer mixture containing a norbornene-based monomer and a complex catalyst comprising at least one heteroatom-containing carbene compound bonded to ruthenium are dissolved in a small amount of a solvent. This is a method of preparing a catalyst mixture, mixing these, and molding.

When an RIM machine is used, two or more kinds of reaction liquids are fed to a mixing head, mixed by the collision energy, and then injected into a molding die, where they are immediately subjected to bulk polymerization to obtain a molded product. In a preferred molding method using a RIM machine, a norbornene-based monomer is divided into two parts, and a ruthenium complex catalyst in which at least one heteroatom-containing carbene compound is bonded to ruthenium as a third liquid is dissolved in a small amount of solvent. In this method, liquids are prepared, and these three liquids are mixed by collision to perform reaction injection molding. As the mold, a conventionally known mold, for example, a mold having a split mold structure, that is, a mold having a core mold and a cavity mold can be used, and the reaction liquid is injected into the voids (cavities) to perform bulk polymerization. . The core mold and the cavity mold are manufactured so as to form a void portion corresponding to the shape of a target molded product. Further, the shape, material, size, and the like of the mold are not particularly limited.

The temperature of the reaction solution before it is injected into the cavity in the mold is preferably 20 to 80 ° C. The viscosity of the reaction solution is usually 2 to 1000 cP at 30 ° C.,
Preferably it is 5-500 cP. The filling pressure (injection pressure) when filling the reaction solution into the cavity is usually 0.1
１００100 kgf / cm ² , preferably 0.2-50 kg
f / cm ² . If the filling pressure is too low, the transfer of the transfer surface formed on the inner peripheral surface of the cavity tends to be not performed well.If the filling pressure is too high, the rigidity of the mold must be increased to be economical. is not. The mold clamping pressure is usually 0.
It is in the range of 1 to 100 kgf / cm ² . The polymerization time may be appropriately selected, but is usually from 10 seconds to 20 minutes, preferably within 5 minutes.

When the reaction liquid mixed by the above-mentioned RTM machine or RIM machine is injected into the cavity of the molding die, the bulk polymerization reaction starts immediately and is cured. Polymerization is an exothermic reaction. According to this polymerization method, even if the temperature of the mold is set at 40 to 100 ° C., the temperature of the reaction solution rapidly rises, and the temperature of the reaction solution is reduced to 140 to 230 in a short time (for example, about 10 seconds to 5 minutes). The peak temperature of ° C. is reached and the molded article can be completely cured.

The molded product obtained by bulk polymerization is usually
The mold can be opened and the molded body can be removed from the mold while being attached to the core mold. The adhesion of the molded article to the core mold is performed by controlling molding conditions. The higher the mold temperature or the longer the cure time, the more it adheres to the core mold. When the curing time is short, when the mold is opened, the molded article adheres to the cavity mold and remains.
However, even if it adheres to the core mold, if the curing time is too long, the shrinkage due to cooling of the molded product proceeds to a considerable extent. What is necessary is just to remove a mold with an apparatus.

The molded article produced according to the present invention is not particularly limited, and the present invention is applicable to all uses, shapes,
Applicable to the production of molded products of a size. Such molded articles include, for example, a septic tank housing, a bathtub pan, a washing pan, a waterproof pan, a wash bowl, and the like. The norbornene-based resin molded product produced by the method of the present invention is excellent in impact resistance, heat resistance, dimensional stability, water absorption resistance, and the like, and has an excellent feature that it can be formed into a thin wall and is lightweight. .

[0080]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to the following examples, and it is possible to freely change the type and amount of the ruthenium complex catalyst, the reaction retarder, the norbornene-based monomer and the like without departing from the gist of the present invention. it can.

Examples 1 to 9 Examples of bulk polymerization in which various delaying agents were added In a 30 ml wide-mouthed glass bottle, a stirrer and dicyclopentadiene (including 10% of cyclopentadiene trimer. 1-propenyl) -2-norbornene and 5-isopropenyl-2-norbornene are contained in a total of 0.05% by weight.)
Further, 0.05 ml of various reaction retarders shown in Table 1 were added, and the mixture was cooled with ice. To this, 0.01 mol / liter of benzylidene (1,3-dimesitylimidazolidine-2) was added.
-Ylidene) (tricyclohexylphosphine) ruthenium dichloride (manufactured by STREM CHEMICAL)
After adding a toluene solution and stirring for 10 seconds, the mixture was heated in a water bath at 35 ° C. Thereafter, the temperature rose rapidly due to the heat of the polymerization reaction, and the polymerization reaction was completed. When the temperature rises sharply, the generation of mist is observed. Table 1 shows the time (SMT) from the start of heating in the water bath to the occurrence of mist. The polymerization reaction was performed in a nitrogen atmosphere.

Comparative Example 1 Example of Bulk Polymerization without Addition of a Reaction Delaying Agent The same operation as in the above example was carried out except that the amount of dicyclopentadiene was changed to 9.9 ml and no delaying agent was added. The results are shown in Table 1.

Comparative Examples 2 to 7 Examples of bulk polymerization in which various olefins were added The same operation as in the above Examples was carried out except that various olefins shown in Table 1 were added instead of the retarders. The results are shown in Table 1.

[0084]

[Table 1]

Comparative Example 8 Effect of Retarder on Molybdenum Catalyst System In a 30 ml wide-mouthed glass bottle, a stirrer, 9.2 ml of dicyclopentadiene (same as in Example 1) and 0.05 ml of 2-isopropenyl-5-norbornene were added. , 1,3-dichloro-2-propoxyethylaluminum chloride in dicyclopentadiene (0.3 mol / l)
0.67 ml was added, and the mixture was ice-cooled. To this was added a solution of tridodecylammonium molybdate in dicyclopentadiene (molybdenum concentration: 0.64 mol / liter).
After adding 08 ml and stirring for 10 seconds, the mixture was heated in a 35 ° C water bath. Thereafter, the temperature rose rapidly due to the heat of the polymerization reaction, and the polymerization reaction was completed. When SMT was measured in the same manner as in Example 1, it was 75 seconds. In addition,
The polymerization reaction was performed in a nitrogen atmosphere, and the same dicyclopentadiene as used in Example 1 for dissolving the catalysts was used.

Comparative Example 9 Example of Bulk Polymerization without Addition of a Reaction Delaying Agent The same operation as in Comparative Example 8 was carried out except that the amount of dicyclopentadiene was changed to 9.25 ml and no retarding agent was added. The SMT was 75 seconds. As described above, in the molybdenum catalyst system, it was found that 2-isopropenyl-5-norbornene had no effect as a reaction retarder.

Examples 10-1 to 10-3 Examples of activity control by the contents of 5- (1-propenyl) -2-norbornene and 5-isopropenyl-2-norbornene in dicyclopentadiene Dicyclopentadiene (purity 95 As impurities, 5- (1-propenyl) -2-norbornene and 5
3.8 total isopropenyl-2-norbornenes
% By weight. ) 738 g was fractionated under a nitrogen atmosphere using a distillation column corresponding to 25 theoretical plates. The amount of each fraction was 37 to 45 g, and after fractionation, the fractionation was completed. The pot residue was 88 g.
The overhead temperature at the time of distillation of fractions 9, 11 and 14 is 52
° C and pressure were 16.5 mmHg.

Further, these fractions were analyzed by gas chromatography for dicyclopentadiene purity and 5- (1-propenyl) -2-norbornene,
Table 2 shows the results of measuring the amount of -isopropenyl-2-norbornene. The analysis conditions were as follows: NB-1 (manufactured by Shimadzu Corporation, length: 30 m) was used as a capillary column, the vaporization chamber temperature was 180 ° C, and the detector (FID) temperature was 280 ° C. Oven temperature is 10 ℃ after holding at 60 ℃ for 5 minutes
/ Min, and further maintained at 240 ° C. for 20 minutes. The retention time of each component is 5- (1-propenyl)-
2-norbornene and 5-isopropenyl-2-norbornene were 13.31 to 13.60 minutes, and dicyclopentadiene was 13.84 to 14.13 minutes. The ratio of each component was determined from the area ratio of the peak of each component to the whole.

Next, benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride (manufactured by STREM CHEMICAL) was placed in a 30 ml wide-mouth glass bottle.
0.85 mg and a stirrer were put. 0.05 ml of toluene
Was added thereto and stirred with a magnetic stirrer to dissolve the ruthenium catalyst.
4.95 ml was added, and the mixture was further stirred for 10 seconds. Thereafter, the temperature rose rapidly due to the heat of the polymerization reaction, and the polymerization reaction was completed. At this time, the internal temperature was measured with a thermocouple, and the time from the monomer injection until the liquid temperature reached 100 ° C. (T100 in Table 2) was determined. The experiment was carried out in a thermostat set at 35 ° C., and the container containing the monomer, the reaction glass bottle, and the syringe were also placed in a thermostat set at 35 ° C., and used at constant temperature.

[0090]

[Table 2]

As shown in Table 2, 5- (1-propenyl) -2
It can be seen that the value of T100 changes according to the amounts of -norbornene and 5-isopropenyl-2-norbornene. As described above, 5- (1-propenyl) -2-norbornene and 5
By controlling the amount of -isopropenyl-2-norbornene, dicyclopentadiene containing the desired amounts of 5- (1-propenyl) -2-norbornene and 5-isopropenyl-2-norbornene is obtained, whereby the catalyst is obtained. It was found that the activity could be controlled.

Examples 11-1 to 11-3 5- (1-propenyl) -2-norbornene, 5-isopropenyl-
Example of activity control by blending two kinds of dicyclopentadiene having different 2-norbornene contents Fraction 6 of Example 7 (the overhead temperature at the time of distillation was 51.5
C. and a pressure of 16.5 mmHg) were analyzed by gas chromatography under the same conditions as in Example 10. As a result, the purity of dicyclopentadiene was 94.5%, and 5- (1-propenyl) -2-norbornene and 5-isopropenyl were used. -2-
The norbornene content was 5.4% in total. This fraction 6 and dicyclopentadiene having a purity of 99.9% (containing 0.1% in total of 5- (1-propenyl) -2-norbornene and 5-isopropenyl-2-norbornene as impurities) 20 / Table 3 shows the results obtained by blending at a weight ratio of 80, 10/90 and 2/98, polymerizing in the same manner as in Example 10, and measuring T100.

Comparative Example 10 Dicyclopentadiene having a purity of 99.9% (containing a total of 0.1% by weight of 5- (1-propenyl) -2-norbornene and 5-isopropenyl-2-norbornene as impurities). And polymerized in the same manner as in Example 10.
Table 3 shows the results of measuring 0.

[0094]

[Table 3]

As described above, 5- (1-propenyl) -2-
It has been found that a desired activity of dicyclopentadiene can be obtained by blending two kinds of dicyclopentadiene having different contents of norbornene and 5-isopropenyl-2-norbornene in an appropriate ratio.

[0096]

As described above, according to the present invention,
When a norbornene-based monomer is polymerized using a ruthenium complex catalyst to which a heteroatom-containing carbene compound is bonded, the use of a reaction retarder suppresses the extremely high activity inherent in the catalyst while allowing the polymerization to be carried out in an easy-to-handle state. Provided is a method for producing a norbornene-based resin that can perform a preparation operation and can promptly proceed with a reaction in a polymerization reaction stage.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Naoki Nishioka 1-2-1 Yoko, Kawasaki-ku, Kawasaki-shi, Kanagawa F-term in the Zeon Corporation General Development Center (reference) 4J032 CA23 CA24 CA28 CA33 CA34 CA35 CA36 CA38 CA45 CA46 CA68 CB01 CB04 CB05 CC02 CD02 CD08 CE00 CE03 CE05 CE06 CE17 CE18 CE22 CE24 CG07

Claims (6)

[Claims] 1. A compound of the general formula (1) or (2) (Wherein, R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or a halogen atom, an oxygen atom, a nitrogen atom,
C which may contain a sulfur atom, a phosphorus atom or a silicon atom
It represents a hydrocarbon group having ₁ -C _20. X ¹ and X ² each independently represent an arbitrary anionic ligand. L ¹ represents a hetero atom-containing carbene compound, and L ² represents a hetero atom-containing carbene compound or a neutral electron donating compound.
Also, R ¹ , R ² , X ¹ , X ² , L ¹ and L ² may combine with each other in any combination to form a polydentate chelating ligand. )) And at least one kind of reaction delay between a compound having a 1,5-diene skeleton (A) or a 1,3,5-triene skeleton (B) represented by the following formula in a molecule: A method for producing a norbornene-based resin, comprising polymerizing a norbornene-based monomer in combination with an agent. Embedded image (In the formula, X, Y, and Z each represent a carbon atom.
When the compound having a skeleton represented by A or B is a polycyclic compound having two or more rings, compounds in which the X = X portion and the Z = Z portion are in different rings are excluded. ) 2. The method for producing a norbornene-based resin according to claim 1, wherein 5-isopropenyl-2-norbornene and / or 5- (1-propenyl) -2-norbornene is used as the reaction retarder. 3. The method according to claim 1, wherein a norbornene-based monomer mixture containing 50% by weight or more of dicyclopentadiene is used as the norbornene-based monomer. 4. The method for producing a norbornene-based resin according to claim 1, wherein the pot life of the reaction solution is controlled by adjusting the amount of the reaction retarder. 5. A norbornene-based monomer mixture containing 50% by weight or more of dicyclopentadiene containing 5-isopropenyl-2-norbornene and / or 5- (1-propenyl) -2-norbornene as an impurity is represented by the general formula: A method for producing a norbornene-based resin which is polymerized using a ruthenium complex catalyst represented by (1) or (2), wherein 5-isopropenyl-2-norbornene and / or 5-isopropenyl contained in dicyclopentadiene used is used. A method for producing a norbornene-based resin, comprising controlling the pot life of a reaction solution by adjusting the content of (1-propenyl) -2-norbornene in a monomer mixture. 6. A method for controlling 5-isopropenyl-2-norbornene and / or 5- (1-propenyl) -2-norbornene by adjusting the mixing ratio of two or more dicyclopentadiene having different contents. Isopropenyl-2-
Norbornene and / or 5- (1-propenyl) -2-
The method for producing a norbornene-based resin according to claim 5, wherein the content of norbornene relative to the monomer mixture is a predetermined value.