JP2000072859A - Production of cyclo-olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cyclo-olefin polymer having a desired molecular weight that can reduce the amount of unreacting monomer, can control its molecular weight with a reduced amount of a catalyst by admixing a metathesis polymerization catalyst and a metathesis polymerizable cyclo-olefin to the reaction system and allowing them to react with each other. SOLUTION: The objective polymer is obtained by introducing (A) a metathesis catalyst, preferably represented by formula I [M is ruthenium or the like; X and X1 are each an anionic ligand; L and L1 are each a neutral electron donor; R and R1 are each H, a (substituted) alkyl or the like] (for example, ruthenium carbene catalyst of formula II), (B) a metathesis polymerizable cyclo- olefin, for example, 2-norbornene or the like and (C) a compound bearing one or more vinyl groups in its molecule (preferably, a styrene derivative such as styrene) into the reaction system and allowing them to react with each other in an organic solvent, for example, toluene or the like, preferably at 0-100 deg.C usually for 1 minute to 24 hours.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a cycloolefin-based polymer.

[0002]

2. Description of the Related Art It is known that cycloolefins undergo ring-opening polymerization using a metathesis polymerization catalyst system. For example, J. Am. Chem. Soc. , 196
0, Vol. 82,2337 describes that ring-opening polymerization of norbornene is carried out by a metathesis catalyst system.
Angew. Chem. Int. Edn. , 1964,
Vol. No. 3,723 describes that cyclopentene undergoes ring-opening polymerization with a metathesis catalyst system [MoCl5 / Al (C2H5) 3]. Further, a method of producing a polymer by ring-opening polymerization of a cycloolefin is also known. For example, JP-A-50-130900 and JP-A-52-33000 disclose a method of producing a ring-opening polymer using a metathesis catalyst system comprising a halide such as tungsten or molybdenum and an organoaluminum compound. A method is disclosed.

In the above-mentioned metathesis catalyst system, it is known that the activator chemically excites the catalyst component and causes ring-opening polymerization of the norbornene-type monomer. In addition, Macr
omolecules, Volume 2, 4707 pages (199
In 5), various norbornene monomers are polymerized using a ruthenium complex catalyst.

[0004]

The organoaluminum compound used as an activator has a high reactivity. When water, oxygen, impurities, etc. are present in the monomer, they react with them immediately, and their action (catalyst component is not used). ) Is lost. Therefore, the raw material monomer needs to be highly purified by repeating distillation many times. Further, the liquid before the reaction needs to be stored in a container filled with an inert gas in order to avoid the influence of oxygen in the air (for example, JP-A-2-263613), and the like. The handling is troublesome.

[0005] Further, the reaction vessel in contact with the reaction solution is liable to adhere to moisture and oxygen, and therefore, there is a problem that the ring-opening polymerization reaction does not sufficiently proceed, and unreacted starting monomers are generated. As a method for solving this problem, a method in which the inside of the container is replaced with an inert gas can be considered. However, there remains a problem that the apparatus becomes large and the operation becomes complicated. Furthermore,
In this method, the effect of reducing moisture and oxygen adhering to the surface of the reaction vessel in contact with the reaction solution is not sufficient. On the other hand, when the polymerization is carried out using a ruthenium complex catalyst, the ruthenium complex catalyst is relatively stable to air and water, so that it can be handled normally, but because the reaction is fast, it is difficult to control the reaction, Therefore, there is a difficulty in controlling the molecular weight. Also,
This reaction is known to be a so-called living polymerization in which the polymerization terminal proceeds while maintaining the activity. Therefore, the molecular weight of the obtained polymer is determined by the amount of the catalyst used, and it is necessary to increase the amount of the catalyst in order to suppress the increase in the molecular weight, which is not economically preferable.

The present invention provides a method for producing a cycloolefin-based polymer which can obtain a desired molecular weight with a small amount of catalyst and can reduce the amount of unreacted monomer.

[0007]

The process for producing a cycloolefin polymer according to the present invention comprises, in a reaction system, a metathesis polymerization catalyst, a metathesis polymerizable cycloolefin compound and a compound having at least one vinyl group in the molecule. It is characterized by including.

The present inventors have studied various methods for producing a cycloolefin-based polymer in the presence of a metathesis polymerization catalyst. As a result, (1) a metathesis polymerization catalyst (2) one or more metathesis polymerization catalysts Cycloolefin-based compounds (3) It is possible to control the molecular weight by reacting a compound containing at least one vinyl group in the molecule, to obtain a desired molecular weight with a small amount of catalyst, and to reduce the amount of unreacted monomer. I found it.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a metathesis polymerization catalyst that can be used is:

[0010]

Embedded image (Where M is ruthenium or osmium, X and X1
Is an anionic ligand, L and L1 are neutral electron donating groups,
R and R1 each independently represent hydrogen, an alkyl group, an alkenyl group or an aromatic group, and the alkyl group, alkenyl group or aromatic group may have a substituent. ) Or

[0011]

Embedded image (Where M is ruthenium or osmium, X and X1
Is an anionic ligand, L and L1 are neutral electron donating groups,
R and R1 each independently represent hydrogen, an alkyl group, an alkenyl group or an aromatic group, and the alkyl group, alkenyl group or aromatic group may have a substituent. ).

These catalysts are different from a conventionally known two-component metathesis catalyst system in which a catalyst component and an activator are combined, without easily losing catalytic activity due to oxygen or moisture in the air. This is a catalyst capable of subjecting a metathesis-polymerizable cycloolefin-based compound to ring-opening polymerization by metathesis (metathesis) reaction.

Specific examples of such compounds (catalysts) are Ru carbene catalysts as shown in formulas (1) to (8).

[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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A method for synthesizing the above compound (catalyst) is already known. For example, Journal of Amer
ican Chemical Society No. 11
Vol. 8, page 100 (1996) shows a method using a cyclopropene derivative (Scheme 1).

[0023]

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In the same document, a method using a diazo compound represented by the following formula is also shown (Scheme 2).

[0025]

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Also, Organometallics
Vol. 16, No. 18, p. 3867 (1997) also discloses a method using propargyl chloride represented by the following formula (Scheme 3).

[0027]

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Further, Organometallics
According to Vol. 16, No. 18, p. 4001 (1997), the following method is also shown (Chem. 16: Scheme 4, Chem. 17: Scheme 5).

[0029]

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[0030]

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The following is an example of the synthesis of a catalyst. Synthesis Example 1 (see Scheme 2, R5: cyclohexyl group) Tris (triphenylphosphine) ruthenium dichloride (2.5 mmol) in dichloromethane (20 ml)
The solution and phenyldiazomethane cooled to -50 ° C (5.
(0 mmol) in dichloromethane solution at -78 ° C. After removing the cooling bath and reacting for 5 minutes, the reaction solution is concentrated to about 3 ml. Add 20 ml of pentane,
The precipitated crystals are filtered and redissolved in dichloromethane. Thereafter, recrystallization from pentane gives bis (triphenylphosphine) benzylidene ruthenium dichloride (yield: about 90%). Next, 0.3 mmol of the obtained bis (triphenylphosphine) benzylidene ruthenium dichloride was taken, and dichloromethane (10
ml) and tricyclohexylphosphine (0.
66 mmol) in dichloromethane (3 ml) is added, and the mixture is reacted at room temperature with stirring for 30 minutes. The insolubles are removed by filtration, the solvent is evaporated, and the remaining solid is thoroughly washed with acetone and methanol. This is dried in a vacuum drier to obtain bis (tricyclohexylphosphine) benzylidene ruthenium dichloride (yield: about 90%) (Reference: Journal of A)
mericam Chemical Society
118, 100 (1996)).

Synthesis Example 2 (see Scheme 4, R8: phenyl group) 500 ml of Fisher-Porter bottle
e is cyclooctadiene ruthenium dichloride (21
mmol), tricyclohexylphosphine (42 mm
ol), sodium hydroxide (7.2 g) and 250 ml of sec-butanol from which oxygen was removed, and heated at 90 ° C. under 2 atm of hydrogen. Pressurization is repeated several times until hydrogen absorption is completed, and stirring is continued overnight. Cool to room temperature while applying hydrogen pressure to obtain a pale yellow precipitate. Water 30
The precipitate was filtered, dried in a stream of hydrogen,
u (H) ₂ (H ₂ ) ₂ (Pcy ₃ ) ₂ is obtained (yield about 8).
0%). Next, the Ru (H) ₂ (H ₂ ) ₂ (Pc
y ₃₎ is added cyclohexene (15 mmol) in pentane solution of ₂ (1.5 mmol). After about 2 minutes, a yellow solution is obtained, and after about 15 minutes, pale yellow crystals precipitate. The mixture is further stirred for one hour, and the solvent and other volatile components are evaporated. Pentane is added, PhCHCl2 (3 mmol) is added and stirred for 45 minutes. After evaporating the solvent, the remaining crystals are washed with cooled methanol to obtain purple crystalline bis (tricyclohexylphosphine) benzylidene ruthenium dichloride (yield about 60%). (Reference: Org
nanometallics Vol. 16, No. 18, 400
1 page (1997)

Synthesis Example 3 (see Scheme 3, R6 and R
7: methyl group) 500 ml of Fisher-Porter bottle
e is cyclooctadiene ruthenium dichloride (21
mmol), tricyclohexylphosphine (42 mm
ol), sodium hydroxide (7.2 g) and 250 ml of sec-butanol from which oxygen was removed, and heated at 90 ° C. under 2 atm of hydrogen. Pressurization is repeated several times until hydrogen absorption is completed, and stirring is continued overnight. Cool to room temperature under hydrogen pressure to give a pale yellow precipitate. Water 30
The precipitate is filtered off, dried in a stream of hydrogen and dried.
u (H) ₂ (H ₂ ) ₂ (Pcy ₃ ) ₂ is obtained (yield about 8).
0%). Next, the Ru (H) ₂ (H ₂ ) ₂ (Pc
y ₃ ) ₂ (1.5 mmol) in dichloroethane solution 30
Dissolve in ml and cool to -30 ° C. 3-chloro-3-
Add methyl-1-butyne (1.5 mmol). The solution immediately turns reddish purple and is allowed to react for 15 minutes. The cooling bath was removed and degassed methanol (20 ml) was added to precipitate purple crystals. Wash with methanol and dry to obtain the desired catalyst (95% yield). (Reference: Organometallics Vol. 16, 18)
No. 3867 (1997))

The metathesis-polymerizable cycloolefin-based compound used as a raw material in the present invention may be any compound that is useful in metathesis polymerization. Among them, substituted or unsubstituted norbornene, dicyclopentadiene,
Norbornene monomers such as dihydrodicyclopentadiene are preferably used. Examples of the norbornene-based monomer include bicyclic norbornenes such as norbornene, methylnorbornene, dimethylnorbornene, ethylnorbornene, ethylidenenorbornene, and butylnorbornene, dicyclopentadiene (a dimer of cyclopentadiene), dihydrodicyclopentadiene, methyldicyclopentadiene, Tricyclic norbornene such as dimethyldicyclopentadiene, tetracyclic dodecene, tetracyclic norbornene such as methyltetracyclododecene, dimethylcyclotetradodecene, tricyclopentadiene (trimer of cyclopentadiene), tetracyclopentadiene (cyclopentadiene Norbornene having five or more rings). A compound having two or more norbornene groups,
For example, norbornadiene, tetracyclododecadiene, symmetric tricyclopentadiene, and the like can be used as the polyfunctional crosslinking agent. These metathesis polymerizable cycloolefin compounds can be used alone or as a mixture of a plurality of them.

It should be noted that cyclobutene (other than norbornene), cyclopentene, cyclooctene, which can be ring-opened copolymerized with the above metathesis polymerizable cycloolefin compound,
Cycloolefins such as cyclododecene, tetrahydroindene, and methyltetrahydroindene can be mixed and used as long as the object of the present invention is not impaired. Incidentally, the usual commercially available dicyclopentadiene may contain vinyl norbornene, tetrahydroindene, methylvinylnorbornene, methyltetrahydroindene, methyldicyclopentadiene, dimethyldicyclopentadiene, tricyclopentadiene, and the like as impurities. Dicyclopentadiene of various purity is commercially available. The dicyclopentadiene used in the present invention varies depending on the intended use of the obtained polymer, but usually has a purity of 80% or more, preferably 90% or more.
% Or more is used.

Further, an antioxidant can be added to the metathesis polymerizable cycloolefin compound used in the present invention, if necessary. Note that ordinary commercially available dicyclopentadiene already contains an antioxidant such as 2,6-di-t-butyl-4-methylphenol and 4-t-butylcatechol. In use, the contained antioxidant can be removed or newly added.

The antioxidant to be used is not particularly limited as long as it has an antioxidant ability, and preferred are hindered phenol-based antioxidants, and 2,6-di-
t-butyl-4-methylphenol, 2,6-di-t-
Butyl-4-ethylphenol, stearyl-β-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate, tetrakis- [methylene-3-
(3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane, 2,2′-methylenebis (4-methyl-6-tert-butylphenol),
2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-methylenebis (2,6-di-t-
Butylphenol), 1,3,5-trimethyl-2,
4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ′,
5'-di-t-butyl-4'-hydroxybenzyl)-
S-triazine-2,4,6- (1H, 3H, 5H) trione and the like. The amount of antioxidant added is usually 1
It is 0 to 10,000 ppm. The catalyst is as described above, and its addition amount is 0.001 to 20% by weight based on the DCPD resin solution, but is preferably 0.01 to 5% by weight for reasons of economy and curing rate. .

The compound having at least one vinyl group in the molecule used in the present invention includes styrene derivatives such as styrene, methylstyrene, hydroxystyrene, cyanostyrene, methoxystyrene and divinylbenzene, ethyl vinyl ether, propyl vinyl ether, Vinyl compounds such as vinyl ethers such as butyl vinyl ether and the like, and these can be used as a mixture of two or more kinds. The amount of the compound containing at least one vinyl group in the molecule is appropriately determined depending on the desired molecular weight, and is usually 0.5 to 3 with respect to the ruthenium complex catalyst.
000 mol%. The compound having a vinyl group used in the present invention acts as a so-called chain transfer agent. Therefore, the degree of dispersion of the obtained polymer is larger than when no vinyl group is used.

The polymerization is carried out in an organic solvent, and the organic solvent is not particularly limited as long as the monomer, the catalyst and the polymer are dissolved and do not adversely affect the reaction. Specifically, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, aromatic solvents such as benzene, toluene and xylene, halogen solvents such as methylene chloride and chloroform, dimethylformamide, dimethylacetamide, N-methyl- A polar solvent such as 2-pyrrolidone is used.

Solvent used at the reaction temperature, usually -50 to 150
° C, preferably from 0 to 100 ° C. The polymerization time can be appropriately determined depending on the amount of the catalyst and the polymerization temperature, but is usually from 1 minute to 24 hours.

In the present invention, a glass reinforcing material, a filler, a modifier, a polymerization rate regulator, a release agent, a colorant, a light stabilizer, a flame retardant, and the like are optionally added to the DCPD resin liquid as required. can do. Glass fiber is preferably used as the glass reinforcing material, and may be in any form of long fiber, short fiber or powder. A roving in which the strands are aligned to form a bundle, a roving cloth in which the roving is woven, a continuous strand mat in which glass long fibers are bonded in a random coil shape with a binder to form a mat, a chopped strand in which glass long fibers are cut, Chopped strand mat, surfacing mat, twill weave mat or 3D glass mat combining cloth and strand (chori Co., Ltd.)
(Trade name: Parabeam), glass non-woven fabric, continuous strand or glass preform formed by three-dimensionally bonding and forming a strand with a binder.

Examples of glass reinforcing materials other than fibers include milled glass, cut fiber, microfiber,
Microballoons, flaky glass powder and the like can also be used. The aspect ratio, particle size, and shape are appropriately selected according to the purpose.

The glass fiber reinforcement may be treated with the silane coupling agent for surface treatment used in the present invention.
The silane coupling agent is generally represented by the formula YSiX (Y is a monovalent group having a functional group and binding to Si, and X is a monovalent group having a hydrolyzing property and binding to Si). Y above
As the functional group in, for example, vinyl, amino, epoxy, chloro, mercapto, methacryloxy, cyano,
There are groups such as carbamate, pyridine, sulfonyl azide, urea, styryl, chloromethyl, ammonium salts, alcohols and the like. X includes, for example, chloro, methoxy, ethoxy, methoxyethoxy and the like.

Specific examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N, N-dimethylaminophenyltriethoxysilane, trimethoxysilylbenzoic acid, chloromethylphenethyltrimethoxysilane, 2-styryle Le triethoxysilane, aminoethyl aminomethyl phenethyltrimethoxysilane,
γ-chlorophenyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, allyltriethoxysilane, 3-aminoprop-8pyrmethyldiethoxysilane, 3-aminotrimethoxysilane, bis (2-hydroxyethyl) aminopropyltriethoxysilane , Bis {3- (triethoxysilyl) propyl} amine, bis {3- (triethoxysilyl) propyl} ethylenediamine, 2-chloroethyltriethoxysilane, chloromethyltriethoxysilane, chlorophenyltriethoxysilane, 3-cyanopropyl Triethoxysilane, N,
N-diethyl-3-aminopropyltrimethoxysilane, N, N-diethylaminophenyltriethoxysilane, 1- (dimethylchlorosilyl) -2- (chloromethylphenyl) ethane, isocyanatopropyltriethoxysilane, mercaptoethyltriethoxy Silane, methacryloxyethyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, N-methylaminopropyltriethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane hydrochloride, 1-trichloro Silyl-2- (chloromethylphenyl) ethane, β-trichlorosilyl-4-ethylpyridine, triethoxysilylpropylethylcarbamate, N- (triethoxysilylpropyl) urea,
1-trimethoxysilyl-2- (aminomethyl) phenylethane, 1-trimethoxysilyl-2- (chloromethyl) phenylethane, 2- (trimethoxysilyl) ethylphenylsulfonyl azide, trimethoxysilylpropyl allylamine, trimethoxy Silylpropyldiethylenetriamine, p-aminophenyltrimethoxysilane, 2-styrylethyltrimethoxysilane, aminoethylmethylphenethyltrimethoxysilane, 6-triethoxysilyl-2-norbornene and derivatives thereof, and the like. It is also possible to use.

The silane coupling agent includes epoxy resin, phenol resin, bismaleimide resin, cyanate S resin, acrylic resin, methacrylic resin, polystyrene, polyimide, polyamide, polyester, siloxane polyimide, polyether polyimide, polyester polyimide, etc. May be included. When these resins are used, a curing agent, a curing accelerator, a catalyst and the like may be used as necessary.

When the above-mentioned silane coupling agent itself is in a liquid state, it can be used as it is as a treatment liquid used for treating the surface of the glass fiber, but it is usually used as a solution of water or an organic solvent. Preferably, it is used.

The organic solvent is not particularly limited as long as it can dissolve the silane coupling agent and other components. In addition to alcohols such as methanol, ethanol, propyl alcohol, and isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene, xylene, dimethylformamide, dimethylacetamide, N-methyl-2-
Pyrrolidone, methyl cellosolve, ethyl cellosolve, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and the like are used, and these may be used as a mixture of two or more kinds including water.

The concentration of the silane coupling agent in the treatment liquid is 0.001 to 10% by weight, preferably 0.01 to 10% by weight.
~ 5% by weight. If the amount is less than 0.001% by weight, the effect of improving the adhesive strength at the interface between the resin and the glass fiber is small, and the effect is not so large.
If it is more than the weight%, it is economically undesirable. The temperature and time of the treatment are not particularly limited, but are usually 0 to 1
00 ° C, 0.5 to 10 minutes, preferably 20 to 50 ° C,
5 seconds to 3 minutes.

Examples of the filler include inorganic fillers such as silica sand, calcium carbonate, aluminum hydroxide and clay, and organic fillers such as wood powder, polyester and polystyrene beads. The amount used depends on the physical properties of the polymer,
It can be appropriately determined according to the viscosity of the resin liquid and the like.

As the modifier, for example, an elastomer,
Natural rubber, butadiene rubber, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), polymethyl methacrylate,
Examples include polyvinyl acetate, polystyrene, epoxy resin, phenol resin, bismaleimide resin, cyanate S resin, acrylic resin, methacrylic resin, polystyrene, polyimide, polyamide, polyester, siloxane polyimide, polyether polyimide, polyester polyimide and the like. The amount to be used depends on the physical properties of the intended cured resin, but usually 1 to 100 parts by weight of the resin.
It can be used in the range of 50 parts by weight.

Examples of the polymerization rate regulator include triphenylphosphine. Examples of the release agent include zinc stearate, silicone oil, fluorine oil and the like. Usually, 0.01 to 5 parts can be added to 100 parts of the resin. As a coloring agent, titanium dioxide, cobalt blue, inorganic pigments such as cadmium yellow,
Organic pigments such as carbon black, aniline black, phthalocyanine, and quinacdrine are exemplified.

Examples of the weather resistance imparting agent include an ultraviolet absorber and a light stabilizer. Examples of the ultraviolet absorber include salicylic acid-based ultraviolet absorbers such as phenyl salicylate and para-t-butylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4, Benzophenone-based ultraviolet absorbers such as 4'dimethoxybenzophenone, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-
3 ′, 5′-di-t-butylphenyl) benzotriazole Benzotriazole ultraviolet absorber such as 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole, 2-ethylhexyl And cyanoacrylate-based ultraviolet absorbers such as -2-cyano-3,3'-diphenylacrylate and ethyl-2-cyano-3,3'-diphenylacrylate. These may be used alone or in combination of two or more.

In order to improve the weather resistance, bis (2,2,6,6-tetramethyl-4-) is added together with the above-mentioned ultraviolet absorber.
Piperidyl) sebacate, bis (1,2,2,6,6-
Hindered amine light stabilizers such as pentamethyl-4-piperidinyl) sebacate and dimethyl succinate / 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate are added. Is also good.

As the flame retardant, hexabromobenzene,
Tetrabromobisphenol A, decabromodiphenyl oxide, tribromophenol, dibromophenyl glycidyl ether, perchloropentacyclodecane,
Halogen compounds such as heptate derivatives may be used alone or in combination of two or more. Further, a phosphate compound such as tris (dichloropropyl) phosphate and tris (dibromopropyl) phosphate, a boric acid compound and the like can also be used in combination. Further, examples of the auxiliary flame retardant include antimony trioxide, iron oxide, aluminum hydride and the like, and the flame retardant effect is enhanced by using these together with the flame retardant. Usually, the halogen-based flame retardant is resin 100
1 to 50 parts per part, and an auxiliary flame retardant such as antimony trioxide is used in the range of 1 to 15 parts. Hydrates such as aluminum hydroxide and magnesium hydroxide can also be used as fillers for flame retardancy. It is preferable to use these additives in the range of 10 to 300 parts with respect to 100 parts of the resin.

[0055]

The present invention will be described below with reference to examples. Note that the present invention is not limited to this embodiment. Example 1 In a 100 ml four-necked flask, 2-norbornene
5 g (26.5 mmol), triphenylphosphine 0.0247 g (0.092 mmol), toluene 10
g, and stirred while flowing nitrogen gas into the flask. When 2-norbornene is dissolved, a solution obtained by dissolving 0.038 g (0.046 mmol) of a ruthenium carbene catalyst in 3.5 g of toluene is dropped into the flask. The reaction was continued as it was, and after 30 minutes, 0.024 g of styrene was used.
(0.23 mmol) was added and the reaction continued further. At predetermined time intervals, a sample was taken from the reaction solution and poured into hexane to precipitate a polymer. Thereafter, the mixture was filtered and dried to obtain a polymer.

Example 2 In a 100 ml four-necked flask, 2-norbornene 2.
5 g (26.5 mmol), triphenylphosphine 0.0247 g (0.092 mmol), toluene 10
g, and stirred while flowing nitrogen gas into the flask. When 2-norbornene is dissolved, a solution of 0.072 g (0.088 mmol) of a ruthenium carbene catalyst dissolved in 3.5 g of acetone is dropped into the flask. Continue the reaction as it is, and after 30 minutes, 0.018 g of styrene
(0.176 mmol) was added and the reaction continued further.
At predetermined time intervals, a sample was taken from the reaction solution and poured into hexane to precipitate a polymer. Thereafter, the mixture was filtered and dried to obtain a polymer.

Example 3 5 g (0.015 mol) of exo-5-norbornene-2,3-dicarboxylic anhydride and 10 g of acetone were placed in a 100 ml four-necked flask, and stirred while flowing nitrogen gas into the flask. I do. exo-5-norbornene-2,
When the 3-dicarboxylic anhydride is dissolved, a solution obtained by dissolving 0.038 g (0.046 mmol) of a ruthenium carbene catalyst in 3.5 g of acetone is dropped into the flask. Continue the reaction as it is, and after 30 minutes 0.005 g of styrene
(0.046 mmol) was added and the reaction continued further.
At predetermined time intervals, a sample was taken from the reaction solution and poured into hexane to precipitate a polymer. Thereafter, the mixture was filtered and dried to obtain a polymer.

Example 4 In a 100 ml four-necked flask, 2-norbornene 2.
5 g (26.5 mmol), triphenylphosphine 0.0247 g (0.092 mmol), styrene
0.024 g (0.23 mmol) and 10 g of toluene are added, and the mixture is stirred while flowing nitrogen gas into the flask. 2
When the norbornene was dissolved, 0.038 g (0.046 mmol) of the ruthenium carbene catalyst was added to 3.
The solution dissolved in 5 g is dropped into the flask. At predetermined time intervals, a sample was taken from the reaction solution and poured into hexane to precipitate a polymer. Thereafter, the mixture was filtered and dried to obtain a polymer.

Comparative Example 1 In a 100 ml four-necked flask, 2-norbornene 2.
5 g (26.5 mmol), triphenylphosphine 0.0247 g (0.092 mmol), toluene 10
g, and stirred while flowing nitrogen gas into the flask. When 2-norbornene is dissolved, a solution in which 0.072 g (0.088 mmol) of a ruthenium carbene catalyst is dissolved in 3.5 g of toluene is dropped into the flask. At predetermined time intervals, the reaction solution was sampled from the reaction solution and poured into hexane to precipitate a polymer. Thereafter, the mixture was filtered and dried to obtain a polymer.

The molecular weights of the polymers obtained in Examples 1 to 4 and Comparative Example 1 were measured by gel permeation chromatography (GPC). FIG. 1 shows the results of the number average molecular weight measured with respect to the sampling time. GPC measuring apparatus Pump L-6000 detector manufactured by Hitachi, Ltd. L-3000 manufactured by Hitachi, Ltd. Degasser Gas-Chrome Industry Model-546 GPC measurement conditions Column Gelpack A-150 manufactured by Hitachi Chemical Solvent Tetrahydrofuran Flow rate 1 ml / min Column temperature 40 ° C.

The following table shows the degree of polymer dispersion (weight average molecular weight / number average molecular weight) and polymer yield.

[0062]

[Table 1]

As shown in Examples 1 to 4, in the system using the vinyl compound, it was found that a polymer was obtained in high yield and the molecular weight was controllable. Further, since the degree of dispersion is increased, the vinyl compound acts as a chain transfer agent.

[0064]

According to the present invention, the molecular weight of the metathesis polymerizable cycloolefin compound can be controlled, a desired molecular weight can be obtained with a small amount of catalyst, and the amount of unreacted monomer can be reduced.

[Brief description of the drawings]

FIG. 1 is a graph showing the measurement results of the number average molecular weight of the polymers obtained in Examples 1 to 4 and Comparative Example 1.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Nobuyoshi Kikuchi 48 Wadai, Tsukuba, Ibaraki Prefecture F-term in Tsukuba Development Laboratory, Hitachi Chemical Co., Ltd. (reference) 4J032 CA22 CA23 CA24 CA27 CA34 CA35 CA36 CA38 CA43 CA45 CA46 CA68 CB01 CB03 CD02 CE03 CE16 CE17 CE18 CE22

Claims (4)

[Claims] 1. A process for producing a cycloolefin polymer, comprising a metathesis polymerization catalyst, a metathesis polymerizable cycloolefin compound and a compound containing at least one vinyl group in the molecule in a reaction system. 2. The metathesis polymerization catalyst is represented by the following general formula (A): (Where M is ruthenium or osmium, X and X1
Is an anionic ligand, L and L1 are neutral electron donating groups,
R and R1 each independently represent hydrogen, an alkyl group, an alkenyl group or an aromatic group, and the alkyl group, alkenyl group or aromatic group may have a substituent. The method for producing a cycloolefin polymer according to claim 1, which is a compound represented by the formula: (3) a metathesis polymerization catalyst represented by the following general formula (B): (Where M is ruthenium or osmium, X and X1
Is an anionic ligand, L and L1 are neutral electron donating groups,
R and R1 each independently represent hydrogen, an alkyl group, an alkenyl group or an aromatic group, and the alkyl group, alkenyl group or aromatic group may have a substituent. The method for producing a cycloolefin polymer according to claim 1, which is a compound represented by the formula: 4. The method according to claim 1, wherein the compound containing at least one vinyl group in the molecule is a styrene derivative.