JP2698160B2 - Method for producing plasticized crosslinked polymer molding and combination of reactive solutions - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION a. Industrial Field of the Invention The present invention relates to a crosslinked polymer molding obtained by simultaneously polymerizing a metathesis polymerizable monomer mainly composed of dicyclopentadiene in the presence of a metathesis polymerization catalyst system. The present invention relates to a method for plasticizing a product. More specifically, the present invention relates to a method of using a specific aromatic hydrocarbon as a plasticizer for a specific crosslinked metathesis polymer molded product.

b. Prior Art It is known that ring-opening polymerization of a strained cyclic olefin is carried out by a metathesis polymerization catalyst system. Utilizing it, a monomer having two cyclic olefin groups, which is obtained at low cost such as dicyclopentadiene and has metathesis polymerizability, is poured into a mold in a liquid state, and bulk polymerization is performed therein, and polymerization and molding are performed. There has been proposed a single-step method (see, for example, Japanese Patent Application Laid-Open No. 58-129013).

According to such a method, a large-sized molded product can be obtained using an inexpensive mold, so that it has a possibility of being used for a wide range of applications. However, such molded products are often required to be plasticized and used in order to improve impact resistance depending on the use.

Such plasticizing methods include, for example, U.S. Pat.
No. 8 proposes the use of ester plasticizers with a solubility parameter of 7.8 to 10.2. On the other hand, a metathesis polymer from a cyclic olefin, for example, poly (dicyclopentadiene) has a solubility parameter of about 9.3 as measured by the present inventors. In that respect, the ester plasticizer has a strong affinity. Poly (dicyclopentadiene) has a structure with no hydrogen bond, whereas the ester is weak but has hydrogen bond, so that the solubility parameter is similar. However, there is a concern that the affinity is not large. In fact, the swelling ratio of the above poly (dicyclopentadiene) with an ester material having a solubility parameter of 9.0 to 9.5 is very small.

On the other hand, it was found that halogens such as chloroform and toluene, hydrocarbons and aromatic hydrocarbons having a solubility parameter of 9.0 to 9.5 exhibited a large swelling ratio.

c. Configuration of the Invention The present inventors have studied the use of a high-boiling hydrocarbon having both an aromatic ring and an aliphatic group as a plasticizer, and have reached the present invention.

 The present invention includes the following inventions.

(1) A reactive solution (solution A) of a metathesis polymerizable monomer mainly containing dicyclopentadiene containing a catalyst component of a metathesis polymerization catalyst system and dicyclopentadiene mainly containing an activator component of a metathesis polymerization catalyst system At least one saturated aliphatic group and at least one benzene nucleus or naphthalene by mixing at least the reactive solution (solution B) of the metathesis polymerizable monomer thus obtained and molding at the same time as polymerization to obtain a polymer molded product. A method for producing a plasticized crosslinked polymer molded product, wherein a hydrocarbon having a core and having fluidity at room temperature having 11 to 35 carbon atoms is added to at least one of the solutions A and B.

(2) (a) a reactive solution (solution A) of a metathesis polymerizable monomer mainly composed of dicyclopentadiene containing a catalyst component of a metathesis polymerization catalyst system and dicyclopentadiene containing an activator component of a metathesis polymerization catalyst system And a fluid having at least one saturated aliphatic group and at least one benzene nucleus or naphthalene nucleus having at least one saturated aliphatic group and having 11 to 35 carbon atoms and having fluidity at room temperature. Is added to at least one of the solutions A or B.

It is not necessary to use a hydrocarbon having a single structure as described above in the present invention, but rather a mixture of isomers and the like. Such a carbon number of 12 to 35 is used, but from the viewpoint of low volatility, the larger the molecular weight, that is, the larger the carbon number is preferable.However, in terms of production, purification, handling, and low-temperature characteristics, the carbon number is Larger ones are more difficult, and those having 14 to 30 carbon atoms are generally preferred. From the viewpoint of the boiling point, those having at least 200 ° C. or higher, more preferably 250 ° C. or higher, and further preferably 300 ° C. or higher at normal pressure are used. In particular, industrially, a Friedel-Crafts reaction of α-olefins of propylene 3- to 4-mers with benzene or naphthalene before sulfonation of a sulfonic acid surfactant such as sodium alkylbenzene sulfonate or sodium alkylnaphthalene sulfonate is carried out. Are preferred because hydrocarbons having one or two bonds at a low cost can be obtained at low cost.

That is, there are obtained dedecenylbenzene (two types of dodecenyl group having a less branched chain and a branched dodecenyl group are selectively used), dodecenylnaphthalene, nonylbenzene, dinonylbenzene, dinonylnaphthalene, and the like. It can be said that it is an example of a hydrocarbon which is easy to perform. Particularly, dodecenylbenzene is preferred. Other industrially readily available hydrocarbons suitable for use in the present invention include a group of compounds used as heating media. These compounds are selected from compounds having a high boiling point, low volatility and excellent thermal stability so that they can be used even at high temperatures, and which do not lose fluidity even at low temperatures, and can be easily obtained in high purity.

Such hydrocarbons include partially hydrogenated terphenyl,
Alkyl-substituted biphenyls such as triethyl-, diethyl- or monoethyl-diphenyl, methyl, dimethyl,
Examples thereof include alkylnaphthalenes such as ethyl and diethyl-naphthalene. Further, 1- (3 ′,
Examples thereof include alkyldiphenylethane and alkyldiphenylmethane such as 5'-dimethylphenyl) -2-phenylethane.

Further, the group itself has a somewhat lower thermal stability than a methyl group or an ethyl group, but an isopropyl group can be mentioned as an alkyl substituent suitably usable for the purpose of the present invention, and isopropyl-substituted benzene or naphthalenes,
For example, tri (isopropyl) benzene, cymens, isopropylnaphthalene, diisopropylnaphthalene and the like can also be used as suitable hydrocarbons.

Such aliphatic aromatic hydrocarbons may have a halogen substituent in addition to the hydrocarbon. However, high-boiling halogen-substituted aromatic hydrocarbons may contain compounds that are difficult to decompose and accumulate, such as polychlorinated biphenyl (PCB), which has become famous.

The hydrocarbons as described above are generally synthesized by petrochemical means, have a good purity, and can be used without inhibiting the metathesis polymerization catalyst system.

In addition to the above-mentioned synthesized hydrocarbons, in the separation of petroleum fractions and the fractions of cracking components, for example, those containing many aromatic groups among those commercially available as process oils,
Products that meet the above conditions on average can be used. However, it should be noted that these may contain impurities such as a polar group or a sulfur component generated by oxidation, and such impurities may inhibit the metathesis polymerization catalyst system.

As described above, the specific aromatic hydrocarbons used in the present invention have good affinity with a crosslinked metathesis polymer containing dicyclopentadiene as a main monomer, and have a rigid aromatic ring as described above. Because it has, it hardly causes bleeding and acts as an effective and excellent plasticizer.

Also, as mentioned above, it is generally unpleasant for both the main catalyst component and the activator of the metathesis polymerization catalyst system, and may be added to either acidic solution. Further, it has generally better solubility than dicyclopentadiene used as a main monomer, and is characterized as being effective as a solubilizing agent for dissolving an additive to be added to a reactive solution.

The amount of the hydrocarbon can be appropriately determined depending on the required degree of plasticization and necessity as a solubilizer, but is generally 1 to 40% by weight, more preferably 3 to 30% by weight based on all monomers. More preferably, a range of 5 to 25% by weight is used.

The present invention uses dicyclopentadiene as the main monomer. The term "used as a main monomer" generally means that at least 50% by weight, more preferably at least 75% by weight, even more preferably at least 90% by weight of all monomers.

Examples of the metathesis polymerizable monomer used together with dicyclopentadiene include a monomer having 1 to 3 other cyclic olefins having a norbornene structure or a metathesis polymerizable equivalent thereto.

Preferred specific examples include oligocyclopentadiene such as tricyclopentadiene, ethylidene norbornene,
Norbornene, 5-methylnorbornene, norbornadiene, 6-ethylidene-1,4,5,8-dimethano-1,4,4a, 5,
6,7,8,8a-octahydronaphthalene, 1,4,5,8-dimethano-1,4,4a, 5,8,8a-hexahydronaphthalene, 1,4,5,8
-Dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-methyl-1,4,5,8-dimethano-1,4,4a, 5,6,7,
8,8a-octahydronaphthalene and the like can be mentioned.

If necessary, metathesis polymerizable cycloolefin monomers having different elements such as oxygen and nitrogen can also be used. Such polar monomers are often used in addition to, for example, about 1 to 20% by weight in copolymerization with dicyclopentadiene or the like.

Such a polar monomer also preferably has a norbornene structural unit, and the polar group is an ester group,
Ether groups, cyano groups, N-substituted imides and the like are preferred.

Specific examples of such a copolymerized monomer include 5-methoxycarbonylnorbornene, 5- (2-ethylhexyloxy) carbonyl-5-methylnorbornene, 5-phenyloxymethylnorbornene, 5-cyanonorbornene, 6-cyano-1, 4,5,8-Dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, N-butylnadic imide and the like.

As described above, the metathesis polymerizable monomer is required to have as few impurities as possible to inactivate the metathesis polymerization catalyst.

As the main catalyst component in the metathesis polymerization catalyst system used in the present invention, salts such as halides such as tungsten, rhenium, tantalum and molybdenum are used, and a compound of tungsten and molybdenum is preferable, and a tungsten compound is particularly preferable. As such a tungsten compound, tungsten halide, tungsten oxyhalide, tungstate, and the like are preferable, and more specifically, tungsten hexachloride, tungsten oxychloride, and the like are preferable. It has been found that such a tungsten salt compound immediately starts cationic polymerization when added directly to a monomer, which is not preferable. Therefore, it is preferable to use the tungsten salt compound after suspending it in an insoluble solvent such as benzene, toluene, chlorobenzene or the like and solubilizing it by adding a small amount of an alcohol compound or a phenol compound.

Further, as described above, it is preferable to add about 1 to 5 mol of a Lewis base or a chelating agent to 1 mol of the tungsten compound in order to prevent undesired polymerization. Examples of such additives include acetylacetone, alkyl acetoacetates, tetrahydrofuran, and benzonitrile.

Thus, a monomer solution containing a catalyst component (solution A)
Has sufficient stability for practical use.

On the other hand, the activator component in the metathesis polymerization catalyst system is
Organometallic compounds, mainly tetraalkyltin, alkylaluminum compounds and alkylaluminum halide compounds, mainly alkylated compounds of metals of Groups I to III of the Periodic Table are preferred, and specific examples include diethylaluminum chloride and ethyldichloride. Aluminum, trioctyl aluminum, dioctyl aluminum iodide, tetrabutyl tin, and the like can be given. The other solution (corresponding to solution B) is formed by dissolving the organometallic compound as the activator component in the raw material monomer.

The hydrocarbon used in the present invention is the above-mentioned reactive solution A,
Any one or both of B and the amount of addition can be used by dividing it arbitrarily. As described above, when an action as a solubilizer is expected, it is sufficient to add a large amount to the required side.

In the present invention, a crosslinked polymer molded product can be basically obtained by mixing the solution A and the solution B. However, if the above composition is maintained, the polymerization reaction starts very quickly. In some cases, curing may occur while not sufficiently flowing into the casting mold, which often poses a problem. As described above, it is preferable to use an activity modifier for this purpose.

As such a regulator, Lewis bases are generally used, and among them, ethers, esters, nitriles and the like are used. Specific examples include ethyl benzoate, butyl ether, diglyme and the like. Such a regulator can be added to both the solutions, but in general, it may be more effective to add the regulator to the solution of the component of the activator of the organometallic compound. When a monomer having a Lewis base group is used as described above, the role of the regulator can be replaced.

The amount of the metathesis polymerization catalyst used is, for example, when a tungsten compound is used as a catalyst component, the ratio of the tungsten compound to the raw material monomer is about
When the alkyl activator component is an alkylaluminum, the activator component is about 100 to 1 to about 2000 to 1, preferably about 200 to 1, preferably about 2000 to 1. A neighborhood of 1 to 500 to 1 is used. Further, as described above, the masking agent and the adjusting agent can be appropriately adjusted and used according to the amount of the catalyst system to be used by experiments.

In practical use, various additives can be further added to the crosslinked polymer molded product obtained by the production method of the present invention in order to improve or maintain its properties. Such additives include fillers, pigments, antioxidants, light stabilizers, flame retardants, polymer improvers, and the above-mentioned plasticizers other than hydrocarbons. In the case of such an additive, it is impossible to add it after the crosslinked polymer is formed as in the case of the plasticizer in the present invention. Therefore, it is necessary to add the additive to the raw material solution beforehand. There is.

The easiest method is a method of adding the solution A and / or the solution B in advance to one or both of the solution A and the solution. It must not react to some extent with the agent component and not react to some extent, and must not inhibit polymerization. Inevitably, even if the reaction cannot be avoided but coexist, if the polymerization is not substantially inhibited, it is mixed with the monomer, and the third liquid is adjusted. . In the case of a solid filler,
Both components are mixed, and immediately before the start of the polymerization reaction or while the polymerization is being performed, for those having a shape that can sufficiently fill the voids, it is also possible to fill in the molding mold in advance. .

Reinforcing agents or fillers as additives are effective in improving flexural modulus. Such materials include glass fiber, mica, wollastonite and the like. Those surface-treated with a silane coupler or the like can be suitably used.

Further, the crosslinked polymer molded product according to the production method of the present invention,
It is preferable to add an antioxidant, and it is therefore desirable to add a phenolic or amine antioxidant to the solution in advance. Specific examples of these antioxidants include 2,6-t-butyl-P-cresol, N, N'-diphenyl-P-phenylenediamine, tetrakis [methylene (3,5-di-t-butyl-4-). Hydroxycinnamate)] methane and the like.

Further, the polymer molded product obtained by the production method of the present invention may be added with another polymer, particularly in a reactive solution state. As described above, the addition of an elastomer as such a polymer additive is effective in enhancing the impact resistance of a molded product and adjusting the viscosity of a solution. Examples of elastomers used for such purposes include styrene-butadiene rubber, styrene-butadiene-styrene triblock rubber, styrene-isoprene-styrene triblock rubber, polybutadiene, polyisoprene, butyl rubber, ethylene propylene-dienter-polymer, and nitrile rubber. Natural elastomers. When a large amount of residual monomer remains in the molded article of the present invention, a peculiar smell may be emitted. Examples of such residual monomer reducing agents include α, α, α-trichlorotoluene, dicycloldiphenylmethane, trichloroacetic acid ester, phthalic acid chloride, benzoic anhydride, phosphorus oxychloride, benzenesulfonic acid chloride and the like.

The present invention is carried out by simultaneously performing polymerization and molding using the combination of the reactive solutions as described above.

As the molding method, as described above, a catalyst and a raw material monomer are mixed by a simple mixer such as a static mixer, or a resin injection method in which a premix mixed in advance is poured into a mold, and a catalyst system. It is possible to employ a RIM method in which the solution A and the solution B divided into two are colliding and mixed at a head portion and then poured into a mold as it is. Especially R
The IM method is generally used.

In either case, the injection pressure into the mold can be relatively low, so that inexpensive molds can be used. Further, when the polymerization reaction in the mold is started, the temperature in the mold is rapidly increased by the reaction heat, and the polymerization reaction is completed in a short time. Unlike polyurethane-RIM, release from the mold is easy and often does not require a special release agent.

In the present invention, since the molded product has many double bonds, an oxide layer is formed on the surface, so that the adhesion to commonly used coating materials such as epoxy and polyurethane is good.

The molded product thus obtained is added with the above-mentioned hydrocarbon, so that it is plasticized as compared with the unadded dicyclopentadiene-based crosslinked polymer, the flexibility is improved, and they are hard to bleed and are stable. Therefore, it can be used as a molded product for a wide range of applications, such as housings for various devices and impact-resistant members.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. It should be noted that the examples are for explanation, and the present invention is not limited thereto.

Examples 1 to 6 Commercially available DCP was purified by distillation under reduced pressure in a nitrogen stream to obtain purified dicyclopentadiene having a freezing point of 33.4 ° C. Purity measurement by gas chromatography showed a purity of 99% or more.

Purity measurement by gas chromatography using a commercially available high-purity ethylidene norbornene (ENB) as a monomer showed 99% or more.

[Preparation of Main Catalyst Concentrate] 19.80 g (0.05 mol) of high-purity tungsten hexachloride was added to 90 ml of dry toluene under a nitrogen stream, and t-butanol was added in an amount of 0.1 g.
A solution of 925 g in 5 ml of toluene was added and stirred for 1 hour. Then, a solution consisting of 11.05 g (0.05 mol) of nonylphenol and 5 ml of toluene was added, and the mixture was stirred for 1 hour under a nitrogen purge. 10 g of acetylacetone was added to the mixture, and stirring was continued overnight under a nitrogen purge while purging out hydrogen chloride gas produced as a by-product.
A catalyst concentrate containing 0.5M tungsten was prepared.

[Preparation of activator concentrate] Di-n-octyl aluminum iodide 5.70 g, tri-n-octyl aluminum 31.17 g, diglyme 13.42
g under a nitrogen stream, then add DCP and add 100 m
The resultant was diluted to 1 to obtain a 1.0 M aluminum-containing activator concentrate.

[Preparation of Reaction Solution A] Dicyclopentadiene, ethylidene norbornene, ethylene-propylene diene terpolymer in a weight ratio of 93/3/4
The reaction solution A was prepared by mixing 20 g of Ethanox702 and 16.2 cc of the main catalyst concentrate under an inert atmosphere with 1000 g of the solution mixed and dissolved in the above.

[Preparation of Reaction Solution B] Dicyclopentadiene, ethylidene norbornene and ethylene-propylene diene terpolymer were added in a weight ratio of 93/3.
Activated activator concentrate 23.7c to 1000g of the solution mixed and dissolved in / 4
The resulting mixture was mixed to obtain a reaction solution B.

To the reaction solutions A and B obtained above, hydrocarbons as shown in Table 1 were added to each of the reaction solutions A and B at a ratio as shown in the same table. Using the solutions A and B after the addition,
Using a micro RIM machine, increase / decrease the mold temperature to 100 ℃ / 80 ℃
The temperature was set to ° C., and a molded plate having a thickness of 3 mm was molded. The obtained molded plate was brown and translucent and highly flexible. The flexural modulus and notched Izod impact strength of these plates were measured and described similarly. For comparison, those without the addition of the hydrocarbons were similarly molded and described. It can be seen that the effect of plasticization appears and the flexibility is increased.

Claims (2)

(57) [Claims] 1. A reactive solution (solution A) of a metathesis polymerizable monomer mainly composed of dicyclopentadiene containing a catalyst component of a metathesis polymerization catalyst system and dicyclopentadiene containing an activator component of a metathesis polymerization catalyst system. In a production method of obtaining a polymer molded product by mixing at least a reactive solution (solution B) of a main metathesis polymerizable monomer and molding at the same time as polymerization, at least one saturated aliphatic group and at least one benzene nucleus or A method for producing a plasticized crosslinked polymer molded product, wherein a hydrocarbon having 11 to 35 carbon atoms and having fluidity at room temperature, which is a naphthalene nucleus, is added to at least one of the solutions A and B. 2. A reactive solution (solution A) of a metathesis polymerizable monomer composed mainly of dicyclopentadiene containing a catalyst component of a metathesis polymerization catalyst system and a dicyclopentadiene containing an activator component of a metathesis polymerization catalyst system. It is composed of at least a reactive solution of a metathesis polymerizable monomer (solution B), and has fluidity at room temperature of 11 to 35 carbon atoms comprising at least one saturated aliphatic group and at least one benzene nucleus or naphthalene nucleus. A combination of reactive solutions, wherein a hydrocarbon is added to at least one of the solutions A or B.