JPH02272016A - Production of molded article of plasticized crosslinked polymer and combination of reactive solution - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention a. Industrial Application Field The present invention provides a crosslinked polymer obtained by simultaneously polymerizing and molding a metathesis polymerizable monomer mainly containing dicyclopentadiene in the presence of a metathesis polymerization catalyst system. This invention relates to a method for plasticizing a molded 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 molding.

b. Prior art presence or absence It is known that cyclic olefins undergo ring-opening polymerization using metathesis polymerization catalyst systems. Utilizing this, a monomer such as dicyclopentadiene, which can be obtained at low cost and has two metathesis-polymerizable cyclic olefin groups, is poured into a mold in a liquid state, and bulk polymerization is performed therein.
A method of performing polymerization and molding in one step has been proposed (see, for example, Japanese Patent Application Laid-open No. 129013/1983).

According to this method, large-sized molded products can be obtained using inexpensive molds, so it has the potential to be used in a wide range of applications. However, depending on the application, such molded products are often required to be plasticized in order to improve their impact resistance.

Such plasticizing methods include, for example, US Pat. No. 4,485.
No. 208 has a trussility parameter of 7.8 to 10.
．． The use of ester plasticizers of No. 2 has been proposed. On the other hand, metathesis polymers from cyclic olefins, such as poly(dicyclopentadiene), have a strubility parameter of about 9.3, as measured by the present inventor.
In this respect, the above ester plasticizers seem to have a strong affinity, but while poly(dicyclopentadiene) has a structure that does not have hydrogen bonds, esters have a weak but strong affinity for hydrogen bonds. Therefore, there is a concern that even if the trussibility parameters are similar, the affinity may not be great. In fact, when measured, the swelling ratio of the poly(dicyclopentadiene) with an ester material having a sturdiness parameter of 9.0 to 9.5 is very small.

On the other hand, it has been found that halogenated hydrocarbons and aromatic hydrocarbons such as chloroform and toluene, which have a tumbleability parameter of 9.0 to 9.5, exhibit a large swelling ratio.

C1 Structure of the Invention Therefore, the present inventor investigated how to use a high boiling point hydrocarbon having both an aromatic ring and an aliphatic group as a plasticizer, and arrived at 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 containing an activator component of a metathesis polymerization catalyst system. A production method for obtaining a molded polymer by mixing at least a reactive solution (solution B) of a main metathesis-polymerizable monomer and molding at the same time as polymerization, wherein at least one saturated aliphatic group and at least one benzene A method for producing a plasticized crosslinked polymer molded article, characterized in that a hydrocarbon having a carbon number of 11 to 35 and having fluidity at room temperature, consisting of a nucleus or a naphthalene nucleus, 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 A reactive solution (solution B) of a metathesis-polymerizable monomer mainly consisting of at least one saturated aliphatic group and at least one benzene nucleus or naphthalene nucleus, having a carbon number of 11 to 35 and being fluid at room temperature. A combination of reactive solutions, characterized in that a hydrocarbon having the following properties is added to at least one of the solutions A and B.

The above-mentioned hydrocarbons used in the present invention do not need to be of a single type, but are preferably mixtures of isomers. Those with a carbon number of 12 to 35 are used,
From the viewpoint of low volatility, a larger molecular weight, that is, a larger number of carbon atoms, is preferable, but a larger number of carbon atoms is more difficult in terms of production, purification, handling, and low-temperature characteristics.
Those having 14 to 30 carbon atoms are preferred. In addition, from the viewpoint of boiling point, a boiling point at normal pressure of at least 200°C or higher, more preferably 250°C or higher, still more preferably 300°C or higher is used. Particularly industrially, Friedelkraft is used to add tri- to tetrameric α-olefins of propylene to benzene or naphthalene before sulfonation of sulfonic acid surfactants such as sodium alkylbenzenesulfonates and sodium alkylnaphthalenesulfonates. 1-2 in reaction
Individually bonded hydrocarbon cords are available at low cost and are preferred.

That is, dodecenylbenzene (two types are used, a chain dodecenyl group with few branches and a branched dodecenyl group), dodecenylnaphthalene, nonylbenzene,
Dinonylbenzene, dinonylnaphthalene, etc. are easily available and preferred examples of hydrocarbons. Particularly preferred is dodecenylbenzene.

Another industrially easily available hydrocarbon suitable for use in the present invention includes a group of compounds used as heat transfer agents.

These compounds are selected to have high boiling points, low volatility, and excellent thermal stability so that they can be used even at high temperatures, and do not lose fluidity even at low temperatures, and are easily available after being purified to a high degree of purity.

Such hydrocarbons include partially hydrogenated terphenyl, alkyl-substituted biphenyls such as triethyl-, diethyl- or monoethyl-diphenyl, and alkylnaphthalenes such as methyl, dimethyl, ethyl or diethyl-naphthalene. Furthermore, 1-(3', 5
Examples include alkyldiphenylethanes and alkyldiphenylmethanes such as '-dimethylphenyl)-2-phenylethane.

Furthermore, although the group itself has somewhat lower thermal stability than methyl or ethyl groups, an isopropyl group can be mentioned as an alkyl substituent that can be suitably used for the purpose of the present invention.
Isopropyl-substituted benzenes or naphthalenes such as tri(inpropyl)benzene, cymenes, inpropylnaphthalene, diisopropylnaphthalene, etc. can also be used as suitable hydrocarbons.

Such aliphatic aromatic hydrocarbons may have one halogen substituent in addition to the hydrocarbon.

However, high boiling point halogen-substituted aromatic hydrocarbons may contain compounds that are difficult to decompose and accumulate, such as the now famous polychlorinated biphenyl (PCB), so care must be taken.

The above-mentioned hydrocarbons are primarily synthesized by petrochemical means, have good purity, and can be used without interfering with the metathesis polymerization catalyst system.

In addition to the above synthesized hydrocarbons, there are also hydrocarbons that contain many aromatic groups among those commercially available as process oils, such as those that are commercially available in the separation of petroleum fractions and cracking component fractions,
Products that on average meet the conditions as described above can be used. However, these may contain impurities such as polar groups and sulfur components generated by oxidation, and such impurities! Care must be taken as @ substances may inhibit the metathesis polymerization catalyst system.

As mentioned above, the specific aromatic hydrocarbons used in the present invention have good affinity with the crosslinked metathesis polymer containing dicyclopentadiene as the main monomer, and have a rigid aromatic ring. Because of this, it is difficult to cause bleeding and acts as an effective and excellent plasticizer.

Furthermore, as mentioned above, -i is inactive to both the main catalyst component and the activator of the metathesis polymerization catalyst system, and can be added to either acidic solution.

Furthermore, it generally has better solubility than dicyclopentadiene, which is used as the main monomer, and is also effective as a solubilizing agent for dissolving additives added to the reactive solution.

The amount of such hydrocarbon added can be determined as appropriate depending on the degree of plasticization required and the necessity as a solubilizing agent, but -ffl should be added in an amount of 1 to 40% by weight, more preferably 3 to 1% by weight, based on the total monomers. A range of 30% by weight and 1% by weight, more preferably from 5 to 25% by weight, is used.

The present invention uses dicyclopentadiene as the ultimate additive. Used as a raw monomer means that -a contains at least 50% by weight or more, more preferably 75% by weight of the total monomers.
Above, more preferably 90% or more is used.

The metathesis-polymerizable monomer used with dicyclopentadiene includes norbornene structure or other cyclic olefins having an equivalent metathesis-polymerizability.
Monomers having ~3 monomers can be mentioned.

Suitable specific examples include oligocyclopentadiene such as tricyclopentadiene, ethylidenenorbornene, norbornene, 5-methylnorbornene, norbornadiene, 6-nitylidene-1.45.8-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-
Examples include dimethanol-1,44a, 5.6.7.8.8a-octahydronaphthalene, and the like.

Furthermore, metathesis-polymerizable cycloolefin monomers containing different elements such as oxygen and nitrogen can also be used, if necessary. Polar monomers that can be easily used are often used in copolymerization with dicyclopentadiene or the like, for example, in an amount of about 1% to 20% by weight.

Such a polar monomer also preferably has a norbornene structural unit, and the polar group is preferably an ester group, an ether group, a cyano group, an N-substituted imide, or the like.

Specific examples of such copolymerizable monomers include 5-methoxycarbonylnorbornene, 5-(2-ethylhexyloxy)carbonyl-5-methylnorbornene, and 5-phenyloxymethylnorbornene.

5-cyanonorbornene, 6-diatu 1.4.58-
Examples include dimethanol-1,4,4a, 5.6.7.8.8a-octahydronaphthalene, and N-butylnadic acid imide.

As mentioned above, the metathesis polymerizable monomer is required to contain as few impurities as possible that would 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 compounds of tungsten and molybdenum are preferred, and tungsten compounds are particularly preferred.

As such a tungsten compound, tungsten halide, tungsten oxyhalide, tungstate salt, etc. are preferable, and more specifically, tungsten hexachloride, tungsten oxychloride, etc. are preferable. It has been found that when a dark tungsten salt compound is added directly to a monomer, cationic polymerization immediately starts, which is not preferable. Therefore, it is preferable to use the tungsten salt compound by suspending it in advance in an inert solvent such as benzene, toluene, chlorobenzene, etc., and solubilizing it by adding a small amount of an alcoholic compound or phenolic compound.

Further, in order to prevent undesirable polymerization as described above, it is preferable to add about 1 to 5 moles of a Lewis base or a chelating agent per mole of the tungsten compound. Examples of such additives include acetylacetone and acetoacetic acid alkyl esters.

Examples include tetrahydrofuran and benzonitrile.

Thus, the monomer solution containing the catalyst component (solution A) is
It has sufficient stability for practical use.

On the other hand, the activator component in the metathesis polymerization catalyst system is preferably an organometallic compound mainly consisting of alkylated products of metals from Groups 1 to 2 of the periodic table, particularly tetraalkyltin, alkylaluminum compounds, and alkylaluminum halide compounds. Specific examples include diethylaluminum chloride, ethylaluminum dichloride, trioctylaluminum, dioctylaluminum iodide, and tetrabutyltin. The other solution (corresponding to solution B) is formed by dissolving these organometallic compounds as activator components in the raw material monomers.

The hydrocarbons used in the present invention are the above-mentioned reactive solution A,
Either or both of B can be used in arbitrary divided amounts. As mentioned above, if it is expected to act as a solubilizing agent, it is sufficient to add a large amount to the side where it is needed.

In the present invention, a crosslinked polymer molded article can basically be obtained by mixing the solution A and solution B, but if the above composition remains unchanged, the polymerization reaction will start very quickly, so the molding Hardening may occur before it flows sufficiently into the casting mold, which is often a problem, and as mentioned above, it is preferable to use an activity regulator for this purpose.

As such regulators, Lewis bases are generally used, among which ethers, esters, nitriles, etc. are used. Specific examples include ethyl benzoate, butyl ether, and diglyme. Such a regulator can be added to both solutions, but generally the effect may be greater when added to the solution of the organometallic compound activator component. If a monomer having a Lewis space group is used as described above, it can also serve as a regulator.

The amount of the metathesis polymerization catalyst system 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 1 on a molar basis.
000:1 to 15000:1, preferably 2000:1
In addition, when using aluminum alkyls, the active ingredient is about 100 to 1 to about 2 on a molar basis.
000:1, preferably around 200:1 to about 500:1. Further, as described above, the masking agent and the regulating agent can be appropriately adjusted and used depending on the amount of the catalyst system to be used through experiments.

In practical use, various additives can be added to the crosslinked polymer molded product produced by the production method of the present invention in order to improve or maintain its properties.

Such additives include fillers, antioxidants, light stabilizers, flame retardants, polymer modifiers, and plasticizers other than the above-mentioned hydrocarbons. Similar to the above-mentioned plasticizer in the present invention, it is impossible to add such additives after the crosslinked polymer has been molded, so when adding them, it is necessary to add them to the raw material solution described above in advance. There is.

The easiest method is to use the solution A and solution B.
One method is to add it in advance to either or both of the above, but in this case, it is necessary to add it to either or both of the liquids, but in this case, it does not react with the highly reactive catalyst components or other active agent components in the liquid to a practical extent, and It must not inhibit polymerization. If the reaction cannot be avoided, but coexistence does not substantially inhibit polymerization, it can be mixed with the monomer to prepare a third liquid and mixed and used immediately before assembly. . In addition, in the case of solid fillers, if the two components are mixed and have a shape that can sufficiently fill the voids immediately before starting the polymerization reaction or during polymerization, it is necessary to It is also possible to pre-fill.

Reinforcing woods or fillers as additives are effective in improving the flexural modulus. Examples of such materials include glass fiber, mica, and wollastonite. Those surface-treated with a so-called silane coupler can also be suitably used.

In addition, it is preferable to add an antioxidant to the crosslinked polymer molded product produced by the production method of the present invention, and therefore it is desirable to add a Fe-, Mer-, or amine-based antioxidant to the solution in advance. . Specific examples of these antioxidants include 2.6-t-butyl-P-cresol, N,
Examples include N'-diphenyl-P-phenylenediamine, tetrakis[methylene (3,5-di-butyl-4-hydroxycinnamate)comethane, and the like.

Furthermore, other polymers, especially in the form of a reactive solution, can be added to the polymer molded article produced by the production method of the present invention. As described above, the addition of an elastomer as such a polymer additive is effective in increasing the impact resistance of the molded product and controlling the viscosity of the solution. Elastomers used for this purpose include a wide range of elastomers such as styrene-butadiene rubber, styrene-butadiene-styrene triblock rubber, styrene-isobrene-styrene 1-riblock rubber, polybutadiene, polyisoprene, butyl rubber, and ethylene propylene-genter polymanitrile rubber. be able to. Furthermore, if a large amount of residual monomer remains in the molded product of the present invention, a unique depth may appear. α, α as such residual monomer reducing agents.

Examples include 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 reactive solutions as described above.

As mentioned above, such molding methods include mixing the catalyst and raw material monomer with a simple mixer such as a static mixer, a resin injection method in which a pre-mixed premix is flowed into a mold, and a method in which the catalyst system is It is possible to adopt the RIM method, in which solution A and solution B, which have been separated into two, are collided and mixed in a head section and poured into a mold as they are. In particular, the RIM method is commonly used.

In either case, the injection pressure into the mold can be relatively low, making it possible to use inexpensive molds. Further, when the polymerization reaction inside the mold starts, the temperature inside the mold rapidly rises due to the reaction heat, and the polymerization reaction ends in a short time.

Unlike polyurethane-RIMs, they are easy to release from the mold and often do not require special mold release agents.

In the present invention, since the molded product has many double bonds, an oxidized layer is formed on the surface, which reduces the adhesion to commonly used paints such as epoxy and polyurethane.
In good condition.

Because the above-mentioned hydrocarbons are added to the molded products thus obtained, they are plasticized and have improved flexibility compared to non-added dicyclopentadiene-based crosslinked polymers, and they are less likely to bleed. Because it is stable, it can be used as a molded product in a wide range of applications, such as housings for various devices and impact-resistant members.

The present invention will be described in detail below with reference to Examples and Comparative Examples. Note that the examples are for illustrative purposes only, and are not limited thereto.

Examples 1 to 6 Commercially available DCI) was purified by distillation under reduced pressure in a nitrogen stream,
Obtain purified dicyclopentadiene with a freezing point of 33.4°C. Purity measurement using a gas chromatograph showed a purity of 99% or more.

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

[Preparation of main catalyst concentrate] Add 19.80 g of high-purity tungsten hexachloride <0.05 mol) to 90 ml of dry 1 to toluene under a nitrogen stream,
Add 0.925 g of L-butanol dissolved in 5 ml of 1 to toluene and stir for 1 hour, then add a solution consisting of 11.05 g of nonylphenol (<0.05 mol) and 5 ml of toluene and stir for 1 hour under nitrogen purge. . 1
0 g of acetylacetone was added to the mixture, stirring was continued overnight under a nitrogen purge while purging by-product hydrogen chloride gas, and then some of the toluene distilled out was supplemented to prepare a 0.5M tungsten-containing catalyst concentrate.

[Preparation of active inhibitor concentrate] Z-Lo octyl aluminum iodide 5.70 g
, ) Lee [1-octyl aluminum 31.17
13.42 g of diglyme was mixed under a nitrogen stream, and then DCP was added to dilute the whole to 100 ml to obtain an activated concentrate containing 1.0M aluminum.

[Preparation of reaction solution A] Dicyclopentadiene, ethylidenenorbornene, ethylene-propylene terpolymer weight ratio of 93/3
/4 mixed and dissolved solution 100 (1; Ethan
A reaction solution A was prepared by mixing 220 g of ox70 and 16.2 cc of the main catalyst concentrate under an inert atmosphere.

[Preparation of reaction solution B] Dicyclopentadiene, ethylidenenorbornene, and ethylene-propylene diene terpolymer were mixed in a ratio of 93/1.
A reaction solution B was prepared by mixing 23.7 cc of the activator concentrate with 1000 g of the 3/4 mixed and dissolved solution.

Hydrocarbons as shown in Table 1 were added to the reaction solutions A and B obtained above in the proportions shown in the table. Using solutions A and B after this addition, 5
Using an ultra-compact RIM machine, the mold temperature can be increased or decreased by 100% each.
A molded plate with a thickness of 3 mm was molded at a temperature of 80°C. The obtained molded plate was brown, translucent and highly flexible. Measure the bending modulus and notched isot impact strength of these plates and record them as well. For comparison, a sample without the addition of hydrocarbons was molded in the same manner and is also shown.

It can be seen that the plasticization effect appears and the flexibility increases.

Procedural amendment (voluntary) 1. In the patent application for indication of the case No. 2, on page 5, line 17 of the description of the title of the invention, amend ``r lord and hand'' to ``main.''

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Claims (2)

[Claims] (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 a solution containing mainly dicyclopentadiene containing an activator component of a metathesis polymerization catalyst system. A method for producing a molded polymer by mixing at least a reactive solution (solution B) of a metathesis-polymerizable monomer and molding at the same time as polymerization, wherein at least one saturated aliphatic group and at least one benzene nucleus or naphthalene nucleus are mixed. A method for producing a plasticized crosslinked polymer molded article, characterized in that a hydrocarbon having 11 to 35 carbon atoms and having fluidity at room temperature is added to at least one of the solutions A and B. (2) (a) A reactive solution (solution A) of a metathesis polymerizable monomer consisting mainly of dicyclopentadiene containing a catalyst component of a metathesis polymerization catalyst system and a reactive solution (solution A) of a metathesis polymerizable monomer consisting mainly of dicyclopentadiene containing a catalyst component of a metathesis polymerization catalyst system; A reactive solution of metathesis-polymerizable monomers (
A hydrocarbon having a carbon number of 11 to 35 and having fluidity at room temperature and consisting of at least one saturated aliphatic group and at least one benzene nucleus or naphthalene nucleus is added to at least one of the solutions A and B) from solution B). A combination of reactive solutions characterized by the addition of: