JPS63256616A - Molded product of polymer, manufacture thereof and combination of reactive solutions - Google Patents

Abstract

PURPOSE:To obtain a molded product improved in the balance between impact resistance and hardness, cure rate and oil resistance, by polymerizing and simultaneously molding an ether norbornene derivative or a mixture of a cycloalkene with an ether norbornene derivative in the presence of a metathesis polymerization catalyst system. CONSTITUTION:A process for producing a molded product of a polymer by polymerizing and simultaneously molding a cyclic olefin compound in the presence of a metathesis polymerization catalyst system is carried out as follows. A raw material monomer is used comprising at least one of ether norbornene derivatives (I) having 1-4 norbornene structural units and 1-4 ether groups in the molecule or a mixture of (I) with at least one of cycloalkenes (II) having at least one metathesis polymerizable cycloolefin group in the molecule. As a suitable example of the ether norbornene derivative (I) to be used, a norbornenylmethyloxy compound can be mentioned.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Industrial Application Field The present invention relates to a polymer molded product obtained by metathesis polymerization, a method for producing the same, and a combination of reactive solutions therefor.

More specifically, a polymer molded product obtained by simultaneous polymerization and molding by metathesis polymerization using a norbornene derivative having an ether group or a mixture thereof with other metathesis-polymerizable cycloalkenes, and its production. The present invention relates to a method and a combination of reaction solutions therefor.

Ql) Prior Art A method of carrying out polymerization and molding in one step, such as the RIM molding method, using a metathesis polymerizable cyclic olefin compound such as dicyclopentadiene using a metathesis polymerization catalyst system is known. However, it has been pointed out that polymers made only from these cyclic olefins require practical improvements, such as the balance between impact resistance and hardness, adjustment of reaction curing rate, and improvement of oil resistance.

On the other hand, polar groups are known to have the effect of terminating the action of metathesis polymerization catalysts.

(To) Structure of the Invention Therefore, the present inventor has found that it is possible to improve the above-mentioned problems by selecting an appropriate monomer having both an appropriate polar group and a cyclic olefin group having metathesis polymerizability. The present invention was achieved as a result of intensive research focusing on gender. That is, as a cyclic olefin group, a norbornene type structure has excellent metathesis polymerizability and can be easily introduced, and as a polar group, an ether has a property as a moderate Lewis space. As a result of focusing on the group and attempting to use an ether group-containing norbornene derivative, it was discovered that an extremely suitable polymer molded product could be obtained.

The present invention has been achieved based on this knowledge and includes the following inventions.

(1) At least one type of ethernorbornene derivative (■) having 1 to 4 norbornene structural units and 1 to 4 ether groups in the molecule, or a cyclic olefin group capable of metathesis polymerization with said (I) in the molecule. A polymer molded product obtained by simultaneously polymerizing and molding a raw material monomer consisting essentially of a mixture with at least one type (II) of cycloalkenes having at least one cycloalkene in the presence of a metathesis polymerization catalyst system. .

(a) In a method of obtaining a polymer molded product by molding a cyclic olefin compound simultaneously with polymerization in the presence of a metathesis polymerization catalyst system, the raw material monomers include 1 to 4 norbornene structural units and 1 ether group in the molecule. At least one type of ether norbornene derivative having ~4 (I)
, or a raw material monomer consisting essentially of a mixture of said (I> and at least one type (II) of cycloalkenes having at least one metathesis-polymerizable cyclic olefin group in the molecule). A method for producing a polymer molded product.

+31 8) A reactive solution of a metathesis polymerizable monomer containing a catalyst component of a metathesis polymerization catalyst system (solution A) b) A reactive solution of a metathesis polymerizable monomer containing an activation inhibitor component of a metathesis polymerization catalyst system (solution B) In the combination of reactive solutions consisting of at least
The composition of the two solutions combined is at least one type of ethernorbornene derivative (1) having 1 to 4 norbornene structural units and 1 to 4 ether groups in the molecule, or a metathesis polymerizable cyclic compound with said (I). At least one cycloalkene having at least one olefin group in the molecule
A reactive solution combination characterized in that the raw monomer consists essentially of a mixture with species (II).

Ether norbornene derivative (I) used in the present invention
Various types can be used as long as they meet the definition. However, in the present invention, since the monomer composition is molded in a mold at the same time as polymerization,
At that point, the raw material monomer must be in a liquid state.

Therefore, the melting point of the raw material monomer is preferably 80°C or lower, more preferably 50°C or lower, and even more preferably 35°C or lower. In the case of a monomer with a high melting point, it is best to dissolve it or mix it with other monomers that can lower the melting point, so that the melting point falls within the above range. preferable.

Such ether norbornene derivative (I) can generally be produced by the following method.

tA) Diets^! of ethers with carbon-carbon unsaturated bonds with cyclopentadiene! A method of converting an unsaturated bond into a norbornene group by performing der addition.

(B) A method of introducing an ether group into a compound having a norbornene structure and a precursor group capable of forming an ether group, such as a hydroxyl group or an alkyl halide group.

In addition to the typical methods (A) and (B) described above, it goes without saying that it can be synthesized by modification that can be easily synthesized by a person with general knowledge in the technical field, and generally from the viewpoint of obtaining raw materials. Which method is more advantageous is often determined by which of the precursors (A) and (B) is more readily available.

Many ether compounds having unsaturated bonds have various uses other than the raw material monomers used in the present invention.
In general, the above method (^) is often advantageous.

Ether norbornene derivative (I) used in the present invention
) is a norbornenylmethyloxy group-containing compound.

Most of such compounds can be represented by the following general formula (III).

The compound of general formula (III) can be expressed by the following reaction formula (IV
) can be easily produced by a Diets-^1der reaction between compound (V) having an allyl ether group and cyclopentadiene.

(V) [However, the definitions of R1, R2, R, and I in the formula are the same as above] The compound (V) having an allyl ether group in the reaction formula (IV) can be, for example, as shown in the following reaction formula (Vl). It can be easily obtained by reacting allyl halide with a corresponding hydroxyl group-containing compound.

...(Vl) [However, in the formula, the definitions of R, , R2, R3 and m are the same as above, and X represents a halogen atom] Examples of specific compounds belonging to the scope of the ether norbornene derivatives of the present invention are: The following can be mentioned.

norbornenylmethyl-2-ethylhexyl ether norbornenylmethyl-butyl ether norbornenylmethyl-phenyl ether norbornenylmethyl-naphthyl ether ethylene glycol bis(norbornenylmethyl) ether trimethylolpropane-tris(norbornenylmethyl) Ether pentaerythritol tetrakis(norbornenylmethyl)ether m-phenylene-bis(norbornenylmethyl)ether Also, as a norbornenylmethyloxy group-containing compound not represented by the general formula (I[[), the following compounds may be used. These can also be used as the ethernorbornene derivatives of the present invention.

Bis(norbornenylmethyl)ether 5.6-bis(
butoxymethyl)norbornene 5.6-bis(phenoxymethyl)norbornene These compounds can be easily obtained by reactions corresponding to the above reaction formulas (TV) and (Vl).

Of course, in the production of norbornenylmethyloxy-containing compounds as described above, it is not necessary to limit the production method to type (A), and it is not necessary to limit the production method to type (B), for example, by using 5-hydroxymethylnorbornene or 5-chloromethylnorbornene as an intermediate. The corresponding norbornenyl methyloxy-containing compound can be produced as a compound.

Examples of ether group-containing norbornene compounds other than norbornenyl methyloxy-containing compounds include norbornenyl ether group-containing compounds such as phenoxynorbornene isopropoxynorbornene, and compounds in which the norbornene group and the ether group are separated by two or more carbon atoms. Compounds such as (p-methoxyphenyl)norbornene and the like can also be used.

Furthermore, ether derivatives having a norbornene ring unit and a polycyclic ring are also included in the ether norbornene derivative (I) in the present invention.

A preferable example of such a polycyclic group having a norbornene ring unit is a 1.4-methano-octahydronaphthalene ring 1.4,5
．． Examples include 8-dimethanookitahydronaphthalene ring. Specific examples of these include the following.

6-(phenoxymethyl)-1,4,5,8-dimethanooctahydronaphthalene 6-(phenoxymethyl) -L4,5.8-1.4-
Methanooquitahydronaphthalene As a special example of the ether norbornene derivative (I) in the present invention, it is also possible to use a compound having at the same time a polar group other than an ether group, such as an ester group or a cyano group.

The ether norbornene derivative (I) used in the present invention is
Generally, highly purified products are required. In particular, any compounds with carbonyl, hydroxyl, or carboxyl groups that may be mixed in as raw materials before decomposing ether groups or forming ether groups can be strong catalyst poisons for metathesis polymerization catalyst systems. It is important to take care to remove it.

On the other hand, in the present invention, the metathesis-polymerizable cycloalkenes (If) used for copolymerization with the ether norbornene derivative (I) have metathesis-polymerizability, and
In the form of a mixture with the above ether norbornenes, any substance within the melting point range as mentioned above is generally used for the purpose of cost advantage or to improve the performance of the resulting polymer moldings. added for a purpose.

Examples of such cycloalkenes (II) include dicyclopentadiene, tricyclopentadiene, 1,4,5°8-dimethano-1,4,4a, 5,8 as hydrocarbon compounds that do not contain a different element. .8a-hexahydronaphthalene, tricyclo[8,2,1,Oltrideca-5,
Hydrocarbon compounds having two or more metathesis-polymerizable cyclic olefins such as 11-diene and norbornadiene; dihydrocyclopentadiene, 5-ethylidenenorbornene, 5-alkylnorbornene, 5-vinylnorbornene, norbornene, 5-cyclohekimonyl norbornene. 1.4-methano-1,4,4a.

5.6,7,8.8a-octahydronaphthalene,
1,4,5.8-dimethano-1,4,4a,5,6,7
, 8.8a-octadronaphthalene, 6-ethylidene-1,4,5,8-dimethano-1,4,4a, 5.7
．． 8.8a Hebutahydronaphthalene.

Hydrocarbon compounds having one metathesis-polymerizable cyclic olefin can be mentioned.

On the other hand, as the metathesis-polymerizable cycloalkenes having different elements such as oxygen and nitrogen 2, cycloalkenes having ester bonds, N-substituted imide bonds, cyano groups, tertiary amino groups, etc. can be used.

Specific examples of these include 5-methoxycarbonylnorbornene, 5.6-bis(methoxycarbonyl)norbornene, 6-diatu-1.4,5.8-dimethanooctahydronaphthalene, 5-(4-pyridyl)norbornene, etc. I can give you.

The cycloalkenes (II) for copolymerization preferably contain as little impurities as possible that would poison the metathesis polymerization catalyst system.

When obtaining the polymer molded product of the present invention, the above-mentioned raw material monomers can be selected as appropriate depending on various requirements including the cost of the polymer molded product.

Ether norbornene derivatives (I>
(A) when it is used as the main component, and (I) when it is used as a main component for modifying polymers mainly composed of cheaper metathesis-polymerizable cycloalkenes (II) such as dicyclopentadiene and ethylidene norbornene. It can be roughly divided into two usage methods: case (0). In the case of (a), 50 to 100 mol% is used, and in the case of (b), 0.1
(I) is used in an amount of 50 to 50 mol%, more preferably 0.5 to 35 mol%, and even more preferably 5 to 25 mol%, and the remainder is (II).

In the case of (a), it is norbornylmethyl phenyl ether.

m-Finidine bis(norbornylmethyl)ether and the like are preferably used.

On the other hand, in the case of H, (If) used as the main component is dicyclopentadiene, as described above.

1.4,5.8-dimethanohexahydronaphthalene.

1.4,5.8-dimethano-octahydronaphthalene.

Examples include 6-ethylidene-1,4,5,8-dimethano-hebutahydronaphthalene and tricyclopentadiene.

On the other hand, as (I), an ether norbornene derivative (I) having an appropriate structure can be selected and used depending on the purpose of copolymerization.

The general function of the ether norbornene derivative (I) is that it can be used as a polymerization initiation rate regulator by forming a complex with the activating agent component of the metathesis polymerization catalyst system due to the Lewis space property of the ether bond. There are things that can be done.

Examples of the ether norbornene derivative (I) for exhibiting such general functions include phenyloxymethylnorbornene (norbornylmethylphenyl ether) and norbornylmethylbutyl ether.

On the other hand, ether-norbornene derivatives having two or more norbornene groups in one molecule are expected to increase the crosslinking density of the polymer molded product and improve its heat resistance, in addition to its effect as a regulator of the polymerization initiation rate described above. I can do it. Examples of such monomers include bisnorbornenyl methyl ether, ethylene glycol bis(norbornenylmethyl) ether, and m-phinidine-bis(norbornenylmethyl) ether.

Examples include trimethylolpropane-tris(norbornenyl-methyl ether) and pentaerythritol tetrakis(norbornenylmethyl) ether.

Similarly, ether norbornene derivatives having a parky rigid cyclic group can be expected to improve heat resistance by increasing the rigidity of the polymer chain of the polymer molded product. Such monomers include 6-(phenoxymethyl')-1,4,
Examples include 5,8-dimethanooctahydronaphthalene and norbornenylmethyl-naphthyl ether.

On the other hand, ether norbornene derivatives with flexible side chains can introduce flexible side chains into the polymer chains of polymer molded products, thereby acting as internal plasticizers and improving impact resistance. I can force it. Examples of such monomers include norbornene methyl-2-ethylhexyl ether and norbornenyl methyl-amyl ether.

The general usage ratio of the ether norbornene derivative (I) corresponding to the case (b) above is as described above,
For each suitable range of use, it is necessary to determine the optimum point by testing depending on the purpose.

As is known, the metathesis polymerization catalyst system used to obtain the polymer molded product in the present invention generally consists of two components: a catalyst component and an active agent component.

If such a catalyst system is applied to bulk polymerization, the active agent component is first added to the monomer system, then the main catalyst component is added, and the molded product is obtained by shaping until polymerization starts and gelation occurs. Alternatively, it is also possible to add the catalyst component and the active agent component at the same time and obtain a molded product in the same way.

However, the metathesis polymerization reaction is exothermic in -fi, and once the polymerization has started, the system is further heated and the reaction is accelerated, and the reaction is completed very quickly, so it is important to prepare the catalyst. If this is not the case, it is often difficult to form large molded products.

Therefore, as mentioned above, two solutions were prepared in advance: a solution consisting mainly of raw material monomers and catalyst components (solution A), and a solution consisting mainly of raw material monomers and other active agent components (solution B). Preferred methods include rapid mixing using a static mixer, impingement mixing (RIM method), immediately pouring into a mold, shaping, and curing within the mold.

In this case, it is not necessary for the monomer to be the same in both liquids, and it can be arbitrarily changed depending on the function of the monomer.

For example, when using the ether norbornene derivative (I) as a polymerization initiation rate regulator, it is possible to add a large amount to the solution (B), and conversely, by adding a small amount, it is possible to not slow down the polymerization initiation rate too much. .

As the catalyst component in the metathesis polymerization catalyst system of the present invention, salts such as halides such as tungsten, rhenium, and tantalum molybdenum are used, and tungsten compounds are particularly preferable. As such tungsten compounds, tungsten halides, tungsten oxyhalides, etc. are preferable. More specifically, tungsten hexachloride, tungsten oxychloride and the like are preferred, and organic ammonium tungstate and the like can also be used. It is known that adding it directly to the monomer immediately starts cationic polymerization, which is not preferable.
Therefore, it is preferable to use such a tungsten compound by first suspending it in an inert solvent such as benzene, toluene, chlorobenzene, etc., and solubilizing it by adding a small amount of an alcoholic compound or a phenolic compound.

Further, in order to prevent undesirable polymerization 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. Such additives include acetylacetone, alkyl acetoacetate, etc. Esters.

As mentioned above, the ether norbornene derivative used in the present invention is a Lewis base and has its effect even without the addition of any of the above compounds. There are many cases.

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

On the other hand, the active component in the metathesis polymerization catalyst system is preferably an organometallic compound mainly consisting of alkylated products of metals from Groups 1 to Ⅰ of the periodic table, particularly tetraalkyltin, alkylaluminum compounds, and alkylalmonium halide compounds. Specifically, diethylaluminum chloride, ethylaluminum dichloride, triochytylaluminum, tetrabutyltin, etc. can be mentioned. The other solution (corresponding to solution B) is formed by dissolving the organometallic compound as the active ingredient in the mixed monomer.

In the present invention, a crosslinked polymer molded article can basically be obtained by mixing the solutions A and B, but the reaction rate is stable because the ether norbornene derivative has a regulating effect. Curing can be carried out under the following conditions, but if it is desired to further adjust the polymerization rate, other Lewis bases can be added.

The amount of the metathesis polymerization catalyst system to be used is, for example, when a tungsten compound is used as a catalyst component, the ratio of the tungsten compound to the above mixed monomers is about 1 on a molar basis.
000:1 to about 15,000:1, preferably around 2,000:1, and when an alkylaluminum is used as the active agent component, the ratio of the aluminum compound to the DCP mixed monomer is on a molar basis. about 100:1 to about 2000:1, preferably about 200:1 to about 50
A value around 0:1 is used. 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 polymer molded article of the present invention in order to improve or maintain its properties. Such additives include fillers, pigments,
These include antioxidants, light stabilizers, flame retardants, and polymer modifiers. Such additives cannot be added after the crosslinked polymer of the present invention has been molded, so if they are added, they must be added to the above-mentioned raw material solution in advance.

The easiest method is to use the solution A and solution B.
One method is to add the compound in advance to either or both of the above, but in this case, it does not react with the highly reactive catalyst component or other active agent component in the liquid to a practical extent, and It must be something that does not inhibit polymerization.
If the reaction cannot be avoided, but polymerization will not be substantially inhibited even if they coexist, mix it with the monomer to prepare a third liquid, and mix and use it immediately before polymerization. You can also do it. In addition, in the case of a solid filler,
It is also possible to fill a mold with a shape that can sufficiently fill the voids immediately before starting the polymerization reaction or while the two components are mixed together.

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

Further, it is preferable to add an antioxidant to the polymer molded article of the present invention, and therefore it is desirable to add a phenol-based or amine-based antioxidant to the solution in advance. As a specific example, 2.6-t-
Butyl-P-cresol, N,N'-diphenyl-P-
Phenylenediamine, tetrakis[methylene (3,5-
Examples include di-t-butyl-4-hydroxycinnamate)]methane.

Furthermore, other polymers can be added to the polymer molded article according to the present invention when it is in a monomer solution state. As such polymer additives, the addition of elastomers is effective in increasing the impact resistance of molded products and adjusting the viscosity of the solution. Elastomers used for this purpose include:
A wide variety of elastomers include styrene-butadiene-styrene triblock rubber, styrene-isoprene-styrene triblock rubber, polybutadiene, polyisoprene, butyl rubber, ethylene propylene-diene terpolymer, and nitrile rubber.

The polymer molded article of the present invention is produced by simultaneously performing polymerization and molding, as described above.

As mentioned above, such molding methods include the resin injection method, in which a premix of the catalyst system and monomer mixture is poured into the mold, and the resin injection method, in which the catalyst system is divided into two parts, solution A and solution B, collide in the head part. It is possible to use the RIM method in which the mixture is mixed and poured directly into a mold. 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 easily released from molds and often do not require special mold release agents.

The adhesion of molded products to commonly used paints such as epoxy and polyurethane decreases due to the formation of an oxidized layer on the surface.
In good condition.

The molded products thus obtained can be used in a wide range of applications, mainly large molded products, such as parts for various transportation equipment, including automobiles, and housings for electrical and electronic devices.

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

Example 1-8. Comparative Example [Preparation of Raw Monomer] 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 using gas chromatography shows a purity of 99% or higher.

On the other hand, commercially available dicyclopentadiene is thermally dissociated to obtain cyclopentadiene, which is then reacted with allyl phenyl ether to produce norbornenylmethyl-phenyl (
Bis(norbornenylmethyl)ether (BNME) was synthesized by reacting NMPE) ether and diallyl ether. These compounds are purified by distillation and purity measurement by gas chromatography shows that the purity is 99%.
Do not show purity greater than %.

[Preparation of catalyst component solution] 20 g of tungsten hexachloride was added to 70 ml of dry toluene under a nitrogen stream, and then a solution consisting of 21 g of nonylphenol and 16 ml of toluene was added to prepare a 0.5 M tungsten-containing catalyst solution. For the solution,
Nitrogen gas was purged overnight to remove hydrogen chloride gas purified by the reaction of tungsten hexachloride and nonylphenol, which was used as a polymerization catalyst.

10 ml of such solution. Mix 1.0ml of acetylacetone monomer mixture 5000111, tungsten content 0
．． Prepare 001 M solution A.

[Preparation of active inhibitor component solution] Trioctyl aluminum 85. Dioctyl aluminum 15. 50 moles of mixed monomer in the proportion of 300 moles of diglyme
Mix 0 ml to give aluminum content of 0°003
Solution B of M was prepared. DCP and norbornenyl methyl phenyl ether (NMPE), bis(norbornenyl methyl) (BNM) in the monomer mixture in such solution
E) The molar ratio of ether used was as follows.

The above solution was added to 10 ml of the catalyst component solution (solution A).
After IQml of the active drug component solution (solution B) was brought to a predetermined temperature, it was taken out into a syringe that had been sufficiently replaced with nitrogen.

Both liquids were simultaneously extruded from the syringe at a constant speed into a glass flask equipped with a stirrer under rapid stirring, and after rapid mixing, the stirrer was raised and a thermocouple was inserted. Time to reach °C (
Polymerization time) was measured.

Furthermore, the solidified crosslinked resin was taken out, cut into sections, and the softening point was measured using the TMA method in the needle penetration mode in a nitrogen stream. The expansion rate was also measured using another rimpull. The results are summarized in Table 2.

As shown in Table 2, it can be seen that the effect of the ether norbornene derivatives increases the time required to initiate polymerization, which is very advantageous in obtaining large molded products or in methods using premixes. It is also seen that in many cases the heat resistance is improved compared to the comparative example in which dicyclopentadiene was used alone.

For the liquids having the compositions of Examples 3 and 7, liquid A was used.

B Each product was taken out into a syringe, mechanically extruded at a constant speed, guided into a nozzle, and molded using an ultra-compact RIM machine that collided with it and poured it into a mold.A brown, durable plate was molded. Ta.

Next, take 5 ml each of the liquid having the composition of Example 1.2,
Stir under a stream of nitrogen to create a premix, which is heated to 90%
Pour it into a mold kept at ℃ and you will get a similarly strong brown plate.

Procedure correction port February 26, 1986

Claims (3)

[Claims] (1) At least one type of ether norbornene derivative (I) having 1 to 4 norbornene structural units and 1 to 4 ether groups in the molecule, or a cyclic olefin group that can be metathesized with said (I) in the molecule. at least 1 in
1. A polymer molded product obtained by simultaneously polymerizing and molding a raw material monomer consisting essentially of a mixture with at least one type (II) of cycloalkenes in the presence of a metathesis polymerization catalyst system. (2) A method for obtaining a molded polymer by molding a cyclic olefin compound simultaneously with polymerization in the presence of a metathesis polymerization catalyst system, in which the raw material monomers contain 1 to 4 norbornene structural units and an ether group in the molecule. At least one kind of ether norbornene derivative having 1 to 4 (I
), or a mixture of (I) and at least one cycloalkene (II) having at least one metathesis-polymerizable cyclic olefin group in the molecule. A method for producing a polymer molded article. (3) a) A reactive solution of a metathesis polymerizable monomer containing a catalyst component of a metathesis polymerization catalyst system (solution A) b) A reactive solution of a metathesis polymerizable monomer containing an activator component of a metathesis polymerization catalyst system (solution B) ), in which the metathesis-polymerizable monomers in solution A and solution B are:
The combined composition of both solutions is at least one type of ether norbornene derivative (I) having 1 to 4 norbornene structural units and 1 to 4 ether groups in the molecule, or a metathesis polymerizable cyclic compound with said (I). A combination of reactive solutions characterized in that the raw material monomer consists essentially of a mixture with at least one type (II) of cycloalkenes having at least one olefin group in the molecule.