JPH0791370B2 - Method for producing polymer molded product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention relates to a method of pouring a metathesis-polymerizable monomer into a molding mold in the presence of a metathesis polymerization catalyst system, and performing molding simultaneously with bulk polymerization in the mold. Is. More specifically, it relates to remarkably improving the impact resistance and heat resistance of the crosslinked polymer molded product by allowing a specific liquid rubber to coexist during the polymerization.

b. Prior Art It is known that cyclic olefins are opened by a metathesis polymerization catalyst system to give crosslinked polymers.

Therefore, a method is proposed in which a monomer, such as dicyclopentadiene, that can be obtained at low cost and that has two metathesis-polymerizable groups is poured into a mold in a liquid state, bulk polymerization is performed in the mold, and molding is performed in one step at the same time as polymerization. (See, for example, JP-A-58-129013).

According to such a method, a large-sized molded product can be obtained by using an inexpensive mold, so that it has a possibility of being used in a wide range of applications. However, there are many applications in which such a large molded article is required to have good impact resistance. However, in general, the impact resistance is often insufficient in the metathesis-polymerizable monomer as described above, particularly in the crosslinkable monomer. As a method for improving it, a method of forming a polymer molded product in the presence of a rubber soluble in a monomer and a method of adding a plasticizer have been proposed. The method of adding a plasticizer generally has a problem of blooming of the added plasticizer, and it cannot be said to be a sufficient method. On the other hand, the method of adding rubber can be said to be an effective method because a considerably large effect is recognized even if it is added in a small amount. However, the performance of addition of such a rubber is greatly affected by the rubber to be added, that is, the impact resistance typified by notched Izod impact resistance and the heat resistance typified by heat deformation temperature. I knew that.

Immediately, it has been found that impact resistance and heat resistance are generally contradictory properties, and one of the properties is likely to be impaired by adding a rubber that gives one of the good properties. Therefore, the present inventor has conducted diligent studies to find a rubber having a good balance between the two, and as a result, it has been found that a rubber having a specific composition can improve both of these contradictory properties to a very high level. Has reached.

c. Composition of the Invention Generally, hydrocarbon rubbers such as styrene-butadiene rubber (SBR), poly-cis-1,4-polybutadiene rubber (BR), poly-cis-1,4-isoprene rubber (IR), natural It is well known that rubber, polyisobutylene rubber, ethylene-propylene rubber, ethylene-propylene-diene-terpolymer rubber and the like can be used for polymer moldings by such metathesis polymerization.

By the way, among these hydrocarbon rubbers, for example, taking styrene-butadiene rubber (SBR) as an example, the heat resistance of the molded product is improved by using SBR having a high styrene content,
Impact resistance The impact resistance especially at low temperature is greatly impaired. SBR with the same styrene content (and roughly the same backbone structure)
Also in, for example, when the reactive solution for obtaining a metathesis polymerization molded product from a metathesis polymerizable monomer mainly composed of DCP is made to have approximately the same viscosity,
The addition amount of SBR having a smaller molecular weight is larger, but in such a case, the molded product has good impact resistance but a low heat distortion temperature. Further, in the case of poly-cis-1,4-butadiene (BR), it was found that there is a similar tendency in that the difference becomes more remarkable. That is, it has been found that it is a general phenomenon that the impact resistance and the heat distortion temperature conflict with each other as described above.

However, ethylene-propylene-diene-terpolymer rubber (EPDM) and ethylene-propylene rubber (EPR)
In general, it is known that the higher the propylene content, the greater the flexibility as a rubber, and conversely, the higher the ethylene content, the easier the crystallinity will come out. Is used.

However, when it is used in the above-mentioned metathesis polymer molded article, surprisingly, not only those having an ethylene content higher than the general one of about 60 mol% improve the heat distortion temperature, but also It has been found that even impact properties can be provided.

Further, they have found that, in a reactive solution having the same viscosity, the viscosity can be reached with a low addition amount, that is, a high polymerization degree can give at least a high impact resistance. However, if the ethylene content becomes too large, the crystallinity will become too large, and insoluble components will come out in the metathesis polymerizable monomer such as DCP at around room temperature, and the degree of polymerization will become too high or the molecular weight distribution will be too high. If it becomes too wide and contains a high degree of polymerization as well, insoluble components and gelled substances will come out as well, which will hinder the production of molded products and cause no inconvenience in use. It has also been found that there is a requirement for solubility.

That is, the present invention provides a method for producing a polymer molded product, which comprises simultaneously polymerizing and molding a metathesis polymerizable monomer in the presence of a metathesis polymerization catalyst system, wherein an ethylene-propylene rubber and / or an ethylene-propylene-diene-terpolymer is used.
At least 3% by weight of a polymer rubber which is substantially soluble at 30 ° C. in a mixed solvent having an ethylene content of 65 mol% or more and 90% by weight of dicyclopentadiene and 10% by weight of ethylidene norbornene. A method for producing a polymer molded product, which comprises adding one kind.

In the present invention, a metathesis polymerizable monomer reactive solution (solution A) containing a metathesis polymerization catalyst system catalyst component and b) a metathesis polymerizable monomer reactive solution containing a metathesis polymerization catalyst system activator component (solution B). ) More at least in a combination of reactive solutions, at least one of these solution A and solution B has ethylene-propylene rubber and / or ethylene-propylene-diene-
Terpolymer rubber having an ethylene content of 65 mol% or more and at least 3% by weight at 30 ° C. substantially dissolved in a mixed solvent of 90% by weight of dicyclopentadiene and 10% by weight of ethylidene norbornene. A combination of reactive solutions containing at least one of can be used.

EPDM and EPR used in the present invention have a large number of different ethylene contents, average molecular weights, molecular weight distributions, diene types, and diene contents on the market in order to cover a wide range of uses for such rubbers. It is possible to select one that satisfies such requirements.

In general, EPDM and EPR are obtained by polymerizing ethylene and propylene with a Ziegler-Natta catalyst and, in the case of EPDM, non-conjugated dienes.

The diene copolymerized as the third component for the purpose of leaving an unsaturated bond as a cross-linking point in EPDM is a non-conjugated diene, and two unsaturated bonds with greatly different polymerization reactivity are used.
Various types were examined during development, but currently, ethylidene norbornene (ENB) and dicyclopentadiene (D
CP), 1,3-hexadiene, etc.
People are mainly used. The copolymerization ratio of these dienes is appropriately adjusted depending on the use and vulcanization conditions, and a copolymerization ratio within 10 mol% is generally used.

As described above, when EPDM and EPR are used for general rubber, the ethylene content is generally around 60 mol%, but as described above, in the present invention, the ethylene content is dominant in the performance of the molded product. It is important to find that it has an effect, the ethylene content is at least 65 mol% or more, and the upper limit is determined by its solubility, but in general, a range of 85 mol% or less is used. In particular, the range of 68 to 82 mol% is preferable.

The rubber binder used in the present invention is not essential for the non-conjugated diene component, but the introduction thereof tends to increase the solubility, and it is preferable to introduce an appropriate amount. When the amount is large, the number of branches is large, and the molecular weight distribution tends to be wide, so that there is a problem in solubility. Therefore, it is generally preferably 5 mol% or less.

Further, as described above, it has been found that one having a large molecular weight as far as the solubility permits is advantageous in improving the impact resistance.

Generally, the magnitude of the molecular weight of a rubber is judged by the Mooney viscosity in a practical sense, but this is one of the melt viscosities, and when the rubber is used in a solution state as in the present invention, it has a constant viscosity. It is more practical to judge by the solution viscosity or the concentration at a constant viscosity. Especially when it is used in a reaction solution for obtaining a polymer molded product as in the present invention, it is practical to use a large or small concentration at a constant viscosity.

Therefore, the rubber concentration, which was dissolved in a mixed solvent of 99% DCP and 1% toluene to give a viscosity of 350 centipoise at 30 ° C., was used as a measure of the molecular weight. At such concentration, 9% by weight or less is preferable, and 6% by weight is more preferable. The following is preferable, and 4.5% by weight or less is particularly preferable.

The lower limit of the concentration is generally 3% by weight or more because it is difficult to use a polymer having a high degree of polymerization in terms of solubility. For solubility, use DCP9
It is necessary to dissolve at least 3% by weight at 30 ° C. in a mixed solvent consisting of 0% by weight and 10% by weight of ENB, but it is preferable that at least 5% by weight be dissolved.

The term “substantially dissolved” does not necessarily mean that it is completely dissolved in a molecular form, and it can be used as a reactive solution for reaction injection molding that flows out from a thin nozzle under high pressure so that it can exhibit fluidity to the extent that it does not interfere. It means that it can be dissolved in.

The amount of EPR or EPDM added may be selected in consideration of the balance between the effect of thickening the reactive solution on the moldability due to the addition of the rubber and the effect of improving the physical properties of the molded product. That is, when used for RIM, the viscosity of the liquid is most preferably about 250 to 500 centipoise, and the rubber concentration giving the viscosity may be selected.

In addition, it is necessary to add another polymer additive, and if there is a thickening effect therefor, it may be adjusted in consideration of it.

In general, the amount of EPR or EPDM added is in the range of 1 to 15% by weight, particularly preferably 3 to 10% by weight (based on the monomer).

By using such EPR and EPDM, for example, SBR or BR in a crosslinked polymer molded product using a metathesis catalyst system composed of tungsten and aluminum based on DCP as a monomer.
In addition, when using materials other than the present invention in EPDM etc., heat distortion temperature (18.5 Kg / cm ² load) (HDT) around 90 ° C Izod with notch (3 mm thickness) 40 to 45 Kg cm / cm But
HDT above 100 ° C and 50Kgcm / c with notched Izod
It is possible to exert the effect of easily improving the value near m.

Considering that if a similar cross-linked polymer is obtained without adding any rubber, it is possible to obtain a value of around 90 ° C. with HDT and a value of about 5 kgg / cm with a notched Izod, the addition of rubber, especially of the present invention. I think that you can feel the remarkable effect of a specific rubber.

On the other hand, with the rubber as described above, the metathesis-polymerizable monomer used for forming the molded product may be any one such as a compound capable of bulk polymerization by metathesis polymerization to give a molded product, but generally a metathesis-polymerizable cyclohexene. Those containing 1 to 4 alkene groups are used. Those having a norbornene-type bond are particularly preferable. Hydrocarbons are particularly preferable, and specific examples include dicyclopentadiene, dihydrodicyclopentadiene, cyclopentadiene-methylcyclopentadiene co-dimer, 5-ethylidenenorbornene, 5-vinylnorbornene, norbornene, 5-cyclohexenyl. 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
-Octahydronaphthalene, 6-ethylidene-1,4,5,8-
Dimethano-1,4,4a, 5,7,8,8a-heptahydronaphthalene,
1,4,5,8-Dimethano-1,4,4a, 5,8,8a-hexahydronaphthalene, tricyclo [8,2,1,0] trideca-5,11-diene, norbornadiene, 5-phenylnorbornene , Ethylene bis (5-norbornene) and the like. Particularly preferred is dicyclopentadiene or a monomer mixture containing 50% or more, more preferably 70% or more of dicyclopentadiene.

Further, if necessary, a metathesis polymerizable monomer containing a polar group having a different element such as oxygen or nitrogen can also be used. Such a metathesis polymerizable 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 group or the like.

Such a polar group has, as a Lewis base, an action of controlling the initiation of the metathesis polymerization reaction, and also has an effect of introducing a polar group into the polymer molded product thus produced, so that the necessity of those actions is satisfied. It is suitably used depending on the situation.

Examples of such polar monomers include (5-norbornenyl)
Methyl-phenyl ether, bis [(5-nornornenyl) methyl] ether, 5-methoxycarbonylbornene, 5-methoxycarbonyl-5-methyl-norbornene, 5 [(2-ethylhexyloxy) carbonyl] norbornene, ethylene-bis (5-norbornenecarboxylate), 5-cyanonorbornene, 6-cyano-1,4,5,8
-Dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, N-butyl nadic imide, 5- (4-pyridyl)
-Norbornene and the like can be mentioned.

Further, a halogen-containing / metathesis polymerizable monomer can be used for improving flame retardancy and softening temperature. Specific examples of such a monomer include 5-chloronorbornene, 5
-Bromonorbornene, 5,5,6-trichloronorbornene, 5,5,6,6-tetrachloronorbornene, 5,6-dibromonorbornene, 5- (2,4-dibromophenyl) norbornene and the like can be mentioned.

It is preferable that the metathesis-polymerizable monomers as described above all have a content of impurities that inhibit the metathesis polymerization catalyst as small as possible.

The metathesis polymerization catalyst system used to obtain polymer moldings in the present invention generally comprises two components, a catalyst component and an activator component, as is known.

However, the metathesis polymerization reaction is generally an exothermic reaction, and once the polymerization is started, the system is further heated to accelerate the reaction.

Therefore, as described above, two solutions, that is, a solution mainly composed of a monomer and a catalyst component (solution A) and a solution mainly composed of a monomer and an activator component (solution B) are prepared in advance and subjected to collision mixing (RIM method). ) Or a static mixer, rapid mixing, immediate injection into a mold, shaping, and curing in a mold can be preferably used. In that case, the composition of the monomer does not have to be the same in both liquids, and can be arbitrarily changed depending on the function of the monomer. Further, the amount of rubber added can be changed depending on the two liquids, but in the reaction injection molding method, it is generally more preferable that the two liquids have the same viscosity because mixing is effectively performed.

As another method for obtaining a polymer molded product, a Lewis base that acts as a regulator that delays the initiation of metathesis polymerization as described above, or a metathesis polymerizable monomer having such a whistle base is added to delay the initiation of polymerization and preliminarily generate it. It is possible to take a method of flowing the prepared premix into the mold. In this case, it is advantageous to obtain a fiber-reinforced molded product by placing a glass fiber mat or the like in the mold in advance.

Salts such as halides of tungsten, rhenium, tantalum, molybdenum, etc. are used as the catalyst component in the metathesis polymerization catalyst system, but tungsten compounds are particularly preferable. As such a tungsten compound, tungsten halide, tungsten oxyhalide and the like are preferable, and more specifically, tungsten hexachloride, tungsten oxychloride and the like are preferable. Further, organic ammonium tungstate or molybdate can also be used. It has been found that such a tungsten compound immediately starts cationic polymerization when added directly to the monomer, which is not preferable. Therefore, such a tungsten compound is preferably suspended in an inert solvent such as benzene, toluene, chlorobenzene or the like in advance, and solubilized by adding a small amount of an alcohol compound or a phenol compound before use.

Further, as described above, in order to prevent undesired polymerization, it is preferable to add about 1 to 5 mol of Lewis base or chelating agent to 1 mol of the tungsten compound. Examples of such additives include acetylacetone, acetoacetic acid alkyl esters, tetrahydrofuran and benzonitrile. The polar monomer for copolymerization used in the present invention may be a Lewis base itself as described above, and may have its action even if the above compound is not particularly added.

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

On the other hand, the activator component in the metathesis polymerization catalyst system is preferably an organometallic compound centered on an alkylated compound of a metal of Group I to Group III of the Periodic Table, particularly tetraalkyltin, an alkylaluminum compound, an alkylaluminum halide compound, Specific examples thereof include diethylaluminum chloride, diethylaluminum chloride, trioctylaluminum, dioctylaluminum iodide, and tetrabutyltin. The other solution (corresponding to solution B) is formed by dissolving the organometallic compound as the activator component in the raw material monomer.

In the present invention, basically, a polymer molded product can be obtained by mixing the solution A and the solution B, but with the above composition as it is, the polymerization reaction is started very quickly. Curing may occur before it is sufficiently poured into the mold, which often causes a problem. Therefore, it is preferable to use the activity modifier as described above.

As such a regulator, Lewis bases are generally used, and ethers, esters, nitriles and the like are used. Specific examples include ethyl benzoate, butyl ether, diglyme and the like. Such a regulator is generally used by adding it to the solution side of the component of the activator of the organometallic compound. When a copolymerizable monomer having a Lewis base 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 the catalyst component, the ratio of the tungsten compound to the raw material monomer is about 10 on a molar basis.
When the activator component is an alkylaluminum, the ratio of the aluminum compound to the raw material monomer is about 100 on a molar basis. Around 1 to about 2000 to 1, preferably about 200 to 1 to about 500 to 1 is used. Further, as described above, the masking agent and the regulator can be appropriately adjusted and used depending on the amount of the catalyst system used by experiments.

The polymer molded product according to the present invention may further contain various additives in order to improve or maintain its properties in practical use. Such additives include fillers,
Content, antioxidants, light stabilizers, flame retardants, polymer modifiers, etc. Since such an additive cannot be added after the polymer of the present invention is formed, when it is added, it is necessary to add it to the above-mentioned raw material solution in advance.

The easiest method is the solution A and the solution B.
Although it is possible to cite a method of adding it to either or both of them in advance, in that case, the catalyst component or the activator component having strong reactivity in the liquid does not react to a certain extent with practical use, and It must not interfere with polymerization. In any case, if the reaction is unavoidable but coexistence does not substantially inhibit the polymerization, it is possible to mix with the monomer to prepare the third liquid, and to use the mixture immediately before the polymerization. . Further, in the case of a solid filler, both components are mixed, just before starting the polymerization reaction or while polymerizing, for the shape that can sufficiently fill the voids, in the molding mold, It is also possible to fill it.

The reinforcing material or filler as an additive is effective in improving the bending modulus. Examples of such materials include glass fiber, mica, carbon black, wollastonite and the like. Those obtained by surface-treating these with a so-called silane gapler can also be suitably used.

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

In the present invention, it is essential to use the specific EPR.EPDM as described above, but in addition to that, other rubber or other polymer is added to the reaction solution to be dissolved or suspended before use. be able to.

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

As the molding method, as described above, the resin injection method in which the catalyst system and the monomer mixture are mixed in advance into the mold, the solution A and the solution B in which the catalyst system is divided into two are collided at the head portion. It is possible to adopt the RIM method in which it is mixed and poured into the mold as it is. In either case, the injection pressure into the mold can be relatively low, and thus inexpensive molds can be used.

Further, when the polymerization reaction in the mold starts, the temperature in the mold rapidly rises due to the reaction heat, and the polymerization reaction ends in a short time. Unlike the case of polyurethane-RIM, it is easy to release from the mold, and a special release agent is often unnecessary.

The molded product has an oxide layer on the surface and has good adhesion to commonly used paints such as epoxy and polyurethane due to the polarity of the cyano group.

The molded product thus obtained has improved impact resistance and heat resistance as compared with conventional ones, and members of various transportation devices including automobiles, electric and electronic device housings, etc.
It can be used for a wide range of purposes, including large moldings.

The present invention will be described in detail below with reference to examples. It should be noted that the embodiment is for the purpose of explanation and is not limited thereto.

Examples 1 to 7 and Comparative Examples 1 to 6 (i) Preparation of Catalyst Concentrated Liquid 19.8 Kg (50 mol) of tungsten hexachloride was dispersed in 90 l of dehydrated toluene under a stream of nitrogen, and 0.925 Kg (12.5 mol) therein. Was dissolved in 5 L of dehydrated toluene, and the mixture was stirred for 3 hours under an added nitrogen stream. Further, into the mixture, 5 l of nonylphenol 11.05 Kg (50 mol) was added.
The solution dissolved in dehydrated toluene of was added and stirred for 3 hours. 10 kg (100 mol) of acetylacetone was added dropwise thereto, and stirring was continued for a whole day and night. Hydrogen chloride generated during these processes is taken out of the system together with nitrogen, neutralized with an aqueous solution of caustic soda, and discarded.

Therefore, part of it was supplemented with toluene that had been reduced, and 0.5M was added.
A tungsten catalyst concentrate was prepared.

(Ii) Preparation of activator concentrate 5.7 Kg of di-n-octylaluminum iodide, 13.4
A 1.0 M aluminum activator concentrate was prepared by adding a mixture of 2 kg of tri-n-octylaluminum and 13.42 kg of diglyme to 100 l of purified dicyclopentadiene.

(Iii) Preparation of Reactive Solution (A) 964.6 parts of a metathesis polymerizable monomer solution having a predetermined composition in which a predetermined amount of a well-defined rubber having a commercially available composition is dissolved, 15.4 parts of a catalyst concentrate, and Ethanox 702 (ethyl ester) as an oxidation stabilizer. (Manufactured by K.K.) 20 parts under a nitrogen stream and mixed with the reactive solution (A)
30 kg was prepared.

(Iv) Preparation of Reactive Solution (B) Under a nitrogen stream, 96.4 parts of a metathesis polymerizable monomer solution having a predetermined composition in which a predetermined amount of a well-defined rubber having a commercially available composition was dissolved and 21.5 parts of an activator concentrate. 30 kg of reactive solution (B) was prepared.

(V) Preparation of polymer molding Using a lance type reaction injection molding machine manufactured by Niigata Iron Works Co., Ltd.
Mixing pressure 60 kg / cm ² Reactive solutions A and B are injected in equivalent amounts at a total amount of about 400 g / sec, and the mold surface having a cavity of 50 cm x 50 cm x 3 mm is held in a flat plate mold at 70 to 90 ° C. Filling and reaction curing were performed to obtain a resin molded product having a thickness of about 3 mm.

Using this plate-shaped molded product, heat deformation temperature (HDT) under load of 18.5 Kg / cm, second-order transition point (Tg) by DMA, notched Izod, bending modulus, bending elastic modulus and toluene from room temperature to low temperature The molded product was extracted with, the residual monomer in the extracted content was quantified by gas chromatography, and a comparison with a comparative example was performed in order to clarify the addition and curing of the rubber (or elastomer).

In Table 1, the types of rubber used in Examples and Comparative Examples, the concentration of the rubber in the monomer solution in which the crude composition and the rubber are dissolved, and the type of the monomer are shown.

Table 2 shows the performance of the molded product.

The reactive solutions A and B used here were both at 30 ° C.
The measured viscosity was in the range of 300-400 cps.

In the examples using the rubber specified in the present invention, the notched Izod shows that the value at room temperature to low temperature is 100 ° C. or more without deteriorating as compared with the comparative example, and the Tg is 150.
Shown above ℃.

Using SBR, BR, IR of Comparative Examples 1, 2, 4, etc., showing notched Izod equivalent or more when compared with the same DCP only as a monomer, and HDT, Tg is 5-13 ° C in HDT, 6 in Tg
It can be seen that the temperature has improved by ~ 20 ° C.

Comparative Example 5 and Example 7 correspond to the same proportion of DCP97.5 and ENB2.5, but different rubbers using monomers,
It is clear that HDT, Tg and notched Izod are improved.

In addition, even if the same EPDM is used, comparing Comparative Examples 3 and 4 in which standard EPDM containing 60 mol% of ethylene is used with Examples 1 to 4, in the case of Comparative Example 3, HDT and Tg are significantly different from other rubbers. It is well understood that the notched Izod shows a poor value as compared with the corresponding examples, and the notched Izod has a low value.

Similarly, when the same type of EPR was used, comparison of Comparative Example 6 using standard EPR with 60 mol% ethylene and Examples 5 and 6 using EPR with high ethylene content showed that HDT, Tg Not only is the latter improved, but the value of notched Izod at low temperature is excellent.

Generally, the degree of immobility of polymer chains, that is, the heat distortion temperature, which is related to stiffness, and the ease of movement of polymer chains, that is, the impact resistance, which is related to softness, are contradictory to each other. It is often difficult to improve both of them at the same time, but it is understood that the rubber of the present invention achieves both of them.

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Claims (1)

[Claims] 1. A method for producing a polymer molded product, which comprises simultaneously polymerizing and molding a metathesis polymerizable monomer in the presence of a metathesis polymerization catalyst system, wherein the ethylene-propylene rubber and / or the ethylene-propylene-diene-polymer are used. A rubber having an ethylene content of 65 mol% or more, 90% by weight of dicyclopentadiene, and 10% of ethylidene norbornene.
A method for producing a polymer molded product, which comprises adding at least one kind of solvent that substantially dissolves at least 3% by weight at 30 ° C. to a mixed solvent of 30% by weight.