KR930007919B1 - Shape-memory molded article of metathesis polymerized crosslinked polymer - Google Patents

Abstract

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Description

Shape Memory Molded Products of Crosslinked Metathesis Polymers

The present invention relates to a shape memory molded article of a novel crosslinked metathesis polymer and a method for producing the same by metathesis polymerization and co-molding.

In the past, several shape memory polymers have been reported. Molded articles made from shape memory polymers are deformed to their original shape when heated above the glass transition temperature under deformation conditions and then cooled while maintaining the deformed shape. Among the shape memory polymers is a high degree of polymerization (high molecular weight) norbornene homopolymer, which is prepared by metathesis polymerization of norbornene alone. However, the modified shape of the norbornene homopolymer is impractical because it returns to its original shape at a temperature as low as about 35 ° C., which is the temperature corresponding to room temperature in summer. Moreover, molded articles of norbornene homopolymers are typically prepared by molding pre-manufactured norbornene homopolymers at high temperatures of about 200 ° C. or higher, and at the same time, due to the low boiling point of norbornene, Molding and polymerization are also difficult. That is, the production of norbornene homopolymer molded articles is rather difficult.

Japanese Patent Laid-Open Publication No. 129013/83 discloses a method for producing a molded article by co-decomposition polymerization and molding of cycloolefin compounds such as dicyclopentadiene in a bulk state, but the production of shape memory polymers and molded articles is described. It is not.

The present inventors have studied diligently to obtain a shape memory polymer and a molded article having a high shape return temperature and easy to manufacture.

As a result, the inventors have carried out the shape memory of the crosslinked metathesis polymer having a shape return temperature of more than 35 ° C by simultaneous metathesis copolymerization and molding under a bulk state of a specific norbornene-type monomer and a cycloolefin compound having two modified cycloolefin groups. It was found that the molded article can be easily produced. This was an unexpected result because the crosslinked metathesis polymers have been considered to be readily deformable beyond the glass transition temperature due to their crosslinking structure.

Accordingly, an object of the present invention is to provide a shape memory molded article of a crosslinked metathesis polymer having a high shape return temperature.

Another object of the present invention is to provide a method for producing a molded article by co-metathesis polymerization and molding.

The present invention relates to 95-25 mol% of repeating units derived from at least one compound selected from (a) norbornene, 5-methylnorbornene and 5-ethylnorbornene and (b) two modified cycloolefin groups. The present invention relates to a shape memory molded article of a crosslinked metathesis polymer composed of 5 to 75 mol% of repeating units derived from one or more cycloolefin compounds.

In addition, the present invention provides (a) 95-25 mol% of at least one compound selected from norbornene, 5-methylnorbornene and 5-ethylnorbornene and (b) at least one having two modified cycloolefin groups. Preparation of a shape memory molded article characterized by injecting a metathesis polymerizable composition containing a monomer mixture consisting of 5 to 75 mol% of a cycloolefin compound and a metathesis polymerization catalyst system into a mold, and metathesis polymerization of the composition in a bulk state to obtain a molded article. It is about a method.

The "mole percent" of repeating units and monomer content mentioned herein refers to one or more compounds and cycloolefins selected from norbornene, 5-methylnorbornene and 5-ethylnorbornene constituting the repeating unit of the metathesis polymer. Based on the total moles of the compound.

Norbornene, 5-methylnorbornene and 5-ethylnorbornene used as component (a) in the present invention are generally subjected to the Diels-Alder addition reaction of cyclopentadiene with ethylene, propylene and butylene, respectively. Is manufactured by. In the case of 5-ethylnorbornene, it is also produced by partial hydration of vinylnorbornene, which is the diels-alder adduct from cyclopentadiene and butadiene. Among these, norbornene is commercially available recently and is generally used as starting monomers, such as norbornene rubber. In the present invention, it is preferable to use norbornene, 5-methylnorbornene and 5 norborneneethylnorbornene having a high purity of about 99% or more.

In the present invention, the cycloolefin compound having two modified cycloolefin groups used as component (b) preferably has a degree of metathesis polymerization comparable to norbornene, 5-methylnorbornene or 5-ethylnorbornene. .

Modified cycloolefin groups of cycloolefin compounds are those in which a modified cycloolefin ring is fused with one or more other cycloolefin rings to form a stronger modified ring structure. Representative modified cycloolefin rings include 4- and 5-membered cycloolefin rings, wherein 5-membered cycloolefin rings are considered the most representative modified rings used in the present invention. Therefore, the modified cycloolefin group of the cycloolefin compound is preferably composed of a cyclopentene group fused with a modified cycloolefin ring such as a 4- or 5-membered cycloolefin ring. Modified cycloolefin groups are exemplified according to the following structural formula (i) or (ii).

In the structure of the above formula, the cyclopentene ring (A) is fused with another cyclopentene ring (B) at the 3 and 5 positions to form a norbornene ring structure.

In the structure of formula (ii), the cyclopentene ring (C) is fused with another cyclopentene ring (D) at the 3 and 4 positions.

Both the structures of formulas (iii) and (ii) have a degree of metathesis polymerization comparable to norbornene, 5-methylnorbornene or 5-ethylnorbornene.

Therefore, it is preferable that the cycloolefin compound used as component (b) has any or all of the structures of Formula (i) and (ii) in a molecule | numerator.

Cycloolefin compounds may have one or more short side chains of one or two carbon atoms. However, the presence of flexible side chains is undesirable since it degrades the shape memory of the polymer.

Examples of the cycloolefin compound as the component (b) include higher oligocyclopentadiene such as dicyclopentadiene, tricyclopentadiene and tetracyclopentadiene. Higher oligocyclopentadienes are generally obtained as thermal equilibrium mixtures of dicyclopentadiene and higher oligocyclopentadiene by thermal polymerization of cyclopentadiene or dicyclopentadiene, and therefore in the form of equilibrium mixtures with dicyclopentadiene. Can be used as

Other examples of cycloolefin compounds that may be used in the present invention include 1, 4-dimethano-1, 4, 4a, 5, 8, 8a-hexahydronaphthalene, 5, 8-dimethano-1, 4 , 4a, 5, 8, 8a-hexahydronaphthalene, 1, 4-trimethano-1, 4, 4a, 5, 8, 8a, 9, 9a, 10, 10a-decahydroanthracene, 5, 8-tree Metano-1, 4, 4a, 5, 8, 8a, 9, 9a, 10, 10a-decahydroanthracene, 9. 10-trimethano-1, 4, 4a, 5, 8, 8a, 9, 9a , 10, 10a-decahydroanthracene and the like.

Among these compounds, the following formula

Dicyclopentadiene having a water bath of is preferable because dicyclopentadiene has a modified ring structure of the formulas (i) and (ii) as described above, and thus, norbornene, 5-methylnorbore than other cycloolefin compounds. This is because it has a metathesis degree of polymerization closer to nene or 5-ethylnorbornene. In addition, dicyclopentadiene can be purchased very easily at low cost.

Cycloolefin compounds other than dicyclopentadiene are preferably used as substitutes for some dicyclopentadiene.

It is desired to use cycloolefin compounds having a high purity of at least about 99.0%.

The shape memory molded article of the present invention is 95-25 mol% of at least one compound selected from norbornene, 5-methylnorbornene and 5-ethylnorbornene and at least one cyclopentadiene having two modified cycloolefin rings. It is prepared by injecting a metathesis polymerizable composition containing a monomer mixture of 5 to 75 mol% and a metathesis polymerization catalyst system into a mold and metathesis polymerizing the metathesis polymerizable composition in a bulk state.

In view of high shape return temperature (ie, high shape memory expression temperature), the molar ratio of norbornene, 5-methylnorbornene or 5-ethylnorbornene to cycloolefin is preferably 85 to 30/15 to 70. 80-40: 20-60 are more preferable.

When both monomers are similar, the shape memory expression temperature depends on the molar ratio of norbornene, 5-methylnorbornene or 5-ethylnorbornene to the cycloolefin compound. In general, shape memory expression temperature increases as the amount of cycloolefin compound increases. When dicyclopentadiene is used as the cycloolefin compound, it is preferable to use a large amount of dicyclopentadiene because dicyclopentadiene provides a molded article which is cheaper than norbornene and has a high shape memory expression temperature.

If necessary in the present invention, the monomer mixture may contain a small amount of the metathesis polymerizable compounds other than the norbornene, 5-methylnorbornene, 5-ethylnorbornene and cycloolefin compounds mentioned above, provided that the shape memoryability does not decrease. It may contain. Examples of these other metathesis polymerizable monomers include 1, 4-dimethano-1, 4, 4a, 5, 6, 7, 8, 8a, -octahydronaphthalene, 5, 8-dimethano-1, 4, 5a, 5, 6, 7, 8, 8a-octahydronaphthalene, norbornadiene, and the like.

The crosslinked metathesis polymers constituting the shape memory molded article of the present invention are formulas derived from norbornene, 5-methylnorbornene or 5-ethylnorbornene.

[Wherein, R ¹ is selected from H, CH ₃ and C ₂ H ₅ . ], And in the case of using dicyclopentadiene as a cycloolefin compound, formulas (i) and (iii)

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And

Has repeating units of.

In the case of using cycloolefin compounds other than dicyclopentadiene, the crosslinked metathesis polymers have repeating units with different repeating units, similar to the above units (i) and (iii).

As is apparent from the above description, the crosslinked metathesis polymer of the present invention contains a linear structure composed of the repeating units of formulas (iii) and (iii) and a crosslinking structure composed of the repeating units of formula (iii).

The metathesis polymerization catalyst system used in the present invention consists of a catalyst component and an activator component.

Metathesis polymerization proceeds very differently as an exothermic reaction. Under such circumstances, polymerization usually occurs before the mixed metathesis composition can be poured into the mold, which makes it difficult to inject the composition into the mold and makes the production of large shaped articles difficult.

Accordingly, in the present invention, the catalyst component and the activator component of the metathesis polymerization catalyst system are added to individual monomer solutions to form a plurality of reactive monomer solutions (ie, the first solution A and the second solution B), and then the plurality of reactive monomer solutions are prepared. Impingement mixing (RIM) or by using an electrostatic or dynamic rotary mixer (premix process), immediately pouring the mixture into the mold and polymerizing and molding in it immediately.

In this method, the plurality of reactive monomer solutions need not have the same monomer composition for each part. The monomer composition of each solution can vary freely if the final monomer ratio is within the scope of the present invention.

As a catalyst component of the metathesis polymerization catalyst system, a salt such as tungsten, molybdenum, rhenium or tantalum, preferably a halide of tungsten and molybdenum is used. Particularly preferred compounds are tungsten compounds. Among the tungsten compounds, tungsten halide and tungsten oxyhalogenated are preferred. More particularly, tungsten hexachloride and tungsten oxychloride are preferred. However, these tungsten halide compounds usually undesirably cause cationic polymerization when added directly to the monomer mixture. Thus, they are previously suspended in an inert solvent such as benzene, toluene or chlorobenzene, and are based on alcoholic compounds or phenolic compounds. Preference is given to adding and solubilizing the compound.

In order to prevent undesired polymerization such as cationic polymerization, it is preferable to add a chelating agent or a Lewis base of a solution containing a tungsten compound. Such additives may include acetylacetone, acetoacetic acid, alkyl esters, tetrahydrofuran, benzonitrile and the like. Preference is given to using about 1 to 5 moles of chelating agent or Lewis base per mole of tungsten compound. In addition, organic tungstates and molybdates soluble in the monomer mixture may be used as catalyst components of the metathesis polymerization catalyst system. Under such circumstances, the reactive monomer solution containing the catalyst component and monomers of the metathesis polymerization catalyst system is kept sufficiently stable for practical use.

The activator component of the metathesis polymerization catalyst system includes organometallic compounds such as alkylation products of metals of Groups I to III of the periodic table, including tetraalkyline and trialkyline hydrides; Alkyl aluminum compounds and alkyl aluminum halide compounds such as diethyl aluminum chloride, ethyl aluminum dichloride, trioctyl aluminum and dioctyl aluminum iodide; Tributyline hydride and the like are preferred. The activator component is dissolved in the monomer mixture to form another reactive monomer solution.

According to the present invention, the molded article is mainly prepared by mixing two reactive monomer solutions as described above. However, the use of the composition described above causes the polymerization to begin too rapidly, thus undesirable initiation of polymerization often results in partial gelation together before the mixed solution is completely filled in the mold. In order to overcome this problem, it is preferable to use a polymerization moderator.

As such a moderator, generally, a Lewis base, especially ethers, esters, nitriles, etc. are used.

Examples of the moderator include ethyl benzoate, butyl ether, diglyme, diethylene glycol dibutyl ether, benzonitrile and the like. Such moderators are generally added to a reactive monomer solution containing an active ingredient.

In this case, when a polar monomer which slows metathesis polymerization in combination with DCP is used in a reactive monomer solution containing an activator component, the polar monomer can be used as a moderator.

When the tungsten compound is used as the catalyst component, the ratio of the tungsten compound to the monomers described above is about 1000: 1 to about 15000: 1 on a molar basis, and about 2000: 1 is preferable. When the alkylaluminum compound is used as an activator component, the ratio of the aluminum compound to the monomer described above is about 100: 1 to about 5000: 1 on a molar basis, with a ratio of about 200: 1 to about 2000: 1 being preferred. The amount of masking agent or moderator can be adjusted experimentally depending on the amount of catalyst system.

In the production of the polymer molded article of the present invention, active anhydride compounds such as trichloromethylbenzene, dichlorodiphenylmethane, ethyltrichloroacetate, isophthaloyl chloride, acid anhydrides such as benzoic anhydride, phosphorus trichloride or diphenyldichlorosilane Small amounts may be added to reduce residual monomer content. The residual monomer content is preferably as low as possible for the expression of the desired shape memory. In general, residual monomer contents of up to 5%, in particular up to 3% are preferred. Therefore, it is desirable to use compounds that reduce residual monomer content.

In the shape memory molded article of the present invention, in order to improve or maintain the properties of the molded article, various additives may be substantially used under conditions that do not cause a marked decrease in shape memory. Additives include fillers, yarns, antioxidants, light stabilizers, flame retardants, polymeric modifiers, and the like. These additives cannot be added after the starting solution has been polymerized, molded and formed into shaped articles, and therefore must be added to the starting solution.

They are most easily added to either or both of Solution A and Solution B. The additive should be one that does not substantially react with and inhibit the polymerization of the highly reactive catalyst component, active agent component and other reagents in Solutions A and B. If the reaction between the additive and the catalyst system is unavoidable but basically does not inhibit polymerization, the third solution can be prepared by mixing the additive with the monomer, which is the first solution (i.e. solution A) just before the polymerization. And / or with a second solution (ie solution B). If the additive is a solid layer premise that can be sufficiently filled in the mold cavity, the mold may be filled with filler prior to pouring the reactive monomer solution into the mold.

Reinforcing agents or fillers may improve the flexural modulus of the polymer. This includes glass fibers, mica, carbon black, wollastonite, and the like. It may be desirable to use fillers whose surfaces have been treated with silane coupling agents. The use of fillers should be limited to the extent that the shape memory of the molded article is maintained.

It may be desirable for the molded article of the present invention to contain an antioxidant. Preferably, a phenol- or amine- antioxidant is added to the solution beforehand. Examples of the antioxidant include 2, 6-t-butyl-p-cresol, N, N'-diphenyl-p-petylenediamine, tetrakis [methylene (3, 5-di-t-butyl-4- Hydroxycinnamate)] methane and the like, and phenols and aromatic amines.

The reactive monomer solutions A and B are preferably injected into the mold in the form of laminar flow after mixing to prevent bubble generation.

In order to achieve laminar flow, the viscosity of the monomer solution and the injection speed in the mold must be properly adjusted. Often addition of midpoints to monomer solutions is required for laminar flow formation. Polymers that are soluble in the monomer solution, do not adversely affect the metathesis polymerization and the properties of the molded article, and which provide some good properties to the molded article are suitable midpoints. Examples of preferred polymers include non-crosslinked hydrocarbon elastomers such as styrene-butadiene-styrenetriblock rubber, styrene-isoprene-styrenetriblock rubber, polybutadiene, polyisoprene, butyl rubber, and ethylene-propylene-diene terpolymers. have.

As described above, the molded article of the present invention is preferably produced by a co-polymerization and molding, that is, by a premix process including a RIM process or an RTM and RI process.

In the RIM process, a plurality of reactive monomer solutions containing one catalyst component and one monomer and the other active agent component and monomer are rapidly mixed in an impingement mixing head of the RIM machine, and the mixture is immediately poured into a mold to polymerize and mold. do. In the premix process, a plurality of monomer solutions are mixed in advance in an electrostatic mixer, a dynamic rotary mixer, or the like to prepare a preliminary mixture, and then the premix is injected into a mold. Usually a RIM process is used.

In both the RIM process and the premix process, the mixture can be injected into the mold under relatively low pressure where low cost molds are available. The internal temperature of the mold is rapidly increased by the heat of polymerization reaction occurring at the start of the polymerization reaction so that the polymerization reaction is completed in a short time. The molded article of the present invention, unlike the polyurethane-RIM process, can be easily separated from the mold without a release agent.

The molded article of the present invention consists essentially of a hydrocarbon polymer with a high number of highly reactive unsaturated bonds. Thus, the surface of the molded article is oxidized by oxygen in the air to achieve high adhesion to polar polyurethane or epoxy resin paints or adhesives. Where paint moldings are required, paint should be selected that does not impair shape memory.

According to the present invention in which metathesis polymerization and molding are simultaneously performed, various shape memory molded articles, even large molded articles can be produced very easily.

In the present invention, the shape memory expression temperature of the molded article is changed within the aforementioned range by changing the molar ratio of norbornene, 5-methylnorbornene or 5-ethylnorbornene to a cycloolefin compound having two modified cycloolefin groups. In this case, it can be easily adjusted over a wide temperature range of about 40 ° C to about 100 ° C, preferably about 50 to 100 ° C. Therefore, the shape memory molded article of the present invention can be used in various fields. For example, when the shape memory molded article manufactured according to the present invention is frequently exposed to impacts or collisions such as bumpers, pandas, engine covers of motorbikes, walker bodies, etc., deformations caused by impacts or collisions, for example, depression The silver deformed molded article can be easily returned to its original shape by heating at a glass transition temperature or higher by hot air, hot water or the like.

Further, the shape memory molded article of the present invention suddenly changes its elastic material near the shape memory expression temperature, so that an article or part having a temperature sensing function, for example, an auto choke part of a engine, a heat exchanger part, or an adjustable heat dissipation function It can be used as a fluid bearing container of a pen with a fan, a fan that can change the pitch angle, and a suspended tire in which studs retreat from the surface of the tire depending on the road surface temperature.

The shape memory molded article of the present invention, which is deformed to a smaller size than the original size, can be returned to the original large shape in the space by inserting into the space through the narrow groove of the space and then heating above its glass transition temperature. Examples of shape-memory molded articles using such characteristics include bottle or pipe linings or mending materials, bottle toys or ornaments such as bottled vessels, and medical members such as baluns or catheters.

In addition, a heat-shrinkable article can be produced by deforming the original molded article into a large article from the shape memory molded article of the present invention. The heat shrinkable article adheres to the substrate and then heats above the glass transition temperature to firmly adhere to the substrate while shrinking to its original size. The heat shrinkage can be easily adjusted by changing the size of the original article and / or by changing the degree of deformation. Examples of shape memory molded articles using heat shrinkability include medical supplies such as zips, corsets, orthodontic materials, packing media such as wrapping materials or packing strings, clothing and accessories such as brasers, bags, shoes, rings, and glasses. .

In addition, other examples of shape memory molded articles include various toys such as snake toys, magic wands, retractable toy flowers, autorestore toys, and other deformable toys.

As can be seen from the above description, the present invention provides various molded articles such as transportation vehicles, machines, industrial articles, medical articles, clothes, daily necessities, toys, and entertainment articles.

The present invention is explained in more detail by the following examples. These examples are illustrative only and are not intended to limit the invention.

EXAMPLES 1-11

Commercial dicyclopentadiene (DCP) was purified by distillation under nitrogen and reduced pressure to produce purified DCP having a freezing point of 33.4 ° C. Purity measured by gas chromatography was greater than 99%.

Norbornene, 5-methylnorbornene and 5-ethylnorbornene were used as mass products or experimental reagents, each of which was measured to be at least 99% pure by gas chromatography.

[Preparation of catalyst component and monomer containing solution]

Tungsten under 20.0 g of salt was added to 70 ml of anhydrous toluene under a stream of nitrogen, followed by a solution containing 0.925 g of t-butanol and 5 ml of toluene, a solution containing 11 g of nonyl phenol and 5 ml of toluene, and 11 g of nonyl phenol. And 5 ml of toluene were added, and a catalyst solution containing 0.5 M tungsten was prepared in terms of metal content. The catalyst solution was purged with nitrogen gas overnight to remove the hydrogen chloride gas produced by the reaction of tungsten hexachloride and nonylphenol. 1 ml of acetylacetone was added to 10 ml of the resulting catalyst solution to prepare a concentrated catalyst component solution.

100 g of a monomer mixture containing each of the purified DCP and the above-described purified norbornene at a ratio shown in Table 1 was 3.0 g of ethylene-propylene-ethylidene-norbornene rubber containing 70 mol% of ethylene and ethanox (an oxidation stabilizer) Ethanox) was mixed with 702.2 g. To the fish mixed solution, the concentrated catalyst component and dichloro-diphenylmethane prepared above were added to form a solution (solution A) containing 0.001 M of tungsten and 0.0075 M of dichloro-diphenylmethane.

[Preparation of solution containing active ingredient and monomer]

Trioctyl aluminum, dioctyl aluminum iodide and diglyme were mixed in a molar ratio of 85: 15: 100 to prepare an active agent-containing solution.

The production-activating agent-containing solution was mixed with 100 g of the monomer mixture containing the purified DCP and the above-described purified norbornene and 3.0 g of the above-described ethylene-propylene-ethylidene-norbornene rubber in the ratio shown in Table 1, In terms of content, a solution containing 0.003 M of aluminum (solution B) was prepared.

[Production of Molding Plate]

80 ml of Solution A and 80 ml of Solution B, respectively, maintained at 30 ° C. were injected into the mixing head of the small-reaction injection molding machine and injected after impingement mixing in the mold maintained at 70 ° C.

Each 3 mm thick crosslinked molded plate was prepared.

Each molded plate was cut into pieces of 200 mm x 15 mm x 3 mm, and each piece was heated to a sufficiently softened state, twisted to form a spiral, and cooled as it was, to prepare a spirally deformed shape memory article.

Each of the spirally deformed articles was immersed in a molar at 25 ° C. and mercury was slowly raised. The temperature at which the spirally deformed article returned to its original non-helical piece shape was measured and recorded as the shape memory expression temperature. The results are shown in Table 1.

Along with the shape memory expression temperature, the mechanical, physical and chemical properties and the amount of residual monomers in the plate are shown in Table 1.

TABLE 1

Note: * Commercialized by Nippon Zeon Co., Ltd.

For each piece, the helix-strain / recovery process described above was repeated. All the pieces showed excellent shape memory even after 10 process repetitions.

Further, the molded plate of Example 1 was cut into dumbbell-shaped pieces and drawn to a strain rate of 500% by a tensile tester while drawing a strain curve. The stretched dumbbell shaped pieces returned to their original unstretched dumbbell shape when heated above the shape memory expression temperature shown in Table 1. The returned dumbbell piece was stretched again according to the above process. The second stress strain curve obtained by the second stretching was the same as in the first stretching.

The results and the experiments shown in Table 1 indicate that the molded article of the present invention has excellent shape memory of the shape memory expression temperature of about 40 ° C. or more, and the shape memory expression temperature increases with increasing DCP content.

Claims (16)

(a) 95-25 mol% of repeating units derived from at least one compound selected from norbornene, 5-methylnorbornene and 5-ethylnorbornene, (b) at least one having two modified cycloolefin groups A shape memory molded article of a crosslinked metathesis polymer composed of 5 to 75 mol% of repeating units derived from a cycloolefin compound. The process of claim 1 wherein the polymer is derived from at least 80-25 mole% of repeating units derived from at least one compound selected from norbornene, 5-methylnorbornene and 5-ethylnorbornene and at least one cycloolefin. Shape memory molded article, characterized in that consisting of 20 to 75 mol% repeat unit. 2. The shape memory molded article according to claim 1, wherein the cycloolefin compound has a degree of metathesis polymerization comparable to norbornene, 5-methylnorbornene and 5-ethylnorbornene. The cycloolefin compound of claim 1, wherein the cycloolefin compound is dicyclopentadiene, tricyclopentadiene, higher cyclopentadiene oligomer, 1, 4-dimethano-1, 4, 4a, 5, 8, 8a-hexahydronaphthalene, 5, 8-dimethano-1, 4, 4a, 5, 8, 8a-hexahydronaphthalene, 1, 4-tridimethanol, 4, 4a, 5, 8, 8a, 9, 9a, 10, 10a-decahydroanthracene, 5, 8-trimethano-1, 4, 4a, 5, 8, 8a, 9, 9a, 10, 10a-decahydroanthracene and 9, 10-trimethano-1, 4, Shape memory molded article, characterized in that selected from 4a, 5, 8, 8a, 9, 9a, 10, 10a- decahydroanthracene. 5. The shape memory molded article according to claim 4, wherein the cycloolefin compound is selected from dicyclopentadiene, tricyclopentadiene and higher cyclopentadiene oligomer. 6. The shape memory molded article according to claim 5, wherein the cycloolefin compound is dicyclopentadiene. The shape memory molded article according to claim 1 or 2, which has a shape memory expression temperature of 40 to 100 ° C. (a) 95-25 mol% of one or more compounds selected from norbornene, 5-methylnorbornene and 5-ethylnorbornene and (b) one or more cycloolefin compounds 5 to 2 modified cycloolefin groups. A method for producing a shaped memory molded article comprising injection of a metathesis polymerizable composition containing a monomer mixture of 75 mol% and a metathesis polymerization catalyst system into a mold, and metathesis polymerization of the metathesis polymerizable composition in a bulk state to produce a molded article. . 9. The metathesis synthesis catalyst system according to claim 8, wherein the metathesis synthesis catalyst system contains a catalyst component and an activator component, and the metathesis polymerizable composition is prepared by mixing a plurality of monomer solutions containing one catalyst component and the other containing the active ingredient. How to. 10. The method of claim 9, wherein the cycloolefin compound and at least one compound selected from norbornene, 5-methylnorbornene and 5-ethylnorbornene are present in the same monomer solution. 10. The method of claim 9, wherein the cycloolefin compound and at least one compound selected from norbornene, 5-methylnorbornene and 5-ethylnorbornene are present in different monomer solutions. The monomer mixture of claim 8, wherein the monomer mixture is 80-25 mol% of at least one compound selected from norbornene, 5-methylnorbornene and 5-ethylnorbornene and 20-75 mol% of at least one cycloolefin compound. Characterized in that it is made. The method according to claim 8, wherein the cycloolefin compound has a degree of metathesis polymerization comparable to norbornene, 5-methylnorbornene or 5-ethylnorbornene. The cycloolefin compound according to claim 8, wherein the cycloolefin compound is dicyclopentadiene, tricyclopentadiene, higher cyclopentadiene oligomer, 1, 4-dimethano-1, 4, a, 5, 8, 8a-hexahydronaphthalene, 5, 8-dimethano-1, 4, 4a, 5, 8, 8a-hexahydronaphthalene, 1, 4-trimethano-1, 4, 4a, 5, 8, 8a, 9, 9a, 10, 10a-decahydroanthracene, 5, 8-trimethano-1, 4, 4a, 5, 8, 8a, 9, 9a, 10, 10a-decahydroanthracene and 9, 10-trimethano-1, 4, At least one compound selected from 4a, 5, 8, 8a, 9, 9a, 10, 10a-decahydroanthracene. 15. The method of claim 14, wherein the cycloolefin compound is at least one compound selected from cyclopentadiene, tricyclopentadiene, and higher cyclopentadiene oligomers. The method of claim 15, wherein the cycloolefin compound is dicyclopentadiene.