JPH06102717B2 - Method for producing crosslinked polymer molding - Google Patents

Description

TECHNICAL FIELD The present invention relates to a crosslinked polymer molding obtained by bulk polymerization of a metathesis polymerizable monomer in a mold in the presence of a metathesis polymerization catalyst system and molding at the same time as polymerization. It relates to the improvement of products. More specifically, it relates to improvement of heat resistance of a polymer molded product produced by coexisting a polymer in which a part of unsaturated bond is converted to norbornene bond by reaction with cyclopentadiene.

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

Therefore, like dicyclopentadiene, it can be obtained cheaply,
And, a monomer having two metathesis-polymerizable groups,
A method has been proposed in which a liquid state is poured into a mold and bulk polymerization is performed therein to obtain polymerization and molding in one step (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-sized 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, especially in the crosslinkable monomer.

As a method for improving it, there has been proposed a method of forming a crosslinked polymer molded product in the coexistence of a soluble elastomer with a monomer-soluble elastomer and a method of adding a plasticizer.
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 an elastomer is an effective method because a considerably large effect is recognized even if a small amount is added.

However, the addition of such an elastomer generally tends to lower the heat resistance in view of heat deformability.

Therefore, the present inventor, if the metathesis-polymerizable cycloolefin group can be introduced into the elastomer-based polymer added to the polymer molded product to be subjected to such metathesis polymerization, the addition of the main chain can be cleaved. The present inventors have focused on the possibility that the heat resistance may be improved rather than preventing the deterioration of the heat resistance by causing the cross-linking without occurring.

Moreover, as a method for introducing such a metathesis-polymerizable cycloolefin group, for example, by adding cyclopentadiene to a carbon-carbon double bond such as polybutadiene having an unsaturated bond by Diels Alder, a norbornene bond is introduced. This is the focus.

c Structure of the Invention That is, generally, at least a part of the double bond of a soluble polymer having a carbon-carbon double bond in a considerable part in all repeating units is replaced with cyclopentadiene and Diels Alde
It is intended to improve the heat resistance by allowing a polymer to which an r addition reaction has occurred to which a norbornene bond has been added to coexist when a molded product is obtained from a metathesis polymerizable monomer.

Furthermore, during the Diels Alder addition, cyclopentadiene is converted into oligocyclopentadiene such as dicyclopentadiene or tricyclopentadiene used as a raw material, which is also compared to dicyclopentadiene. As a metathesis-polymerizable monomer, it is intended to give a molded product having a higher heat resistance, and it was also industrially advantageous to use them as a mixture without separating them from the norbornene polymer. It is a thing.

That is, the present invention includes the following inventions.

In a method for producing a crosslinked polymer molded product by simultaneously polymerizing and molding a metathesis polymerizable monomer in the presence of a metathesis polymerization catalyst system, at least 30 mol% of all repeating units are non-conjugated carbon-carbon double bonds. Carbon in the polymer (a) obtained by reacting a soluble polymer (a) having a repeating unit having at least one bond and having an average molecular weight of 500 or more with dicyclopentadiene and / or cyclopentadiene -A polymer (b) in which at least a part of carbon double bonds is converted to a norbornene structural unit or a reaction mixture (c) containing the polymer is added as at least a part of the metathesis polymerization reaction component. A method for producing a crosslinked polymer molded article.

In the present invention, (a) a reactive solution of a metathesis polymerizable monomer containing a catalyst component of a metathesis polymerization catalyst system (solution A) and (b) a reaction of a metathesis polymerizable monomer containing an activator component of a metathesis polymerization catalyst system Repeating solution having at least one non-conjugated carbon-carbon double bond in at least 30 mol% of all repeating units in a combination of reactive solutions consisting of at least one solution (solution B) And has an average molecular weight of 500
At least a part of the carbon-carbon double bond in the polymer (a) obtained by reacting the soluble polymer (a) with dicyclopentadiene and / or cyclopentadiene is converted to a norbornene structural unit. It is possible to use a combination of reactive solutions characterized in that the polymer (B) or the reaction mixture (C) containing the polymer is added.

In the present invention, the polymer (a) for introducing a norbornene bond by the reaction with dicyclopentadiene and / or cyclopentadiene has an average molecular weight of 500
As described above, it is necessary that the compound be soluble and that at least 30 mol% of all repeating units be composed of a repeating unit having at least one non-conjugated carbon-carbon double bond.

Further, as an important requirement, it is preferable to have as much as possible a polar group having an active hydrogen which generally inhibits the metathesis polymerization catalyst system such as a carboxyl group, a hydroxyl group and an amino group, and after the norbornene conversion, Those compatible with the metathesis-polymerizable monomer used are preferred.

The polymer (a) can be divided into a hydrocarbon type and a type containing a hetero atom, but the former is particularly preferable. As a specific example of the former, a soluble polymer in which at least 30 mol% or more of conjugated dienes are used as a monomer is preferable.

Specific examples of such conjugated dienes include butadiene, isoprene and piperylene, but butadiene and isoprene are particularly preferable.

Specific examples of the polymer (a) using a certain conjugated diene as a monomer include poly-1,4-butadiene, poly-1,2-butadiene, poly-1,4-isopun, and polyethylene-butadiene alternation. Examples thereof include copolymers, alternating polypropylene butadiene copolymers, polystyrene-butadiene, polybutylene-butadiene, and polybutylene-isoprene.

Among them, poly-1,4-butadiene and poly-1,4-isoprene are mostly composed of cis-type main chain structure.
Many trans-type structures can be used. For styrene-butadiene, if butadiene is 30 mol% or more, styrene and butadiene are random copolymers, block-shaped ones. Any of these may be used, but in consideration of the effect on impact resistance, the former preferably has a large cis structure and the latter preferably has a styrene content of 10 mol% or less.

As the hydrocarbon-based unsaturated polymer as described above, a wide range of polymers can be used from a liquid polymer having a molecular weight of 500 to several thousand to a solid polymer having a molecular weight of tens to hundreds of thousands.

As another group of hydrocarbon-based polymers having unsaturated bonds, there can be mentioned chained 5-tathesis polymers of cyclic olefins. Examples thereof include chain ring-opening polymers such as cyclopentadiene, cycloheptene, cyclooctene, cycloocta-1,4-diene, cyclododecene, norbornene, and 5-ethylidene norbornene.
These are structurally and property similar to the above-mentioned polymer using the conjugated diene and can be used similarly.

In the polymer (a), those having a hetero atom can be roughly classified into those having a carbon chain as a main chain and having a hetero atom in a side chain and those having a hetero atom in the main chain.

Examples of the former include acrylonitrile butadiene copolymer, chloroprene polymer, acrylic acid (or methacrylic acid) ester-butadiene copolymer, maleimide-butadiene copolymer, polybutadiene partial hydrogen chloride adduct, and partial chlorine adduct. Examples thereof include a copolymer of a conjugated diene and a vinyl polymer containing a hetero atom, a polymer of a halogenated conjugated diene, and a conjugated diene polymer in which a hetero atom is introduced. In addition, anionic polymer of unsaturated bond-containing polar vinyl monomer such as anionic polymer of allyl acrylate, conversely, unsaturated alcohol such as aryl alcohol is introduced into the side chain by transesterification by polymer reaction to acrylic ester rubber. You can also give what you have done.

As those having a hetero atom in the main chain, unsaturated polyethers such as polyethers obtained by anionic polymerization of acrylic glycidyl ether, unsaturated diols such as 2-butene-1,4-diol 1,4-dichlorobutene-2, etc. Unsaturated Polyesters by Reaction of Unsaturated Active Dihalides with Dicarboxylic Acids or Functional Derivatives thereof. Conversely, unsaturated polyesters from unsaturated dicarboxylic acids such as maleic acid and fumaric acid or their functional derivative groups and diols. And so on.

As described above, in the heteroatom-containing unsaturated polymer, it is necessary that the active hydrogen-containing polar group, including the terminal group, does not substantially inhibit the metathesis polymerization catalyst. Non-Lewis-based polar groups such as nitriles, esters, ethers, N-substituted imides delay metathesis polymerization by forming a complex with the transition element of the main catalyst of the metathesis catalyst system and the metal element in the activator. Therefore, it can be used for controlling the polymerization rate depending on the application.

In the present invention, such an unsaturated group-containing polymer (a) is used in which at least a part of the unsaturated group in the polymer is norbornene-ized by cyclopentadiene and Diels Alder addition.

Such norbornene formation is carried out by reacting cyclopentadiene and / or dicyclopentadiene with the polymer (a) by heating.

In general, cyclopentadiene is more stable in dicyclopentadiene than in monomeric cyclopentadiene,
And it is cheap and easy to obtain. Therefore, such dicyclopentadiene can be advantageously used in the present invention rather than cyclopentadiene.

That is, in the state of being heated for the reaction with the unsaturated group-containing polymer (a), even if dicyclopentadiene or cyclopentadiene is used, an equilibrium structure at that temperature is obtained. However, since dicyclopentadiene is superior in stability, it can be said that it is rather small in terms of side reaction.

Due to the reaction between the unsaturated group-containing polymer (a) and the cyclopentadiene, the mixing ratio is the desired ratio of norbornene groups, reaction temperature, time, and after the reaction, the mixture may be used as it is or the norbornene polymer may be separated. An appropriate ratio can be selected depending on conditions such as whether or not to use. Generally, a range of about 50 wt% is used with respect to (a). The reaction temperature is 100 ° C to 200 ° C, particularly preferably 140 ° C to 190 ° C. The reaction time is generally in the range of 1 to 30 hours.

It is generally preferable to use a closed autoclave as the reaction vessel.

However, even in this case, the internal pressure does not generally rise to several atmospheres or more even if a low boiling point cyclopentadiene is used as the initial reaction reagent because the cyclopentadiene forms an equilibrium structure based on the reaction temperature. Further, it is preferable to carefully replace the reaction reagent with an inert gas such as nitrogen gas so that the reaction reagent is not subjected to side reactions such as oxidation during the reaction.

The norbornenation reaction is an equilibrium reaction, and the amount of cyclopentadiene used and the type and amount of unsaturated bond in (a),
Although it depends on the reaction temperature and the like, it is generally preferable to add about 3 to 30 mol% of the unsaturated bond. Regarding the degree of norbornene, by separating the polymer component from the reaction mixture and redissolving it in a solvent such as deuterium chloroform,
It can be measured by measuring NMR.

Thus, the norbornene-ized polymer (b) can be used once separated from the reaction mixture, but the dicyclopentadiene used for norbornene-formation is a typical and most common metathesis-polymerizable monomer. It is possible to prepare a reactive solution by adding a metathesis polymerizable monomer, if necessary, while keeping the reaction mixture as it is. When used in such a method, in this case, the cyclopentadiene has an equilibrium structure at the reaction temperature as described above. When heated to a temperature of 140 ° C, a considerable amount of oligocyclopentadiene such as tricyclopentadiene is formed, but this one forms a polymer chain having a softening point and a rigid chain when metathesized by polymerization than dicyclopentadiene. Therefore, it can be advantageously used for the purpose of the present invention.

However, since cyclopentadiene generally does not cause metathesis polymerization and also has an adverse effect on the metathesis polymerization catalyst system, it is preferable to keep the content of cyclopentadiene as low as possible when the reaction mixture is used as it is. .

As such a method, cyclopentadiene is unstable at around room temperature and almost all of it is added to dicyclopentadiene.Therefore, the reaction mixture is allowed to stand at 60 ° C to room temperature for a certain period of time until the equilibrium composition at that temperature is reached. The method of reducing pentadiene can be mentioned. Further, as described above, since cyclopentadiene has a boiling point, it can be removed by topping. When the above two methods are used together, they can be completely removed.

Regarding the amount of the norbornenated polymer (b) to be used for the metathesis-polymerizable monomer, the norborneneization rate of the norbornene polymer (b), the molecular weight, the desired molding method of the reactive solution, that is, the reaction injection molding method by collision mixing Depending on the method such as the resin transfer method or the required performance of the target molded product, it is generally 1
A range of 2% to 15% by weight is particularly preferably used in the range of 40% by weight to 40% by weight.

As the metathesis polymerizable monomer used for forming a molded product together with the norbornene polymer (b), any compound such as a compound capable of giving a bulk-polymerized molded product by metathesis polymerization may be used, but it is generally a metathesis-polymerizable cyclohexene. Those containing 1 to 4 alkene groups are used. Those having a norbornene-type bond are particularly preferable. Especially hydrocarbon type is preferable,
Specific examples include dicyclopentadiene, dihydrodicyclopentadiene, cyclopentadiene-methylcyclopentadiene co-dimer, 5-ethylidene norbornene, 5-
Vinyl norbornene, 1,4-methano-1,4,4a, 5,6,7,8,8a
-Octahydronaphthalene, 1,4,5,8-dimethano-1,4,4
a, 5,6,7,8,8a-octahydronaphthalene, 6-ethylidene-1,4,5,8-dimethino-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 Examples include bis (5-norbornene). Particularly preferred is dicyclopentadiene or a monomer mixture containing 50% or more thereof.

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, as a Lewis base, has the effect of controlling the initiation of the metathesis polymerization reaction, and also has the effect of introducing a polar group into the formed polymer molding, and further the norbornene polymer (II) Depending on the type, it may have an effect of increasing the solubility, and therefore it is preferably used depending on the necessity of their action.

Examples of the polar monomer include 5-norbornenyl) methyl-phenyl ether, bis [(5-norbornenyl) methyl] ether, 5-methoxycarbonylnorbornene, 5-methoxycarbonyl-5-methyl-norbornene, 5 [(2-ethylhexene). Siloxy) carbonyl] norbornene, ethylene-bis (5-norbornenecarboxylate), 5-cyanonorbornene, 6-diano-1,4,5,8
-Dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, N-butyl nadic acid 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 the 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 (solution B) are prepared in advance,
A method in which rapid mixing is performed by means such as collision mixing (RIM method) or static mixer, the mixture is immediately poured into a mold, shaped, and then cured in the mold can be suitably 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. The addition amount of the liquid rubber can be changed depending on the two liquids. However, 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 polymerization monomer having such a Lewis base is added to delay the initiation of polymerization and preliminarily generate it. A method of injecting the prepared premix into the mold, that is, a method of resin injection can be used. 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. RIM
Also in the method, such a glass fiber mat can be used in a mold.

Salts such as halides of tungsten, rhenium, tantalum, molybdenum, etc. are used as the catalyst component in the metathesis polymerization catalyst system, but tungsten and molybdenum are preferred, and tungsten compounds are particularly preferred. 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 the like can also be used. It has been found that when such a tungsten halide compound is directly added to a monomer, it immediately starts cationic polymerization, which is not preferable. Therefore, such a tungsten halide compound is preferably suspended in an inert solvent such as benzene, toluene, chlorobenzene or the like in advance, and a small amount of an alcohol compound or a phenol compound is added to solubilize the tungsten halide compound for use.

Further, as described above, it is preferable to add about 1 to 5 mol of Lewis base or chelating agent to 1 mol of the tungsten compound in order to prevent unfavorable polymerization. Examples of such additives include acetylacetone, acetoacetic acid alkyl esters, tetrahydrofuran and benzonitrile. The polar monomer for copolymerization used in the present invention may itself be a Lewis base as described above, and may have its function even if the above compound is not 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 an organometallic compound centered on a metal alkyl compound of Group I to III of the periodic table, particularly tetraalkyltin, trialkylhydrogentin, triallylhydrogentin, alkylaluminum compound. , Alkyl aluminum halide compounds are preferable, and specific examples thereof include diethyl aluminum chloride, diethyl aluminum dichloride, trioctyl aluminum, dioctyl aluminum iodide, tetrabutyl tin, and tributyl hydrogen tin. 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, the solution A and the solution B are
Although it is possible to obtain a crosslinked polymer molded product by mixing the above, the above-mentioned composition will cause the polymerization reaction to start very quickly, so that curing may occur before it sufficiently flows into the molding mold. However, this often causes problems, and for that reason, it is preferable to use the activity regulator 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, regarding the masking agent and the adjusting agent as described above, the masking agent and the adjusting agent as described above can be appropriately adjusted according to the amount of the catalyst system used by experiments.

The crosslinked 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, contents, antioxidants, light stabilizers, flame retardants, polymer modifiers and the like. Since such an additive cannot be added after the crosslinked 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 can be mixed with the monomer to prepare the third liquid and mixed and used immediately before the polymerization. . Further, in the case of a solid filler, both components are mixed, and immediately before the initiation of the polymerization reaction or during the polymerization, those having a shape capable of sufficiently filling 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.

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

The polymer molded product of the present invention is a norbornene polymer (B).
Is added to improve the flexibility and the impact resistance, and the norbornene group participates in the metathesis polymerization to appropriately increase the crosslinking, thereby improving the heat resistance. However, when a polymer having a high norbornene ratio (b) is used, the heat resistance is remarkably improved, but the impact resistance may be less improved than in the case of an elastomer. An appropriate amount, generally 10% by weight or less, and generally 5% by weight or less can be used in combination within a range that does not impair the characteristics of the present invention. Elastomers used for this purpose include styrene-butadiene-styrene triblock rubber, styrene-isoprene-styrene triblock rubber, polybutadiene, polyisoprene, butyl rubber, ethylene-propylene rubber, ethylene propylene-diene terpolymer. I can.

The crosslinked 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.

Since the molded product has an oxide layer on the surface, it has good adhesion to commonly used paints such as epoxy and polyurethane.

The molded products thus obtained have particularly improved heat resistance as compared with conventional ones, and include large molded products such as parts of various transportation equipment including automobiles, housings of electric and electronic devices, etc. Can be used for a wide range of purposes.

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 13 and Comparative Examples 1 and 2 Commercially available dicyclopentadiene (DCP) was purified by distillation in a nitrogen stream under reduced pressure. Purified dicyclopentadiene has a melting point
The purity was 99% or higher when measured by gas chromatography at 33.6 ℃.

[Norbornenation of unsaturated polymer] Distilled and purified DCP and the unsaturated polymer shown in Table 1 were put into an autoclave at a ratio shown in Table 1, and after nitrogen substitution, the unsaturated polymer was uniformly dissolved. 12 at 60 ℃ to let
The mixture was heated and stirred for an hour. Thereafter, the temperature was raised, and the mixture was heated and stirred so as to reach the temperature shown in Table 1 to carry out norbornene conversion. After cooling, the sample was taken out and dissolved in DCP and used as it was when preparing the catalyst component liquid / activator liquid.

The norbornene conversion ratio was determined by dissolving the sample in toluene once, reprecipitating the rubber component with notanol, filtering, and drying at 50 ° C. in a nitrogen atmosphere for isolation. The isolated rubber was dissolved in deuterated chloroform and calculated from the ratio of double-bonded hydrogen in the measurement of NMR (nuclear magnetic resonance) spectrum.

The amount of cyclopentadiene trimer was measured by quantitative analysis of a solution chromatograph using a mixed solution of methanol and toluene used for reprecipitation.

A mixture of these norbornene-unsaturated polymers and DCP was mixed in a composition as shown in Table 2 below to prepare a DCP mixture containing a norbornene-unsaturated polymer.

[Preparation of Catalyst Component Solution] 20 parts by weight of hexachlorinated tanksten was added to 70 parts by weight of dry toluene under a nitrogen stream, and then a solution of 21 parts by weight of nonylphenol and 16 parts by volume of toluene was added to contain 0.5 M tungsten. Prepare a catalyst solution, and for this solution,
Nitrogen gas was purged overnight to remove hydrogen chloride gas purified by the reaction of tungsten hexachloride and nonylphenol to obtain a polymerization catalyst.

10 parts by volume of such a solution and 1.0 part by volume of acetylacetone were mixed with 500 parts by volume of a monomer mixture to obtain a tungsten content of 0.001M.
Solution A was prepared.

[Preparation of Activator Component Solution] Trioctylaluminum 85 was prepared at a molar ratio of dioctylaluminum iodide 15 and diglyme 100, and 500 parts by volume of the monomer mixture was mixed to obtain 0.003M of solution B as an aluminum component. Was prepared.

10 ml of the catalyst component solution (Solution A) and 10 ml of the activator component solution (Solution B) were heated to a predetermined temperature and then taken out into a syringe which was sufficiently replaced with nitrogen. The liquid was rapidly stirred and extruded into a glass flask equipped with a stirrer from a syringe at a constant speed at the same time, and the time required to reach 100 ° C. from the time when the injection of the liquid from the syringe was completed was measured.

Further, the solidified cross-linked resin was taken out, a section was cut out, and the softening point was measured by a TMA method-needle penetration mode in a nitrogen stream.

The results are shown in Table 3.

From the above results, the crosslinked polymer obtained in the reactive solution using the product mixture of the partial norbornene compound of the unsaturated polymer as it is is the polymer obtained in the same manner in the presence of the unsaturated polymer which does not norbornene In comparison, the heat resistance was greatly improved, and a norbornene unsaturated polymer was obtained. It can be seen that the polymerizability is hardly changed even when the reaction mixture is used as it is.

Example 14 Instead of dicyclopentadiene, cyclopentadiene obtained by thermally dissociating dicyclopentadiene was used, and poly-1,4-cis butadiene (BR-11) manufactured by Japan Synthetic Rubber was used as an unsaturated polymer in a weight ratio. The reaction was carried out in an autoclave at 4: 1 in the same manner as in Example 1 at 150 ° C for 3 hours, the reaction mixture was diluted with toluene and then reprecipitated in notanol, and after separating the rubber component, the temperature was kept between room temperature and 50 ° C. After that, it was sufficiently dried in a nitrogen stream for a long time to sufficiently remove the methanol content.

The norbornene conversion of this reaction polymer was 5% as measured by NMR in the same manner as in Examples 1 to 7.

The norbornene polymer was dissolved in DCP to have a concentration of 3.5% by weight. This was used as a monomer mixture and the results of Examples 8 to
Prepare reactive solutions A and B in the same manner as in 13, obtain a cured polymer in the same manner, and measure Tg by the TMA, which indicates 128 ° C,
It can be seen that it is improved as compared with Comparative Example 1.

Example 15 Liquid poly-cis-butadiene (Sumitomo Chemical Sumika Oil
150: average molecular weight 1500) and dicyclopentadiene (DCP)
Were reacted at a weight ratio of 1: 1 in an autoclave at 150 ° C for 12 hours. I tried to distill off unreacted dicyclopentadiene from the reaction product, but the viscosity increased and DCP
It was found that there was almost no distillation even at the boiling point of, and the DCP component reacted. In this case, since it is a liquid rubber, it is difficult to separate it by reprecipitation from a low molecular weight substance, and thus the infrared spectrum was measured to see the change. As can be understood from the attached infrared absorption spectrum, changes are observed before and after the reaction, and it is recognized that the Diels-Alder reaction is occurring.

Using the product as a monomer, a monomer mixture having the composition shown in Table 4 below was prepared, and a crosslinked polymer molded product was prepared in the same manner as in Example 1.

In the same manner as in Example 1, the molded product was cut at the mixing temperature, the polymerization time, and cut from the molded product to measure the softening point and the swelling ratio by TMA. The results are shown in Table 5 below.

In Example 15, it can be seen that the softening point is improved as compared with the DCP homopolymer (Comparative Example).

[Brief description of drawings]

16 is an infrared absorption spectrum shown in Example 15 of the present invention for comparing infrared absorption spectra of polybutadiene before norbornene and polybutadiene after norbornene.

Claims (1)

[Claims] 1. A method for producing a crosslinked polymer molded product by simultaneously polymerizing and molding a metathesis polymerizable monomer in the presence of a metathesis polymerization catalyst system, wherein at least 30 mol% of all repeating units are non-conjugated. A polymer (a) comprising a repeating unit having at least one carbon-carbon double bond and having an average molecular weight of 500 or more, and the polymer (a) obtained by reacting dicyclopentadiene and / or cyclopentadiene ( The polymer (b) obtained by converting at least a part of the carbon-carbon double bond in (a) into a norbornene structural unit or the reaction mixture (c) containing the polymer is added as at least a part of the metathesis polymerization reaction component. A method for producing a crosslinked polymer molded article, comprising: