JPH07693B2 - Method for producing crosslinked polymer molding - 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 coexistence of a metathesis polymerization catalyst system, and carrying out molding simultaneously with bulk polymerization in the mold, whereby The present invention relates to a combination of the obtained polymer molded product and a reactive solution therefor.

More specifically, the present invention relates to an improved polymer molded product which is excellent in impact resistance and has very little residual monomer by polymerizing and molding by adding a specific elastomer and a specific compound in the above technique. .

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, it has been found that a great improvement is required for actually using these polymer molded products with high practicality. Of these, the three most important are the improvement of impact resistance, the improvement of heat resistance, and the reduction of the odor emitted from the molded product due to residual monomers.

First, regarding the improvement of impact resistance, as described above, large-sized molded articles are often 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 is difficult to say that it is a sufficient method.However, the method of adding a rubber has a considerably large effect even if added in a small amount, and is an effective method. Can be said. Such rubbers or elastomers are generally hydrocarbon rubbers such as poly-cis-
1,4-butadiene rubber (BR), polystyrene-butadiene rubber (SBR), poly-cis-1,4-isoprene rubber (I
R), polyethylene propylene rubber (EPR), polyethylene-propylene-diene terpolymer rubber (EPDM), polyisobutylene rubber (IIR), etc. have been found to be easy to use.

On the other hand, in the case of such a polymerized molded product, the unreacted monomer will inevitably remain due to the characteristics of the polymerization reaction.

Such residual monomers are, for example, in the case where the monomer is dicyclopentadiene (DCP), DCP and cyclopentadiene dissociated from such residual monomer, but such metathesis polymerizable monomers including them generally have a characteristic strong and unpleasant odor. In many cases, the molded product emits such an odor, which is a major problem for the molded product as a product.

Furthermore, it has been found that when the amount of residual monomer is large, the plastic action thereof impairs the heat resistance represented by the heat distortion temperature (HDT). Moreover, the reactive solution containing such a catalyst may lose its polymerization activity during storage, and in that case, the residual monomer may increase due to deviation of the mixing ratio of the reactive solution as described later. Often, in that case, not only the odor but also the heat resistance is impaired as described above. Therefore, reducing the residual monomer as much as possible in the production of such a polymer molded product is effective in both improving the odor and improving the heat resistance.

As a method for reducing such residual monomers, US Pat.
The specification of 1,344 discloses a method of adding a hydrocarbon compound having a trihalogenated methyl group or a hydrocarbon compound having a halogen atom activated by a double bond at the β-position.

The mechanism of action of monomer reduction of such a compound has not been clarified yet, but when it is contained in the reactive solution before the initiation of metathesis polymerization, it does not seem to exert any action, and therefore the polymerization It is considered that the action is initiated by the reaction with the catalyst system after the reaction is started or after the reaction is completed.

In this case, the present inventors have found that the transition metal ion, which is the active center element of the metathesis polymerization catalyst, for example, the maximum valence of tungsten is reduced by the action of alkylaluminum used as an activator and has a lower valence. It is considered that the compound having the above formula forms a redox system to oxidize a transition metal ion and at the same time to reduce itself by abstraction of a halide ion to generate a radical. It is considered that the residual monomer is further reacted and reduced by the action of either the oxidized metal ion or the generated radical, and in addition to the halogenated hydrocarbon as described above, a compound having such a possibility, for example, It has been confirmed that similar effects can be obtained with compounds such as carboxylic acid halides, halogenated silicon, phosphorus and sulfur.

By the way, in the polymer molded product to which these residual monomer reducing agents have been added and the elastomer has been added, it is recognized that the residual monomer is reduced and the heat resistance is improved.

c Structure of the invention Therefore, it is possible to realize the above-mentioned three important improvement problems, namely, improvement of impact resistance, improvement of heat resistance and reduction of residual monomer, by the above two additives. . However, it has been found that there is a case where there is an interaction between these two additives and the effect is diminished.

That is, it has been found that the impact resistance may be impaired when the monomer reducing agent is used in an amount sufficient to reduce the residual monomer as described above. Therefore, the present inventor, in more detail, when examining this phenomenon, it can be found that the impact resistance due to the monomer reducing agent is not substantially reduced if a specific elastomer is selected.
The present invention has been reached. Immediately, the present invention, in the method for producing a polymer molded product, wherein the metathesis polymerizable monomer is polymerized and molded simultaneously in the coexistence of a metathesis polymerization catalyst system, and is mainly composed of a hydrocarbon, and
The soluble elastomer (I) in which the repeating unit having a carbon-carbon double bond contained in the main chain or the side chain is 10 mol% or less in all repeating units, and the maximum of transition metal elements in the metathesis polymerization catalyst system A method for producing a polymer molded product, comprising adding at least one compound (II) each capable of forming a radical by being reduced by a redox reaction with a valence state lower than the valence Is.

In the present invention, a) a reactive solution of a metathesis polymerizable monomer containing a catalyst component of a metathesis polymerization catalyst (solution A) and b) a reactive solution of a metathesis polymerizable monomer containing an activating component of a metathesis polymerization catalyst system (solution) B) in the combination of at least one reactive solution, at least one of these solution A and solution B has a repeating unit mainly composed of a hydrocarbon and having a carbon-carbon double bond contained in a main chain and a side chain. Soluble elastomer (I) in an amount of 10 mol% or less in all repeating units, a valence state lower than the highest valence of the transition metal element in the metathesis polymerization catalyst system, and a radical reduced by a redox reaction It is possible to use a combination of reactive solutions containing at least one compound (II) capable of forming (However, the double bond in the above elastomer does not include the conjugated double bond in the aromatic group.) Hydrocarbon type elastomers are roughly classified into unsaturated type and saturated type. It is known. That is, the former uses a conjugated diene such as butadiene or isoprene as a main monomer, and the carbon-carbon double bond remains in most of the repeating units constituting the elastomer, at least 50 mol% or more. Elastomers belonging to this group include poly-1,4-cis butadiene and poly-1,4-
Examples thereof include cis-isoprene, natural rubber, poly-styrene-butadiene copolymer elastomer, and poly-styrene-isoprene copolymer elastomer.

On the other hand, in the case of a saturated system, an α-olefin is obtained as a main monomer instead of a conjugated diene, and in principle, a main repeating unit does not have a carbon-carbon double bond. However, even in a saturated rubber, if the unsaturated unit is not completely contained in the repeating unit, only a small amount of a vulcanizing agent can be vulcanized because it can be vulcanized only by a strong vulcanizing agent such as peroxide. Copolymers of conjugated dienes, non-conjugated dienes, etc. are used so that unsaturated bonds are contained in repeating units.

The introduction of unsaturated bonds for such vulcanization is generally 10 mol% or less in all repeating units.

As such a saturated rubber, ethylene-propylene rubber (EPR), ethylene-butylene rubber (EBR) and the like can be cited as those consisting only of α-olefin monomers. As a component containing a small amount of diene as a copolymerization component, ethylene-propylene-diene-terpolymer rubber (EPDM), ethylene-butylene-dieneter-polymer rubber (EBDM), isobutylene rubber (IIR) [generally a small amount of isoprene is copolymerized You can list them.

As a result of detailed study, the present inventor has found that in the case of the latter saturated rubber, the above-mentioned decrease in impact resistance does not occur.

As the elastomer (I) used in the present invention,
First, ethylene-propylene rubber (EPR), ethylene-
Propylene diene polymer rubber (EPDM) may be mentioned.

Although it is possible to use commercially available products for both EPR and EPDM as they are, for the purpose of the present invention, the metathesis polymerizable monomers to be used are dissolved to the extent that there is no inconvenience when used as a reactive solution. Required to be done.

In such EPR and EPDM, the ethylene content is 50 to 90 mol%
Is used, and particularly preferably 60 to 85 mol%. As the non-conjugated diene used in EPDM, ethylidene norbornene (ENB) or dicyclopentadiene (DCP) is generally used. Such non-conjugated dienes are used in an amount of 10 mol% or less, more preferably 6 to 1 mol% in all repeating units.

Similar to EPR and EPDM, EBR and E with propylene replaced by butylene
BDM can be used as well.

The reason for using butylene instead of propylene is that it is used for the purpose of preventing crystallization and deterioration of rubber elasticity even if the ethylene content is increased.
It is used with the same ethylene content and non-conjugated diene content as R and EPDM, but particularly high ethylene content, that is, the range of 75 to 95 mol% is more preferable, and the range of 80 to 90 mol% is used.

As described above, as the saturated elastomer used in the present invention, polyisobutylene rubber can be used in addition to the above. However, although IIR is favored for tubes due to its low gas permeability, it should be kept in mind that the effect when used for the purpose of increasing impact resistance is not so great.

As a specific example of the saturated elastomer in the present invention, as described above, a polystyrene-isoprene copolymer rubber or a polystyrene-butadiene copolymer rubber is hydrogenated, and the residual amount of the double bond excluding the aromatic ring is saturated as described above. Those adapted to the definition of system rubber can be included in this.

The suitable amount of the saturated elastomer (or rubber) (I) as described above is determined by two factors.

That is, there are two factors, the improvement of the impact resistance of the obtained molded product and the viscosity of the reactive solution.

That is, the amount of the elastomer (I) added is required to be sufficiently effective to improve the impact resistance of the resin molded product, which is the intended purpose. However, in general, the rigidity may decrease as the impact resistance increases, so the rigidity must be maintained within a range that can be maintained according to the purpose of use of the resin.

On the other hand, in terms of viscosity, it depends on which molding method is used to mold such a reactive solution. For example, when the most efficient reaction injection molding method is used, efficient mixing is achieved by collision mixing. In addition, when such a mixed reactive solution flows into the mold, if it does not enter in a laminar flow state, bubbles will be caught and a large amount of bubbles will remain in the molded product. In order to satisfy the latter requirement, a viscosity above a certain level is required, as analyzed by the Reynolds number, while the former requirement requires a large amount of energy for collision mixing, which is too viscous. The injection pressure must be increased, which causes a mechanical problem.

A viscosity that can satisfy both such requirements is generally 200 to 1
The range of about 000 cps is more preferable, and the range of 250 to 500 cps is more preferable. Therefore, it is sufficient to select and use the elastomer (I) which has such a viscosity and can sufficiently improve impact resistance and a molecular weight which can be added. The molecular weight of the elastomer (I) is often expressed using the Mooney viscosity, which is one of the melt viscosities, as a parameter, and the one in the range of 5 to 20 is used in 100 ° C. measurement. Also,
The addition amount is 1 to 15% by weight, more preferably 3 to 10% by weight in the reactive solution.

The elastomer (I) is generally used by dissolving it in the reactive solutions (A) and (B). Therefore, as described above, it is necessary to substantially dissolve the metathesis-polymerizable monomer in the solution mainly under the use conditions as described above.

The term “substantially” means that the reactive solution is melted so that fluidity can be maintained to the extent that no inconvenience occurs during collision mixing or inflow into the mold.

The elastomer (I) is dissolved in at least one of the reactive solutions (A) and (B). Generally, when used in reaction injection molding, two liquids to be collision-mixed have the same viscosity so that mixing efficiency is higher. It is known to be good, and it is preferable to use it by dissolving it in both of the reactive solutions at almost the same concentration.

On the other hand, as a preferable example of the residual monomer reducing agent (II) which is another essential component in the present invention, it has at least one bond of halogen and carbon, sulfur, phosphorus or silicon, and this component is halogen. One that is activated by a substituent for an element bonded to

As the compound having a bond between a halogen and a carbon, a compound in which the carbon bonded to the halogen is activated by a double bond at the α-position as described above is preferable, and preferable examples include trichloromethylbenzene, ω , Ω'-dichlorodiphenylmethane, m-, or p-bis (trichloromethyl) benzene, ω, ω, ω ', ω'-tetrachloro-1,
4-dibenzylbenzene, ω-chlorodiphenylmethane, ω-chlorotriphenylmethane, benzyl chloride, m- or p-xylylene dichloride, ethyl trichloroacetate and the like can be mentioned.

Another preferred group having a halogen-carbon bond is carboxylic acid halides, and preferred examples include terephthalic acid chloride, isophthalic acid chloride, o-phthalic acid chloride, trimesyl acid chloride and the like. Can be given.

As a compound having a bond between halogen and silicon,
Those activated by a double bond at the α-position similar to carbon are preferable, and trichlorosilylbenzene, diphenyldichlorosilane, p-bis (trichlorosilyl)-
Examples thereof include benzene and vinyl-trichlorosilane.

Examples of the compound having a bond between halogen and phosphorus include phosphorus oxychloride and benzenephosphonic acid dichloride.

Further, as the compound having a bond of halogen and sulfur, benzenesulfonic acid chloride, trienesulfonic acid chloride and the like can be mentioned as easily available compounds. Examples of these halogen-containing residual monomer reducing agents include carboxylic acid anhydrides. An example of this is benzoic anhydride.

It is believed that the residual monomer reducing agent (II) acts by interacting with the transition metal element ion of the main catalyst of the metathesis polymerization catalyst, and therefore the addition amount should be determined based on this transition metal-containing molar concentration. Easy to think. In this case, when the residual monomer reducing agent (II) has two or more groups capable of acting with a transition metal element ion, it is considered that the two groups can act separately, and the molar equivalent used is divided by the number of functional groups. Will be considered as a standard.

With this use equivalent, generally, it is used in an amount of 0.2 to 4 times, and preferably 0.5 to 1.5 times the amount of the transition metal used.

Such a compound is preferably added to the side of the reaction solution (A).

By using such suitable amounts of (I) and (II), DCP is used as a metathesis-polymerizable monomer, and a 3 mm thick plaque is used in a crosslinked polymer molded product using a metathesis catalyst system composed of a tungsten type and an aluminum type. ,
Notched Izod is 40kgcm / cm ~ 55kgcm / cm, heat distortion temperature (18.5kg / cm ² load) 95 ~ 105 ℃ 1.0% residual monomer
You will get the following:

Under the same conditions, if (I) and (II) are not added at all, the notched Izod under the same conditions is 5-10 kgcm.
Considering that the heat distortion temperature is around 90 ° C / cm and the residual monomer is only about 2 to 3.5%, it is considered that the effect is remarkable.

On the other hand, as the metathesis polymerizable monomer used for forming the molded product together with the elastomer (I) and the residual monomer reducing agent (II) as described above, those which can be bulk-polymerized by metathesis polymerization to give a molded product,
Any substance may be used, but one containing 1 to 4 metathesis-polymerizable cycloalkene groups is generally used. Those having a norbornene-type bond are particularly preferable. Hydrocarbons are particularly preferable, and specific examples thereof include dicyclopentadiene, dihydrodicyclopentadiene, cyclopentadiene-methylcyclopentadiene co-dimer, 5-ethylidenenorbornene, 5-vinylnorbornene, norbornene, 5-cyclopentadiene. Hexenyl 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, ethylenebis ( 5-norbornene) and the like. Particularly preferred is dicyclopentadiene or a monomer mixture containing 50% or more, more preferably 70% or more of dicyclopentadiene.

If necessary, a metathesis-polymerizable monomer containing a polar group having a different element such as oxygen or nitrogen can also be used. Such metathesis-polymerizable monomers are also preferably those having 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-methoxycarbonylnorbornene, 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 flame retardancy and for improving the 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 component (solution B) are prepared in advance and subjected to collision mixing (RIM method). ), A static mixer, or the like, rapid mixing, immediate injection into a mold, shaping, and curing 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. Further, as described above, the addition amount of the elastomer (I) can be changed depending on both liquids, but generally in a reaction injection molding method, mixing is more effective when the viscosity of both liquids is more effective, which is more preferable. preferable.

As another method for obtaining a polymer molded product, a polymerization base is added in advance by delaying the polymerization start by adding a metathesis polymerization monomer having a Lewis base or a Lewis base acting as a regulator for delaying the start of metathesis polymerization as described above. 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 previously placing a glass fiber mat or the like in the 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 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 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 include diethyl aluminum chloride, diethyl aluminum chloride, trioctyl aluminum, dioctyl aluminum iodide, and tetrabutyl 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, a crosslinked 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, Since curing often occurs before it sufficiently flows into the casting mold, this 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 among them. Specific examples thereof 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 about 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.
It is possible to cite a method of adding it to either or both of them in advance, but in that case, the catalyst component having a strong reactivity in the liquid or the activator component does not react to some extent practically, 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 thereof 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-type or amino-type 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.

In the present invention, it is essential to use the specific elastomer as described above, but in addition to this, other polymers can be added to the reaction solution and dissolved or suspended before use.

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 catalyst system and the monomer mixture are mixed in advance so that the mixed premix is allowed to flow into the mold. Solution A and solution B, which are divided into two parts of the catalyst system, are mixed by collision at the head part. RIM that is poured into the mold as it is
You can take the method. 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 its surface, it has good adhesion to commonly used paints such as epoxy and polyurethane.

The molded products thus obtained have improved heat resistance compared to conventional ones, and are mainly used for 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 21, Comparative Examples 1 to 21 (i) Preparation of Catalyst Concentrated Liquid 19.8 kg (50 mol) of tungsten hexachloride was dispersed in 90 l of dehydrated toluene under a nitrogen stream, and 0.925 kg (12.5
(5 mol) of t-butanol dissolved in 5 l of dehydrated toluene was added, and the mixture was stirred under a nitrogen stream for 3 hours. Further, 5.15 kg (50 mol) of nonylphenol was added to the mixture.
A solution of 1 of dehydrated toluene was added and stirred for 3 hours. In it, 10kg (100mol) of acetylacetone,
Add dropwise and continue stirring for a whole day and night. Hydrogen chloride generated during these processes is taken out of the system together with nitrogen, neutralized with a caustic soda aqueous solution, and discarded.

Then, supplemented with toluene that was partly reduced, 0.5M
A tungsten catalyst concentrate was prepared.

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

(Iii) Preparation of Reactive Solution (A) Metathesis Polymerizable Monomer Solution 964.6 having a predetermined composition in which a predetermined amount of a well-defined elastomer having a commercially available composition is dissolved
Parts and catalyst concentrate 15.4 parts, Ethanox 70 as an oxidation stabilizer
20 parts of 2 (manufactured by Ethyl Co.) were mixed under a nitrogen stream to prepare 30 kg of each reactive solution (A).

(Iv) Preparation of Reactive Solution (B) Metathesis Polymerizable Monomer Solution 978.5 having a predetermined composition in which a predetermined amount of a commercially available elastomer having a well-defined composition is dissolved
And 21.5 parts of the activator concentrate were mixed under a nitrogen stream to prepare 30 kg of each reactive solution (B).

Unless otherwise specified, the monomer reducing agent was used for molding by adding a predetermined amount to the reactive solution (A).

(V) Preparation of polymer molding Using a lance type reaction injection molding machine manufactured by Niigata Iron Works Co., Ltd.
Mixing pressure 60kg / cm ² Injection amount of reactive solutions A and B in equal amount, total amount of about 400g / sec, metal for flat plate with cavity of 50cm × 50cm × 3mm at 70-90 ℃. It was filled in a mold and cured by reaction to obtain a resin molded product having a thickness of about 3 mm.

Using this plate-shaped molded product, heat distortion temperature (HDT) under load of 18.5 kg / cm, secondary dislocation point (Tg) by DMA, notched Izod at normal temperature to low temperature, flexural modulus, flexural modulus and toluene The molded product is extracted with, and the residual monomer in the extract is quantified by gas chromatography, and the elastomer (I)
In order to clarify the effect of addition of the residual monomer reducing agent (II), a comparison was made with Comparative Example.

In Table 1, the types and compositions of the elastomers used in Examples and Comparative Examples and the concentration of the elastomer in the monomer solution in which the elastomer used in the preparation of the reactive solution is dissolved are also shown.

In Table 2, the performance of the molded product is shown together with the addition amount of the monomer reducing agent and the composition of the monomer. The reactive solutions A and B used here both have a viscosity of 300 to 40 measured at 30 ° C.
It was in the range of 0 cps.

In the case of unsaturated rubbers such as SBR and BR, it is found that the residual monomer is reduced by the addition of the residual monomer reducing agent, but the resin molding becomes brittle and the impact strength is greatly impaired especially at low temperature. (Comparative Examples 1 to 5, 7 to 10) Furthermore, when an appropriate amount of the residual monomer reducing agent is added, HDT and Tg are slightly improved (Comparative Examples 2 and 3), but the addition amount of the residual monomer reducing agent is large. It turns out that it also drops significantly. (Comparative Examples 4 and 5) In contrast, in the case of the combination of the saturated rubber of the present invention and the monomer reducing agent, in addition to the reduction of the residual monomer (generally 1%
It can be seen that the impact resistance is not affected at room temperature to low temperature, and that HDT and Tg are generally improved.

Also, even if a large amount of residual monomer reducer is added, there is no significant decrease in HDT and Tg as in the case of unsaturated rubber, and the impact resistance is rather improved near room temperature, and the residual monomer reducer is good. It can be seen that it acts as a plasticizer. Further, the saturated rubber used in the present invention is generally compared with the unsaturated rubber even when the same monomer is used,
It can be seen that HDT and Tg are improved, and that they can be further improved without sacrificing impact resistance by using the residual monomer reducing agent together.

That is, it is understood that the combination of the saturated rubber of the present invention and the residual monomer reducing agent realizes three important problems, namely, improvement of heat resistance, improvement of impact resistance, and reduction of odor due to reduction of residual monomer.

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Claims (3)

[Claims] 1. A method for producing a polymer molded product, which comprises simultaneously polymerizing and molding a metathesis polymerizable monomer in the coexistence of a metathesis polymerization catalyst system, wherein the polymer mainly comprises hydrocarbon and is contained in a main chain or a side chain. A soluble elastomer (I) having a repeating unit having a carbon-carbon double bond in an amount of 10 mol% or less based on all repeating units, and a valence state lower than the highest valence of a transition metal element in a metathesis polymerization catalyst system. A method for producing a polymer molded article, which comprises adding at least one of each of the compounds (II) which can be reduced by an oxidation-reduction reaction with the above compound to form a radical. 2. The method according to claim 1, wherein the elastomer (I) is at least one elastomer selected from the group consisting of ethylene-propylene rubber and ethylene-propylene diene-polymer rubber. 3. The compound (II) is ω, ω'-dichlorodiphenylmethane, ω, ω, ω ', ω'-tetrachloro-1,
It is at least one compound selected from the group consisting of 4-dibenzylbenzene, m-bis (trichloromethyl) benzene, p-bis (trichloromethyl) benzene, isophthalic acid chloride, phosphorus oxychloride, and benzenesulfonic acid chloride. Item 2. The manufacturing method according to Item 1.