JPH01204924A - Molded item of crosslinked polymer, preparation thereof and combination with reactive solution - Google Patents

Abstract

PURPOSE:To attempt to improve impact resistance and heat resistance and to decrease remaining monomer, by adding specified elastomer and compd. in carrying out simultaneously bulk-polymn. and molding of a metathesis- polymerizable monomer in a mold in the presence of a metathesis polymn. catalyst. CONSTITUTION:In a molded item obtd. by polymerizing a metathesis- polymerizable monomer (e.g., a cyclic olefin such as dicyclopentadiene) by using a metathesis polymn. catalyst such as a W-Al system, the title molded item is obtd. by a soln. contg. a soluble elastomer wherein the content of repeating units having carbon-carbon double bonds is 10mol% or less based on the total repeating units (e.g., an ethylene-propylene rubber or an ethylene-propylene-diene terpolymer) and a remaining monomer decreasing agent forming a radical when reduced by oxidation-reduction reaction with a compd. having a valence which is lower than the highest valence of a transition metal element in said catalyst (e.g., omega,omega'-dichlorodiphenylmethane).

Description

DETAILED DESCRIPTION OF THE INVENTION a. Industrial Application Field The present invention relates to a method of pouring a metathesis-polymerizable monomer into a mold in the coexistence of a metathesis-polymerization catalyst system, and performing molding simultaneously with bulk polymerization in the mold; This invention relates to a combination of a polymer molded product obtained by and a reactive solution therefor.

More specifically, in the above technology, by adding a specific elastomer and a specific compound to polymerize it,
This invention relates to an improved polymer molding having excellent f+ impact properties and containing very little residual monomer.

b. Prior Art It is known that cyclic olefins can be ring-opened by metathesis polymerization catalyst systems to give crosslinked polymers.

Therefore, there is a method in which a monomer such as dicyclopentadiene, which can be obtained at low cost and has two metathesis-polymerizable groups, is poured into a mold in a liquid state, bulk polymerized in the mold, and molded simultaneously with polymerization in one step. proposed (for example, see Japanese Patent Laid-Open No. 129013/1983).

According to this method, a large-sized molded product can be obtained using an inexpensive mold, so it has the possibility of being used in a wide range of applications.

However, it has been found that major improvements are required in order for these polymer molded products to be used with high practicality. Of these, three are particularly important: improvement in impact resistance, improvement in heat resistance, and reduction in depth emitted from molded products due to residual monomers.

First, regarding the improvement of impact resistance, as mentioned above, there are many uses for large molded products that require good impact resistance. However, in general, the above metathesis polymerizable monomers, especially Crosslinking monomers often lack this impact resistance.

As methods for improving this, a method has been proposed in which a polymer molded product is formed in the coexistence of a soluble rubber in a monomer, and a method in which a plasticizer is added. The method of adding a plasticizer generally has problems such as the blooming of the added plasticizer, so it is difficult to say that it is a sufficient method, whereas the method of adding rubber has a considerable effect even with a small amount of addition, and is an effective method. It can be said to be a method. Such rubbers or elastomers are generally hydrocarbon rubbers, such as poly-cis-1,4-butadiene rubber (BR), polystyrene-butadiene rubber (SBR), etc.
), poly-cis-1,4-isoprene rubber iR), polyethylene propylene rubber (EPR), polyethylene-propylene-dienther polymer rubber (EPDM), polyisoptylene rubber (IIR), etc. It has turned out to be easy.

On the other hand, in the case of such polymerized products, unreacted monomers inevitably remain due to the characteristics of the polymerization reaction.

Such residual monomers, for example, when the monomer is dicitalopentadiene (DCP), become DCP and cyclopentadiene which is dissociated from this, but such metasense polymerizable monomers, including these, generally have a unique strong and unpleasant odor. Because molded products often have
The generation of such odors is a major problem with molded products used as commercial products.

Furthermore, it has been found that when there is a large amount of residual monomer, the heat resistance expressed by heat distortion temperature (HD'r) etc. is impaired due to its plasticizing action. Moreover, the polymerization activity of the reactive solution containing such a catalyst may decrease during storage, or when the mixing ratio of the reactive solution deviates as described later, residual monomer may increase. As mentioned above, this is common and in such cases, not only the odor but also the heat resistance is impaired. Therefore, reducing the amount of residual monomer as much as possible in the production of such polymer molded products is effective in improving both odor and heat resistance.

As a method for reducing such residual monomers, US Patent No. 4,
No. 481,344 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 such compounds in monomer reduction is not yet clear, but it seems that they do not have any effect when they are contained in the reactive solution before the initiation of metathesis polymerization, and therefore, It is thought that its action begins by reacting with the catalyst system after the polymerization reaction has started or after it has ended.

In this case, the present inventor has discovered that the transition metal ion, which is the active center element of the metathesis polymerization catalyst, such as tungsten, is reduced from its highest valence by the action of the alkyl aluminum used as an activator, and has a lower valence. It is thought that the compound forms a redox system, oxidizes transition metal ions, and is itself reduced by abstracting halide ions to generate radicals. It is thought that the residual monomer will further react and be reduced by the action of either the oxidized metal ions or the generated radicals, and in addition to the halogenated hydrocarbons mentioned above, compounds that have the potential to do so, such as It was confirmed that compounds such as carboxylic acid halides, halogenated silicon, phosphorus, and sulfur can have similar effects.

By the way, in the polymer molded product to which these residual monomer reducing agents are added and an elastomer is added,
Along with a decrease in residual monomer, an improvement in heat resistance was also observed.

Structure of the C8 invention Therefore, it is now possible to achieve the three important improvement tasks mentioned above, namely, improvement of impact resistance, improvement of heat resistance, and reduction of residual monomer by using the above two additives. . However, it has been found that there is an interaction between these two additives, which may reduce their effectiveness.

That is, it has been found that when a monomer reducing agent such as the one described above is used to sufficiently reduce residual monomer, the impact resistance may be impaired. Therefore, the present inventor investigated this phenomenon in more detail and found that if a specific elastomer is selected, the impact resistance is not substantially lowered by the monomer reducing agent, This has led to the present invention. That is, the present invention provides: (1) A polymer molded product obtained by simultaneously polymerizing and molding a metathesis polymerizable monomer in the coexistence of a metathesis polymerization catalyst system, which is mainly composed of hydrocarbons and has no main chain or side A soluble elastomer (1) in which the repeating unit having a carbon-carbon double bond contained in the chain is 10 mol% or less of the total repeating units, and the highest valence of the transition metal element in the metathesis polymerization catalyst system. A polymer molded product obtained by adding at least one of each of compounds (II) that can be reduced to form radicals by redox reaction with low valence state.

(2) A method for producing a polymer molded product in which a metathesis-polymerizable monomer is simultaneously polymerized and molded in the coexistence of a metathesis-polymerization catalyst system, comprising mainly hydrocarbons,
and a soluble elastomer (I) in which the repeating unit having a carbon-carbon double bond contained in the main chain or 1fjl 3n is 10 mol% or less of the total repeating units, and a transition metal element in the metathesis polymerization catalyst system. Production of a polymer molded product characterized by adding at least one of each of a compound (II) in a valence state lower than the highest valence of Method.

(3) 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 a combination of reactive solutions consisting of at least one of these solutions A and IB, at least one of them consists primarily of hydrocarbons and has a main chain and 11'l! A soluble elastomer (I
), a transition metal element in a valence state lower than the highest valence of the transition metal element in the metathesis polymerization catalyst system, and a compound (II) that can be reduced to form a radical by a redox reaction. This is a combination of reactive solutions. (However, the double bonds in the above elastomers do not include conjugated double bonds in aromatic groups.) Hydrocarbon-based elastomers are roughly divided into two types: unsaturated types and saturated types. It is known. That is, the former uses a conjugated diene such as butadiene or isoprene as the main monomer, and carbon-carbon double bonds remain in most of the repeating units constituting the elastomer, at least 50 mol% or more. Elastomers belonging to this group include poly-1,4-cisbutadiene, poly-1
, 4-cis isoprene, natural rubber 1 poly-styrene-butadiene copolymer elastomer, 1 poly-styrene-isoprene copolymer elastomer, and the like.

On the other hand, in the case of a saturated type, it is obtained using an α-olefin as the main monomer instead of a conjugated diene, and as a general rule does not have a carbon-carbon double bond in the main repeating unit. However, even in saturated rubbers, if the repeating units do not have completely unsaturated bonds, they can only be vulcanized with strong vulcanizing agents such as peroxides, so a small amount of Copolymers of conjugated dienes, non-conjugated dienes, etc. are used so that they have unsaturated bonds in their repeating units.

The introduction of unsaturated bonds for such vulcanization is generally not more than 10 mol% of the total repeating units.

Examples of such saturated rubbers include ethylene-propylene rubber (EPR), which consists only of α-olefin monomers;
Examples include ethylene-butylene rubber (EBR). Ethylene propylene-dienter polymer rubber (EPDM) contains a small amount of diene as a copolymerization component.

Ethylene-butylene-genterpolymer rubber (EBD
M), isobutylene rubber (TIR) [- generally copolymerized with a small amount of isoprene.

As a result of detailed studies, the present inventors have found that in the case of the latter saturated rubber, the drop in impact resistance as described above does not occur.

As the elastomer (I) used in the present invention,
First, ethylene-propylene rubber (EPR) and ethylene-propylene diene terpolymer rubber (EPDM) can be mentioned.

It is possible to use commercially available F, PR, and EPDM as they are, but for the purposes of the present invention, the metathesis polymerizable monomers used should be used to the extent that there is no inconvenience when used as a reactive solution. required to be dissolved in

In such EPR and EPDM, ethylene-containing i50
As the non-conjugated diene used in EPDM, which is used in an amount of ~90 mol %, preferably 60-85 mol %, -m is ethylidene norbornene (END) or dicyclopentadiene (DCP). Such non-conjugated dienes are used in an amount of 10 mol% or less, more preferably 6 to 1 mol%, based on the total repeating units.

BPRJ? ? Like EPDM, BBR and BBDM in which propylene is replaced with butylene can also be used.

The reason why butylene is used instead of propylene is to prevent crystallization and loss of rubber elasticity even if the ethylene content is increased.
It is used with the same ethylene content and non-conjugated diene content as PR and EPDM, but especially high ethylene content, i.e. 75-95
More preferably, a range of 80 to 90 mol% is used.

As mentioned above, polyisobutylene rubber can be used as the saturated elastomer used in the present invention in addition to the above. However, although IIR is prized for use in tubes due to its low gas permeability, it must be kept in mind that the effect is not so great when used for purposes without increasing impact resistance.

As a special example of the saturated elastomer in the present invention, polystyrene-isoprene copolymer rubber or polystyrene-butadiene copolymer rubber as described above is hydrogenated, and the remaining amount of double bonds after removing the aromatic ring is saturated as described above. Rubbers that have come to meet the definition of rubber can be included in this category.

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

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

That is, the amount of elastomer (I) to be added needs to be such that it is sufficiently effective to improve the impact resistance of the resin molded product, which is the intended purpose. However, since there is a possibility that the rigidity generally decreases as the RTT impact resistance increases, the rigidity must be maintained within a range that corresponds to the intended use of the resin.

On the other hand, the viscosity differs depending on the molding method used to mold such a reactive solution, but for example, when using the most efficient reaction injection molding method, efficient mixing is achieved by collisional mixing. When the mixed reactive solution flows into the mold, unless it flows in a laminar flow state, it will trap bubbles and leave many bubbles in the molded product. In order to satisfy the latter requirement, as analyzed by the Reynolds number, a viscosity greater than or equal to chamber is required; on the other hand, the former requirement indicates that if the viscosity is too high, the energy required for collisional mixing increases. Therefore, the injection pressure must be eliminated, which causes mechanical problems.

The viscosity that can satisfy both of these requirements is generally 200
~1000cps, more preferably 250~5o
The range is ocps. Therefore, it is sufficient to select and use an elastomer (I) having a molecular weight that can be added in an amount that provides such a viscosity and sufficiently improves impact resistance. The molecular weight of the elastomer (I) is often expressed using Mooney viscosity, which is a type of melt viscosity, as a parameter, and a molecular weight in the range of 5 to 20 is used when measured at 100°C. Further, the amount to be added is in the range of 1 to 15% by weight, more preferably 3 to 10% by weight, in the reactive solution.

Such an elastomer (1) can be prepared using a reactive solution (8) and (
It is generally used by dissolving it in B). Therefore, as mentioned above,
Under the conditions of use as described above, it is necessary to substantially dissolve the monomer in a solution containing the metathesis-polymerizable monomer.

"Substantially" means that the above-mentioned reactive solution is dissolved in such a manner that fluidity can be maintained to the extent that no inconvenience occurs during impact mixing or flowing into a mold during molding.

Such an elastomer (I) can be prepared using a reactive solution (8) or F
Generally speaking, when used in reaction injection molding, it is known that the mixing efficiency is better when the two liquids collidingly mixed have the same viscosity. It is preferable to dissolve and use them at approximately the same concentration.

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

The compound having a halogen-carbon bond is preferably one in which the carbon bonded to the halogen is activated by a double bond at the alpha position, and a preferable example is l-dichloromethylbenzene. , w, w'-dichlorodiphenylmethane, m-1 or p-bis(trichloromethyl)benzene, Lw, w'yw'-tetrachloro-1,4-dibenzylbenzene, W-chlorodiphenylmethane, V-talolotriphenyl Examples include methane, benzyl chloride, m- or P-xylylene dichloride, ethyl trichloroacetate, and the like.

Another suitable group having a halogen-carbon bond includes carboxylic acid halides, and preferred examples include terephthalic acid chloride, isophthalic acid chloride, 0-phthalic acid chloride, trimesic acid chloride, etc. I can give you something.

Compounds containing halogen and silicon bonds include:
Those activated by a double bond at the α position similar to the case of carbon are preferable, and trichlorosilylbenzene, diphenyldichlorosilane, p-bis(trichlorosilyl)
-benzene, vinyl-1-dichlorosilane, etc.

Examples of compounds having a halogen-phosphorus bond include phosphorus oxychloride, benzenephosponyl dichloride, and the like.

Further, as compounds having a bond between halogen and sulfur, benzenesulfonic acid chloride, toluenesulfonic acid chloride, etc. can be cited as readily available compounds. Examples of these halogen-containing residual monomer reducing agents include carboxylic acid anhydrides. An example of such is benzoic anhydride.

It is believed that such residual monomer reducing agent i) acts through interaction with transition metal element ions of the main catalyst of the metathesis polymerization catalyst, and therefore, it is a good idea to determine the amount added based on this transition metal content molar concentration. In this case, when the residual monomer reducing agent (I[) has two or more groups that can act with transition metal element ions, it is assumed that the two groups can act separately, and the molar amount used is divided by the number of functional groups. The equivalent amount used will be considered as the standard.

The equivalent amount used is generally 0.2 to 4 times, more preferably 0.5 to 1.5 times the number of moles of transition metal used.

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

By using suitable amounts of (1) and (If), it is possible to use DCP as a metathesis polymerizable monomer and use a 3III thick plaque in a crosslinked polymer molded product using a metathesis catalyst system consisting of tungsten and aluminum. , Izod 1~ with notch is 40kg cw
/cx ~55kgcs/ex, heat distortion temperature (1
8,51 qr/- load) at 95 to 105°C with residual monomer content of 1.0% or less.

Under the same conditions, if (I) and (U) are not added at all, the notched Izod under the same conditions will be 5 to 10k.
Considering that only products with a g am/ex heat deformation temperature of around 90° C. and a residual monomer content of around 2 to 3.5% can be obtained, the remarkable effect can be felt.

On the other hand, the metathesis-polymerizable monomers used to form a molded product together with the elastomer (I) and residual monomer reducing agent (I[) as described above include those that can be bulk-polymerized by metathesis polymerization to give a molded product. Although any type of polymer may be used, those containing 1 to 4 metathesis-polymerizable cycloalkene groups are generally used. Particularly preferred are those having norbornene type bonds.

Hydrocarbons are particularly preferred, and specific examples include dicyclopentadiene, dihydrodicyclopentadiene,
Cyclopentadiene-methylcyclopentadiene codimer, 5-ethylidenenorbornene, 5-vinylnorbornene, norbornene.

5-cyclohecymonylnorbornene. 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-nitylidene-1.4゜5.8-dimethano-1,4,
4a,5,7,8.8a-hebutahydronaphthalene,
1,4,5.8-dimethano-1,4,4a,5,8.8
a-hexahydronaphthalene, tricyclo[8,2,1
, 01 trideca-5,11-diene, norbornadiene, 5-phenylnorbornene, ethylenebis(5-norbornene), and the like.

Among these, dicyclopentadiene or a monomer mixture containing dicyclopentadiene in an amount of 50% or more, preferably 70% or more is preferred.

Further, if necessary, a metathesis polymerizable monomer containing a polar group having a different element such as oxygen or nitrogen can also be used. The metathesis polymerizable monomer preferably has a norbornene structural unit, and the polar group is preferably an ester group, an ether group, a cyano group, or an N-substituted imide group.

Such a polar group has the function of regulating the initiation of metathesis polymerization reaction as Lewis space, and also has the effect of introducing a polar group into the formed polymer product.
They are suitably used depending on the necessity of their action.

Such polar monomers include (5-norbornenyl)
Methyl-phenyl ether 1bis[(5-norbornene)methyl]ether, 5-methoxycarbonylnorbornene, 5-methoxycarbonyl-5-methyl-norbornene, 5'[(2-ethylhexyloxy)carbonyl]norbornene, ethylene- Bis(5-norbornenecarboxylate), 5-cyanonorbornene, 6-dia2 1°4, 5.8-dimethano-t, 4.4a, 5,6
, 7,8.8a-octahydronaphthalene, N-butylnadichimide.

Examples include 5-(4-pyridyl)-norbornene.

Further, halogen-containing metathesis polymerizable monomers can also be used for flame retardancy and for improving the softening temperature. Specific examples of such monomers include 5-chloronorbornene,
5-bromonorbornene.

5.5.6- Trichloronorbornene, 5,5,6
．． Examples include 6-titrachlornorbornene, 5,6-dibromonorbornene, and 5-(2,4-dibromophenyl)norbornene.

All of the metathesis-polymerizable monomers mentioned above preferably have as low a content of impurities that inhibit the metathesis-polymerization catalyst as possible.

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

However, the metathesis polymerization reaction is -a) an exothermic reaction, and once the polymerization has started, the system is further heated and the reaction is accelerated.

Therefore, as mentioned above, two solutions were prepared in advance: a solution consisting mainly of monomers and catalyst components (solution A), and a solution consisting mainly of monomers and deactivator components (solution B). A preferred method is to rapidly mix the mixture using a static mixer or the like, immediately pour it into a mold, shape it, and then harden it in the mold.

In that case, the composition of the monomers does not need to be the same in both solutions, and can be arbitrarily changed depending on the monomer's ability. Also, as mentioned above, elastomer (I)
Although it is possible to change the amount of addition of both liquids, it is generally preferable in the reaction injection molding method that both liquids have the same viscosity because mixing is performed more effectively.

Another method for obtaining a polymer molded product is to delay the initiation of polymerization by adding Lewis space, which acts as a regulator to delay the initiation of metathesis polymerization, or a metathesis polymerization monomer containing such Lewis space, as described above. It is also possible to use a method in which the prepared premix is poured into the mold. In this case, it is advantageous to place a glass fiber mat or the like in the mold in advance to obtain a fiber-reinforced molded product.

Salts such as halides such as tungsten, rhenium, tantalum, and molybdenum are used as catalyst components in the metathesis polymerization catalyst system, and tungsten compounds are particularly preferred.Tungsten halides are particularly preferred as such tungsten compounds.

Tungsten oxyhalide is preferable, and more specifically, tungsten hexachloride, tungsten oxychloride, etc. are preferable, and organic ammonium tungstates or molybdates can also be used. Such tungsten compounds are known to immediately start cationic polymerization when added directly to monomers, which is undesirable. Therefore, such tungsten compounds are suspended in advance in an inert solvent such as benzene, toluene, or tetrabenzene, and mixed with a small amount of alcohol. It is preferable to use it by solubilizing it by adding a type compound or a phenol type compound.

Furthermore, in order to prevent undesirable polymerization as described above, it is preferable to add about 1 to 5 mol of a Lewis base or a chelating agent to 1 mol of the tungsten compound. Such additives include acetylacetone, alkyl acetoacetate, etc. As mentioned above, the polar monomer for copolymerization used in the present invention may include esters, tetrahydrofuran, benzonitrile, etc. In some cases, the polar monomer itself is a Lewis base, and the above-mentioned compounds are not particularly added. may also have this effect.

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

On the other hand, the activation inhibitor component in the metathesis polymerization catalyst system is preferably an organometallic compound mainly consisting of alkylated products of metals of Groups 1 to Ⅰ of the periodic table, particularly tetraalkyltin, alkylaluminum compounds, and alkylaluminum halide compounds. Specific examples include diethylaluminum chloride, ethylaluminum dichloride, trioctylaluminum, dioctylaluminum iodide, and tetrabutyltin. The other solution (corresponding to solution B) is formed by dissolving these organometallic compounds as activator components in the raw material monomers.

In the present invention, a crosslinked polymer molded product can basically be obtained by mixing the solution A and solution B, but if the above composition remains unchanged, the polymerization reaction will start very quickly, so the molding Hardening may occur before it has sufficiently flowed into the casting mold, which is often a problem, and for this reason it is preferable to use an activity modifier as described above.

As such regulators, Lewis bases are generally used, among which ethers, esters, nitriles, etc. are used. Specific examples include ethyl benzoate, butyl ether, diglyme, etc. Such regulators are generally added to the solution of the organometallic compound activator component. When a copolymerizable monomer having a Lewis space 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 a catalyst component, the ratio of the tungsten compound to the raw material monomer is about 1 on a molar basis.
000:1 to 15000:1, preferably 2000:1
In addition, when an alkyl aluminum is used as the activation inhibitor component, the ratio of the aluminum compound to the raw material monomer is about 100:1 to about 2 on a molar basis.
000 to 1, preferably about 200 to 1 to about 500
Further, the masking agent and regulating agent as described above, which are used in the vicinity of 1:1, can be appropriately adjusted and used depending on the amount of the catalyst system used through experiments.

In practical use, various additives may be added to the polymer molded product of the present invention in order to improve or maintain its properties. Such additives include fillers,
Content, antioxidants, light stabilizers.

These include flame retardants and polymer modifiers. Such additives cannot be added after the polymer of the present invention is formed, so if they are added, they must be added to the above-mentioned raw material solution in advance.

The easiest method is to use the solution A and the solution iB.
One method is to add it in advance to either or both of the above, but in that case, it does not react with the highly reactive catalyst component or deactivator component in the liquid to a practical extent, and It must be something that does not inhibit polymerization.For some reason, the reaction cannot be avoided, but if it does not substantially inhibit polymerization even if it coexists, mix it with the monomer and prepare the third liquid. However, they can also be mixed and used immediately before polymerization. In the case of a solid filler, in the case of a filler in a shape that can sufficiently fill the voids immediately before starting the polymerization reaction or during polymerization when both components are mixed, in the mold for forming the filler, It is also possible to fill it.

Additive reinforcements or fillers are effective in improving the flexural modulus. Examples of such materials include glass fiber, mica, carbon black, and wollastonite. Those surface-treated with a so-called silanga puller can also be suitably used.

Further, 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. As a specific example, 2.6-
t-Butyl-p-cresol, N,N'-diphenyl-
p-phenylenediamine, tetrakis[methylene (3,
Examples include 5-di-t-butyl-4-hydroxycinnamate) methane.

In the present invention, it is essential to use the above-mentioned specific elastomer, but in addition to that, other polymers can be added to the reaction solution and used by dissolving or suspending them, if necessary.

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

As described above, such molding methods include a method in which a premix in which a catalyst system and a monomer mixture are mixed in advance is flowed into a mold, and a method in which the catalyst system is divided into two parts, solution A and solution B, and mixed by collision in the head section. RI, which is poured directly into the mold.
M method can be used. In either case (the injection pressure into the J mold (mold) can be relatively low pressure,
Therefore, it is possible to use inexpensive molds.

Further, when the polymerization reaction inside the mold starts, the temperature inside the mold rapidly rises due to the reaction heat, and the polymerization reaction ends in a short time. Unlike the case of polyurethane-RIM, it is easy to release from the mold and often does not require a special mold release agent.

The molded product has good adhesion to commonly used paints such as epoxy and polyurethane due to the formation of an oxidized layer on the surface.

The molded product thus obtained has improved heat resistance compared to conventional products, and can be used in various vehicles including automobiles.
It can be used in a wide range of applications, including large molded items such as equipment parts and housings for electrical and electronic equipment.

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

Examples 1-21. Comparative Examples 1 to 21 (+) Catalyst Source wI Liquid Preparation 19.8 bg (50 mol) of tungsten hexachloride was dehydrated in toluene under a nitrogen stream to 90% of the total amount. Disperse within; into it;
A solution of 0.925 kg (12.5 moles) of t-butanol in 51 dehydrated toluene was added and stirred for 3 hours under a nitrogen stream. A solution of 11.05 kF (5σ mol) of nonylphenol dissolved in 51 dehydrated toluene was further added to the mixture and stirred for 3 hours. 10 kg (100 mol) of acetylacetone was added dropwise into the mixture, and stirring was continued day and night. Hydrogen chloride generated during this process is taken out of the system together with nitrogen, neutralized with an aqueous solution of caustic soda, and disposed of.

Therefore, some of the toluene that had been reduced was replenished to reduce the amount to 0.
A 5M tungsten catalyst concentrate was prepared.

(6) activator e4 condensate preparation 5.7 kg of di-n-octylaluminum idide;
13.42 kr tree n-octyl aluminum and 1
3.42 kg of a mixture of diglyme with a total weight of 1001
Add purified dicyclopentadiene so that 1.
A 0M aluminum activated concentrate was prepared.

(g) Preparation of reactive solution (A) Metathesis polymerizable monomer solution 964 having a predetermined composition in which a predetermined amount of a commercially available elastomer with a definite composition is dissolved.
．． 6 parts and 15.4 parts of catalyst concentrate, E as an oxidation stabilizer.
20 parts of thanox 702 (manufactured by Ethyl Corporation) were mixed under a nitrogen stream to prepare a reactive solution (^) of 30 parts each.

(f) Preparation of reactive solution CB) Metathesis polymerizable monomer solution 978 having a predetermined composition in which a predetermined amount of a commercially available elastomer with a definite composition is dissolved.
．． 5 parts of the activator and 21.5 parts of the concentrated aqueous activator were mixed under a nitrogen stream to prepare 30 kg of each reactive solution (B).

Monomer reducers are used in reactive solutions (unless otherwise specified).
A predetermined amount was added to A) and used for molding.

(v) Preparation of polymer molded product Using a lance-type reaction injection molding machine manufactured by Niigata Tekkoros, a mixing pressure of 60 kr/(J) Reactive solutions A and B were injected in equal amounts at a total injection rate of approximately 400 g/sec. , 50CIIIX 50C
The mixture was filled into a flat plate mold having a cavity of 1 11 × 3 tsv+ and whose mold surface was kept at 70 to 90°C, and was reacted and cured to obtain a resin molded product about 3 cm thick.

Using this plate-shaped molded product, a notched isot was formed at a load of 18.5 bl (heat distortion temperature CHD'r' under /■) and a secondary dislocation point (Tg) of DMA at room temperature to low temperature.

The molded product was extracted with flexural modulus, flexural modulus, and toluene, and the residual monomer on the extraction back was quantified by gas chromatography.
In order to clarify the effect of addition of I), a comparison was made with comparative examples.

In Table 1, the composition of each type of elastomer used in Examples and Comparative Examples and the concentration of the elastomer in the monomer solution in which the elastomer was dissolved used to prepare the reactive solution are also listed.

Table 2 shows the amount of monomer reducing agent added and the composition of the monomer, as well as the performance of the molded product. In addition, both reactive solutions A and B used here have a viscosity of 3 when measured at 30°C.
It was in the range of 00 to 400 cps.

In the case of unsaturated rubbers such as SBR and BR, the residual monomer is reduced by adding a residual monomer reducing agent, but the resin molding becomes brittle and the impact strength is significantly impaired, especially at low temperatures.

(Comparative Examples 1 to 5.7 to 10) Furthermore, when an appropriate amount of residual monomer reducing agent was added, HD TJ? ? Although Tg is improved (Comparative Example 2゜3),
It can be seen that as the amount of residual monomer reducing agent added increases, it also decreases significantly. (Comparative Example 4゜In contrast, in the case of the combination of the saturated rubber and monomer reducing agent of the present invention, in addition to reducing residual monomer (generally 1% or less), impact resistance is not affected even at room temperature to low temperature. and generally H
It can be seen that both DT and TO have improved.

In addition, even when a large amount of residual monomer reducing agent is added, there is no significant decrease in HDT or Tg as in the case of unsaturated rubber, and the impact resistance is rather improved at around room temperature, and the residual monomer reducing agent is good. It can be seen that it acts like a strong plasticizer. Furthermore, the saturated rubber used in the present invention generally has improved HDT and TO compared to unsaturated rubber even when the same monomers are used, and this can be improved by using a residual monomer reducing agent. It can be seen that the impact resistance is further improved without sacrificing it.

That is, it can be seen that the combination of the saturated rubber of the present invention and the residual monomer reducing agent achieves improvements in three important issues: improvement in heat resistance, improvement in impact resistance, and reduction in depth due to reduction in residual monomer.

Claims (9)

[Claims] (1) In a polymer molded product obtained by simultaneously polymerizing and molding a metathesis polymerizable monomer in the coexistence of a metathesis polymerization catalyst system, carbon- A soluble elastomer (I) in which repeating units having a carbon double bond account for 10 mol% or less of all repeating units, and one in a valence state lower than the highest valence of the transition metal element in the metathesis polymerization catalyst system. and a compound (II) which can be reduced to form radicals by redox reaction. (2) The polymer molded product 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 terpolymer rubber. (3) The compound (II) is w,w'-dichlorodiphenylmethane, w,w,w',w'-tetrachloro-1,4-
Claim 1: The compound is at least one compound selected from the group consisting of dibenzylbenzene, m-bis(trichloromethyl)benzene, p-bis(trichloromethyl)benzene, isophthalic acid chloride, phosphorus oxychloride, and benzenesulfonic acid chloride. Polymerized molded product as described. (4) In a method for producing a polymer molded product in which a metathesis polymerizable monomer is simultaneously polymerized and molded in the coexistence of a metathesis polymerization catalyst system, carbon- A soluble elastomer (I) in which repeating units having a carbon double bond account for 10 mol% or less of all repeating units, and one in a valence state lower than the highest valence of the transition metal element in the metathesis polymerization catalyst system. 1. A method for producing a polymer molded article, which comprises adding at least one of each of compound (II) which can be reduced to form a radical by an oxidation-reduction reaction. (5) The manufacturing method according to claim 4, wherein the elastomer (I) is at least one elastomer selected from the group consisting of ethylene-propylene rubber and ethylene-propylene diene terpolymer rubber. (6) The compound (II) is w,w'-dichlorodiphenylmethane, w,w,w',w'-tetrachloro-1,4-
Claim 4: The compound is at least one compound selected from the group consisting of dibenzylbenzene, m-bis(trichloromethyl)benzene, p-bis(trichloromethyl)benzene, isophthalic acid chloride, phosphorus oxychloride, and benzenesulfonic acid chloride. Manufacturing method described. (7) a) a reactive solution of metathesis polymerizable monomers containing the catalyst component of the metathesis polymerization catalyst system (solution A); and b) a reactive solution of metathesis polymerizable monomers containing the activating component of the metathesis polymerization catalyst system (solution B). ) In a combination of reactive solutions consisting of at least one of these solutions A and B, at least one of these solutions A and B contains all repeating units that are mainly composed of hydrocarbons and that have carbon-carbon double bonds contained in the main chain and side chains. 10 in repeat unit
A soluble elastomer (I) with a mol% or less and a compound (I) that can be reduced by a redox reaction to form a radical with a valence state lower than the highest valence of the transition metal element in the metathesis polymerization catalyst system. A combination of reactive solutions containing at least one of each of II). (8) The reactive solution combination according to claim 7, wherein the elastomer (I) is at least one elastomer selected from the group consisting of ethylene-propylene rubber and ethylene-propylene diene terpolymer rubber. (9) The compound (II) is w,w'-dichlorodiphenylmethane, w,w,w',w'-tetrachloro-1,4-
Claim 7: The compound is at least one compound selected from the group consisting of dibenzylbenzene, m-bis(trichloromethyl)benzene, p-bis(trichloromethyl)benzene, isophthalic acid chloride, phosphorus oxychloride, and benzenesulfonic acid chloride. Combination of reactive solutions as described.