JPH01304115A - Molded item of crosslinked polymer, preparation thereof and combination of reactive solutions - Google Patents

Abstract

PURPOSE:To improve heat resistance and impact resistance by performing simultaneously polymn. and molding of a metathesis polymerizable monomer in the presence of a specified soluble polymer and a catalytic system. CONSTITUTION:Polymn. and molding of a metathesis-polymerizable monomer (A) are simultaneously performed by incorporating a soluble polymer (D) which contains norbornene structural units, is substantially free from any group inhibiting a metathesis polymn. catalyst system (B) and is obtd. by introducing at least partly a functional compd. having both one or more norbornene structures and one or more other functional groups into the polymer structural units based on the action of the functional group, in at least one of the soln. in the combination (C) of the reactive soln. consisting of a reactive soln. (a) of the component A contg. a catalytic component of the metathesis polymn. catalyst system (B) consisting of the catalytic component and a component of an activating agent and a reactive soln. (b) of the component A contg. the component of the activating agent of the component B.

Description

Detailed description of the invention a. Industrial application field The present invention relates to a polymer molded product obtained by bulk polymerizing a metathesis polymerizable monomer in a mold in the presence of a metathesis polymerization catalyst system and molding simultaneously with polymerization. It is about improving things.

More specifically, a method for producing a polymer molded product with improved heat resistance and, in some cases, simultaneously improved impact resistance, by adding a soluble polymer having a norbornene structural unit as a metathesis polymerization reactive component, and a method for obtaining the same. It concerns the combination of reactive solutions for.

b. Prior art cyclic olefin is ring-opened by a metathesis polymerization catalyst,
It is well known to provide polymers.

Therefore, a method has been proposed in which a metathesis-polymerizable monomer, which can be obtained at low cost, such as dicyclopentadiene, is poured into a mold in a liquid state, and bulk polymerization is carried out within the mold, thereby obtaining polymerization and molding in one step. (See, for example, Japanese Patent Laid-Open No. 129013/1983) According to this method, a large molded product can be obtained using an inexpensive mold, so it has the possibility of being used in a wide range of applications.

However, there are many applications in which such large molded products require good heat resistance and impact resistance. However, as mentioned above, when dicyclopentadiene, which is the cheapest available, is used alone as a monomer for such polymer moldings, the required heat resistance and impact resistance are often insufficient. In order to improve heat resistance, copolymerizing monomers with higher crosslink density or monomers with rigid bonds has a great effect on increasing the softening point, but on the other hand, impact resistance decreases more. There are many cases where you will have to do so.

On the other hand, as methods for improving impact resistance, a method of forming a polymer molded product in the coexistence of an elastomer and a method of adding a plasticizer have been proposed. However, the method of adding a plasticizer not only significantly lowers the softening point due to its plasticizing action, but also has the problem of blooming during long-term use, and is therefore not considered to be a sufficient method. On the other hand, the method of adding an elastomer can be said to be an effective method because by selecting an appropriate elastomer, a small amount of addition can have a large effect on improving impact resistance. However, the addition of such an elastomer generally tends to lower the above-mentioned heat resistance in terms of thermal deformability.

Therefore, the present inventors believe that if it is possible to introduce a norbornene group having good metathesis polymerizability into a polymer such as an elastomer added to a polymer molded product by such metathesis polymerization, the main component of the added polymer will be This study focused on the possibility of obtaining a polymer molded product with a good balance of heat resistance and impact resistance by involving the crosslinking reaction without chain scission.

Furthermore, as a method for introducing metathesis-polymerizable norbornene groups, a functional compound having at least one norbornene group and at least one functional group that can be used as a polymer constituent unit is used as at least a part of the raw materials for producing the polymer. As a result, they were able to obtain a soluble polymer having norbornene structural units and use it for this purpose.

Structure of C0 invention That is, the present invention includes the following inventions.

(1) In a crosslinked polymer molded product obtained by simultaneously polymerizing and molding a metathesis polymerizable monomer in the coexistence of a metathesis polymerization catalyst system, functionality having at least one norbornene structural unit and at least one other functional group A soluble compound containing a norbornene structural unit and substantially free of groups that inhibit metathesis polymerization catalysts, obtained by introducing the compound (a) into at least a part of the polymer structural units through its functional group. A crosslinked polymer molded product, characterized in that a polymer (0) is added to the metathesis polymerizable monomer.

(2) A method for producing a crosslinked polymer molded product in which a metathesis-polymerizable monomer is simultaneously polymerized and molded in the coexistence of a metathesis-polymerization catalyst system, wherein the functionality has at least one norbornene structural unit and at least one other functional group. A soluble polymer containing a norbornene structural unit and substantially free of groups that inhibit a metathesis polymerization catalyst, obtained by introducing the compound (a) into at least a part of the polymerization structural units through its functional group. A method for producing a crosslinked polymer molded article, characterized in that (○) is added to the metathesis polymerizable monomer.

(3) a) a reactive solution of a metathesis polymerizable monomer containing a catalyst component of a metathesis polymerization catalyst system (solution A); and b) a reactive solution of a metathesis polymerizable monomer containing an activator component of a metathesis polymerization catalyst system (solution B) In a combination of reactive solutions consisting of at least one of the following, at least one of the solutions contains a functional compound (a) having at least one norbornene structural unit and at least one other functional group, which forms a polymer structure using the functional group. Adding to the metathesis polymerizable monomer a soluble polymer (0) containing the obtained norbornene structural unit and substantially free of groups that inhibit the metathesis polymerization catalyst by introducing it into at least a portion of the units. A combination of reactive solutions characterized by:

The soluble polymer <01 having a norbornene structural unit used in the present invention needs to be substantially free of functional groups that inhibit metathesis polymerization.

Therefore, those having a functional group having such inhibitory properties in their repeating units should not be used.

Such inhibitory functional groups generally include those having active hydrogen and those having strong basicity, such as hydroxyl groups, carboxyl groups, aldehyde groups, aliphatic ketone groups,
Examples include primary to tertiary amine groups and amide groups.

Weakly polar groups that do not have active hydrogen, such as ester groups,
An ether group, an N-substituted imide group, a cyano group, etc. can be used because they delay the initiation and progress of metathesis polymerization but do not substantially inhibit it.

As mentioned above, such a polymer (○) can be obtained by introducing a functional compound (a) having at least one norbornene structural unit and at least one other functional group into the polymerized structural unit through its functional group. I can do it.

The functional groups of such functional compound (a) can be classified as follows. That is, (A) it has two functional groups capable of forming a main chain by polycondensation or polyaddition reaction, and can thereby be introduced into the main chain of soluble polymer (01).

(B) has one polymerizable unsaturated bond such as a vinyl group or vinylene group or a cyclic group having ring-opening polymerizability;
Thereby, it can be introduced into the main chain of the soluble polymer (○).

(C) Contains one functional group that can be introduced into the side chain of the soluble polymer that has already been formed by a condensation reaction or addition reaction, and is thereby introduced into the side chain of the soluble polymer (0). can.

Phase (A) Generally, a heteroatom is involved in the polycondensation/polyaddition reaction. Therefore, it becomes a polymer containing a non-inhibitory polar group in its main chain. As mentioned above, examples of such polar groups include eight groups such as ester, ether, and N-substituted imide, and examples of such polymers include polyester, polyether, polyimide, etc. having a norbornene structure. However, polyester and polyether are particularly preferred.

Such a polyester can be obtained by using a dicarboxylic acid having a norbornene structure or a functional derivative thereof and/or a dihydric compound having a norbornene structural unit or a functional derivative thereof as at least a part of the monomers.

Suitable examples of such dicarboxylic acids include functional derivatives of nadic acids, which are adducts of maleic acids and cyclopentadiene. Also,
As a dihydric compound, norbornene-5,6-
Suitable examples include simethanol and the like.

In the case of polyether, it is generally obtained by reacting a bishalogen compound and a dihydric compound, which are as activated as possible, in the coexistence of a dehydrohalogenating agent. A material containing a norbornene structural unit in part can be used. Examples of such bishalogen compounds include 5,6-cyclomethylnorbornene.

Among the polyesters and polyethers mentioned above, polyesters made from nadic acid derivatives and common glycols such as diethylene glycol and neopentyl glycol are most preferred.

Nadic acids are commercially produced and easily available, and various types of glycols are also industrially produced, and an appropriate one can be selected depending on the required properties.

Such polyesters and polyethers as mentioned above.

Polymers such as polyimide often have groups at their terminals that inhibit metathesis polymerization reactions, such as carboxylic acid or alcohol groups, so care must be taken to avoid this as much as possible.

In the case of (B), it is necessary to select a functional group in which the norbornene structural unit can be polymerized under conditions that do not involve polymerization.

It is known that norbornene structural units are susceptible to cationic polymerization and may also be involved in radical polymerization to some extent. Therefore, it is generally preferable to use an anionic polymerization to polymerize only the functional groups and leave the norbornene structural units as they are in the i-chain. From this point of view, the polymerizable functional group is preferably one that is easily anionically polymerized, and examples of such monomers include 5-acryloxymethylnorbornene 5-methacryloxymethylnorbornene C-C-0-C
H2-c)-(ii) 5-(styryl)norbornene N-(5-norbornenyl)methylmaleimide 5-norbornenyl glycidyl ether, etc. can be used. A polymer corresponding to (B) can be obtained by using such a monomer alone or by copolymerizing it with other monomers having similar polymerizability. In particular, monomers (il to (iiil) are preferred.

In the case of (C), a norbornene structural unit is introduced into the side chain by reacting the functional group of the side chain of the soluble polymer with (a).

The soluble polymer used for this purpose is preferably an elastomer having a functional group or a relatively soft plastic, such as polyvinyl acetate, polyacrylic acid ester, polymethacrylic acid ester, polyethylene-vinyl acetate copolymer, polyethylene-vinyl acetate, etc. Examples include acid ester copolymers, polychloromethylstyrene, polychloromethylstyrene-butadiene copolymers, polyepichlorohydrin, polyethylene oxide-epichlorohydrin copolymers, and the like.

For polyvinyl esters (including copolymers), 5
It is preferred to introduce a norbornene ring through the ester group by reacting a norbornene ring-containing carboxylic acid ester such as -methoxycarbonylnorbornene.

In the case of polyacrylate or polymethacrylate (including copolymerization), on the contrary, it is preferable to use an ester of a norbornene ring-containing alcohol such as 5-7cetoxymethylnorbornene to introduce a norbornene ring through the ester group.

In addition, in the case of polyepichlorohydrin and polychloromethylstyrene, 5-methylolnorbornene, 5-(p
It is common to introduce a norbornene ring through an ether bond by reaction with a norbornene-containing monohydric compound such as -hydroxyphenyl)norbornene.

In the above examples, other types of polyvinyl acetate and polyacrylate are available at low cost, including copolymers with ethylene, and the soluble polymer (0) is formed by reaction with their side chains. The most preferred method is to obtain

Among (A) to (C), (C) is a commercially available polymer,
By a simple reaction, the soluble polymer (0
), which is the most preferable. On the other hand, in A) and (8), it is necessary to perform a polymerization reaction to obtain the soluble polymer (0), which may be expensive, but the introduction of the norbornene structure can be controlled at a certain level. That's easy.

Such soluble polymer (0) does not necessarily have to be a high polymer, and an oligomer may be sufficient, and in general, one with an average molecular weight of 500 or more, preferably iooo or more may be selected according to its effect. It turns out.

The content of norbornene structures in such a soluble polymer is preferably 2 or more on average, more preferably 3 or more in one molecule.

In addition, the ratio of the norbornene structure in the repeating unit of soluble polymer (01) satisfies the above-mentioned preferred range of content, and the proportion of the norbornene structure in the repeating unit of soluble polymer (01 is at least 1 mol % or more in the repeating unit of 4, generally 2 to 100%). A mole %, particularly a range of 3.0 to 50 mole % is preferably used.

Further, the proportion of the soluble polymer (0) to be used in the polymer can be determined depending on its effect and viscosity.

That is, in order to obtain the crosslinked polymer of the present invention, the suitable viscosity of the reactive solution is determined by the molding method. The soluble polymer (0) is a polymer, and its dissolution affects the viscosity of the reactive solution.

Therefore, if the molecule 4 of the soluble polymer (0) is large, the viscosity will increase, and the amount used may be restricted in order to balance processability.

On the other hand, if a sufficient amount of soluble polymer (0) is added in terms of its effectiveness, but the viscosity does not reach the desired processability, another elastomer or the like may be added and dissolved as described below. Norbornene-containing soluble polymer (the amount of 01 to be used based on the total metathesis-polymerizable polymer is selected as described above, but generally 1 to 6
A range of 0% by weight, more preferably 2 to 40% by weight, and most preferably 3 to 30% by weight is used.

It is not necessarily necessary to add the soluble polymer (0) to solutions A and B at the same concentration, but in consideration of the effects of polar groups contained in the soluble polymer (0), it is necessary to add more to one solution. Alternatively, it is possible to add it to only one side.

The metathesis-polymerizable monomer used to form a molded product together with such soluble polymer (01) can be bulk polymerized by metathesis polymerization to give a molded product.
Any type of cycloalkene group may be used as long as the cycloalkene group has 1 to 4 metathesis-polymerizable cycloalkene groups.

Particularly preferred are those having norbornene type bonds. Hydrocarbons are particularly preferred; specific examples include dicyclopentadiene, dihydrodicyclopentadiene, Schiff convex pentadiene-methylcyclopentadiene codimer, 5-ethylidenenorbornene, 5-vinylnorhornene. , norbornene, 5-cyclohexenylnorbornene, 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-methyl-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]]tridecar5.11-
Diennorbornadiene, 5-phenylnorbornene,
Examples include ethylene bis(5-norbornene). Especially dicyclopentadiene or 50% of it
% 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. Such a metathesis polymerizable monomer preferably has a norbornene structural unit, and as a polar group,
Ester groups, ether groups, cyano groups, N-substituted imide groups, etc. are preferred.

Such polar groups have the function of regulating the initiation of metathesis polymerization reaction as Lewis space, and also have the effect of introducing polar groups into the produced polymer molded product. ) may have the effect of increasing its solubility depending on the type, so it is suitably used depending on the necessity of its action.

As such a polar additive, (5-norbornenyl)
Methyl-phenyl ether, bis[(-norbornenyl)methyl]ether, 5-methoxycarbonylnorbornenyl-5-methyl-norbornene, 5[(2-ethylhexyloxy)carbonylethylene-bis(5-norbornenecarboxylate)
, 5-cyanonorbornene, 6-diatu 1, 4, 5.
8-dimethano-1, 4. 4a, 5, 6, 7
, 8. Examples include 8a-octahydronaphthalene, N-butylnadic acid imide, and 5-(4-pyridyl)-norbornene.

Furthermore, halogen-containing metathesis polymerizable monomers can also be used to improve flame retardancy and 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 contain as small a content m of impurities that inhibit the metathesis-polymerization catalyst.

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 generally an exothermic reaction, and once the polymerization starts, the system is heated roughly 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 activator components (solution B), and collisional mixing (RIM method) was carried out. ) or a static mixer, the mixture is immediately poured into a mold, shaped, and then hardened in the mold. In that case, the composition of the monomers does not need to be the same in both liquids, and can be arbitrarily changed depending on the function of the monomers. Although the amount of liquid rubber added can be varied depending on the two liquids, it is generally preferable in the reaction injection molding method that the two liquids have the same viscosity because mixing can be performed more effectively.

Another method for obtaining a polymer molded product is to delay the initiation of polymerization by adding Lewis space that acts as a regulator to delay the initiation of metathesis polymerization, or a metathesis polymerizable monomer having such Lewis space, as described above. A method of flowing the generated premix into a mold, ie, a resin injection method can also be used. In this case, it is advantageous to prepare a fiber-reinforced molded product by placing a glass fiber mat or the like in the mold in advance.

In the RIM method, such a glass Qlillt mat can also be used in the mold.

As the catalyst component in the metathesis polymerization catalyst system, salts such as halides such as tungsten, rhenium, tantalum, and molybdenum are used, and tungsten and molybdenum are preferred, with tungsten compounds being particularly preferred. As such a tungsten compound, tungsten halide, tungsten oxyhalide, etc. are preferable, and more specifically, tungsten hexachloride, tungsten oxychloride, etc. are preferable. Furthermore, organic ammonium tungstate and the like can also be used.

Such tungsten halide compounds can be directly applied to
It is known that if it is added to water, cationic polymerization will immediately start, which is not preferable. Therefore, such tungsten halide compounds can be used in inert solvents such as benzene, toluene,
It is preferable to use it after solubilizing it by pre-suspending it in chlorobenzene or the like and adding a small amount of an alcoholic compound or a phenolic compound.

Generally speaking, it is preferable to add about 1 to 5 moles of Lewis base or chelating agent to 1 mole of the tungsten compound in order to prevent undesirable polymerization as described above. Examples of such additives include acetylacetone, acetoacetic acid alkyl esters, tetrahydrofuran, and benzonitrile. The copolymerization compound used in the present invention may itself be a Lewis base as described above, and may have its effect even without the addition of any of the above-mentioned compounds.

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

On the other hand, the activator component in the metathesis polymerization catalyst system is an organometallic compound mainly consisting of alkylated products of metals of Groups I to II of the Periodic Table, particularly tetraalkyltin, trialkylhydrogentin, and triallylhydrogentin.

Alkylaluminum compounds and alkylaluminium halide compounds are preferred, and specifically, salt or diethylaluminum, di-salt or ethylaluminum, trioctylaluminum, dioctylaluminum iodide,
Tetrabutyltin, tributylhydrogentin, etc. can be mentioned. These organometallic compounds as activator components,
The other solution (corresponding to solution B) is formed by dissolving it in the raw material monomer.

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, and diglyme. 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 activator component, the ratio of the aluminum compound to the raw material monomer is about 100:1 to about 2 on a molar basis.
000:1, preferably around 200:1 to about 500:1.

The masking agent and regulator, as briefly described above, can be appropriately adjusted through experiments depending on the amount of the catalyst system used.

In practical use, various additives can be added to the crosslinked polymer molded product of the present invention in order to improve or maintain its properties. Such additives include fillers, pigments, antioxidants, light stabilizers, flame retardants, polymer modifiers, residual snail reducers, and the like. Such additives cannot be added after the crosslinked 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 add it to either or both of solution A and solution B in advance, but in that case, the highly reactive catalyst component in the solution or the It must not react with the ingredients of the agent to a practical extent and must not interfere with the procedure. Although this reaction cannot be avoided, even if they coexist,
If it does not substantially inhibit polymerization, it can be mixed with a monomer to prepare a third liquid and used in combination immediately before polymerization. In the case of a solid filler, if the filler is 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.

Reinforcements or fillers as additives are effective in improving the flexural modulus. Such materials include glass fiber, mica, and carbon black.

Wolastonite etc. can be given. these,
Those that have been surface-treated with a so-called silanga puller or the like 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. 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 etc. are required.

The polymer molded product of the present invention is characterized in that by adding solubilized polymer containing norbornene structure (01), norbornene groups participate in metathesis polymerization and moderately increase crosslinking, thereby improving heat resistance. .moreover,
When such a soluble polymer (0) consists of a flexible main chain, it may necessarily contribute to improving the flexibility of the crosslinked polymer and its impact resistance, but it is difficult to efficiently improve both heat resistance and impact resistance. It is often difficult to improve the flexibility with just the soluble polymer (0), and ordinary elastomers also contain an appropriate amount, generally 15% by weight or less, and generally 8% by weight, for the purpose of improving flexibility. The following can be used in combination. Examples of 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, etc. can be used.

In addition, in the present invention, if there is a large amount of residual top jam in the molded product, not only the softening point will be lowered but also a characteristic odor may be emitted, so it is preferable that the residual top jam is as small as possible. As additives for reducing such residual monomers, α, α, α-trichlorotoluene, ω, ω-
Dichlorodiphenylmethane, phthalic acid chloride, benzoic anhydride, pengansulfonic acid chloride.

Very small amounts of halides and acid anhydrides such as phosphorus oxychloride can be added.

The crosslinked 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 the resin injection method in which the catalyst system and the seven-mer mixture are mixed in advance and a premix is flowed into the mold, and the catalyst system is divided into two parts, solution A and solution B, into the head. It is possible to use the RIM method, in which the mixture is mixed by collision at a stage and then poured directly into a mold.

In either case, the injection pressure into the mold can be relatively low, making it 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 polyurethane-RIMs, they are easy to release from the mold and often do not require special mold release agents.

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 products obtained in this way have particularly improved heat resistance compared to conventional products, and are suitable for use in large molded products such as parts for various transportation equipment, including automobiles, and housings for electrical and electronic devices. It can be used for a wide range of purposes.

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 1-3. Comparative Example 1 [Preparation 1 of Soluble Polymer (B)] - Preparation by method (B) Die of allyl alcohol and cyclopentadiene
5-(Hydroxymethyl)norbornene was produced by Is-Al der reaction, and 5-(methacryoxymethyl)norbornene [MNN] was obtained by reacting it with methacryloyl chloride.

A solution consisting of 60 parts by weight of thoroughly purified MNN and 300 parts of dry toluene was added in an amount of 1.64 mol/j! under a nitrogen atmosphere. After adding 10 parts by weight of a hexane solution of butyllithium and carrying out a polymerization reaction for 24 hours at a bath temperature of 75°C, methanol was added to inactivate the anion terminal, and the solution was further poured into methanol to produce Soluble polymer (01-A' (poly[
(5-norbornenyl)methyl methacrylate] was rewashed and recovered twice. The ηing of this soluble polymer (0)-A' in a 0.2M 100 dl' luene solution was 0.46 dl/g.

Next, a soluble polymer (01-8' (poly[( A poly(5-norbornenyl) methyl methacrylate copolymer was obtained. ηinh under the same measurement conditions was 0.
．． It was 48 dl/g.

[Preparation of main catalyst concentrate] 19.80 g (0.05 mol) of high-purity tungsten hexachloride was added to dry toluene 9 (7) under a nitrogen stream, and t-
Add butanol 0.925 (l) dissolved in toluene and stir for 1 hour, then nonylphenol 11
．． 05g (0.05 mol) and toluene 5Inf! Add the solution and stir for 1 hour under a nitrogen purge. 1°Q of acedelacetone was added to the mixture, stirring was continued overnight under a nitrogen purge while purging by-product hydrogen chloride gas, and then some of the toluene distilled out was supplemented to form a 0.58 tungsten-containing ts concentrate. adjusted.

[Preparation of active inhibitor concentrate] D-n-octyl aluminum iodide 5°70g
, tri-n-octylaluminium, 31.17 g.

Diglyme 13.420 was mixed under a nitrogen stream, then dicyclopentadiene (DCP>) was added to give a total of 100
1n1. The mixture was diluted to give 1.0)1 aluminum-containing activator concentrate.

[Preparation of reactive solution] Purified DCP obtained by distilling and purifying commercially available dicyclopentadiene (DCP>) and the soluble polymer (0) prepared as above.
And, the main touch! Reactive solutions A and B were prepared by using the X concentrated solution and the activator concentrated solution as shown in Table 1.

[Preparation of cross-linked polymer and measurement of its properties] After heating 10 ml of the above catalyst component solution (solution A>10rd!) and activator component solution (solution B) to the specified temperature, place each in a syringe that has been sufficiently replaced with nitrogen. The liquids were simultaneously extruded from the two syringes at a constant rate into a glass flask equipped with a stirrer under rapid stirring, and after rapid mixing, the stirring chamber was raised and a thermocouple was inserted. The time it took for the temperature to reach 100°C was measured.

Roughly, the solidified crosslinked resin was taken out, a section was cut out, and the softening point was measured in a nitrogen stream in TMA needle penetration mode. The results are also listed in Table 1.

It can be seen that the softening point of the crosslinked polymer is greatly improved by adding a small amount of soluble polymer (0)-A' and B'.

Examples 4-11. Comparative Examples 2 to 6 [Preparation 2 of Soluble Polymer (0)] - Preparation by (C) Method (1) Commercially available ethylene vinyl acetate copolymers (C to F) were dissolved in toluene, and 5-(methoxycarbonyl ) with addition of norbornene and t-butylthianate as a catalyst.
A soluble polymer (0
) (C'-E') were prepared.

In addition, commercially available ethylene-acrylic copolymers (F to G) were dissolved in toluene, and 5-(acetoxymethyl)norbornene and t-butylthianate were added as a catalyst.
A soluble polymer (01(F
'~G') were prepared.

The properties and trade name of C-G used are shown in Table 2, and the preparation conditions and transesterification ratios of soluble polymers (0) C' to G'' are shown in Table 3.

The rate of transesterification was calculated from the ratio of the integral value of the olefin hydrogen in the norbornene skeleton and the hydrogen at the α-position of the ester using nuclear magnetic resonance method.

Reactive solutions A and B8 were prepared in the same manner as in Examples 1 to 3 except that the soluble polymers (01-C' to G') produced in this way were used, and a crosslinked polymer was obtained from this, and the ioo'
The time taken to reach c was measured, and the softening temperature of the resulting crosslinked polymer was measured and summarized in Table 4. As a comparative example, we decided to compare the cases in which the same amount of soluble polymer before introduction of norbornene groups was added.

Depending on the soluble polymer, as shown in Comparative Example 1, the polymerizability may decrease at the same tungsten/aluminum ratio as when no polymer is added, so the ratio may be changed to increase ioo'c. Adjust the tungsten/aluminum ratio by keeping the tungsten concentration constant and changing the aluminum concentration so that the arrival time is the shortest, and in that case, record the arrival time and aluminum concentration, and the softening temperature of the resulting polymer. were measured and compared.

The thermal softening point of each sample is improved compared to the corresponding comparative example in which the same amount of soluble polymer before norbornene group introduction was added. In particular, even if the introduction of norbornene groups is small, about 3 mol% of the total repeating units of the soluble polymer, the temperature is 5°C.
This shows that the introduction of the norbornene group has a great effect.

Claims (3)

[Claims] (1) In a crosslinked polymer molded product obtained by simultaneously polymerizing and molding a metathesis polymerizable monomer in the coexistence of a metathesis polymerization catalyst system, functionality having at least one norbornene structural unit and at least one other functional group A soluble compound containing a norbornene structural unit and substantially free of groups that inhibit metathesis polymerization catalysts, obtained by introducing the compound (a) into at least a part of the polymer structural units through its functional group. A crosslinked polymer molded product, characterized in that a polymer (b) is added to the metathesis polymerizable monomer. (2) A method for producing a crosslinked polymer molded product in which a metathesis-polymerizable monomer is simultaneously polymerized and molded in the coexistence of a metathesis-polymerization catalyst system, wherein the functionality has at least one norbornene structural unit and at least one other functional group. A soluble polymer containing a norbornene structural unit and substantially free of groups that inhibit a metathesis polymerization catalyst, obtained by introducing the compound (a) into at least a part of the polymerization structural units through its functional group. A method for producing a crosslinked polymer molded article, characterized in that (b) is added to the metathesis polymerizable monomer. (3) a) a reactive solution of a metathesis polymerizable monomer containing a catalyst component of a metathesis polymerization catalyst system (solution A); and b) a reactive solution of a metathesis polymerizable monomer containing an activator component of a metathesis polymerization catalyst system (solution B) In a combination of reactive solutions consisting of at least one of the following, at least one of the solutions contains a functional compound (a) having at least one norbornene structural unit and at least one other functional group, which forms a polymer structure using the functional group. Adding a soluble polymer (b) containing the obtained norbornene structural unit and substantially free of groups that inhibit the metathesis polymerization catalyst to the metathesis polymerizable monomer by introducing it into at least a part of the units. A combination of reactive solutions characterized by: