JPH01306418A - Crosslinked polymer moldings, production thereof and combination of reactive solutions - Google Patents

Abstract

PURPOSE:To obtain the subject moldings with well-balanced rigidity, impact resistance, etc., composed of a crosslinked polymer containing a rubber component as a block unit by blending a specified lower polymer having metathesis- polymerizable groups at the ends and carrying out simultaneous polymerization and molding. CONSTITUTION:(A) A lower polymer with 350-10000 number-average molecular weight having a main chain containing an aliphatic acyclic hydrocarbon unit or an ester linkage, etc., is prepared by reacting (i) a telechelic liquid rubber such as an oligoethylene glycol dimethacrylate with (ii) a metathesis- polymerizable monomer having a functional group reactive with the ends of (i). The resultant lower polymer is blended with (B) a metathesis-polymerizable monomer (e.g., dicyclopentadiene) preferably in an amount of 1-60wt.% based on the monomer (B) and (C) a metathesis-polymerization catalyst-based substance (e.g., tungsten hexachloride) is added thereto. The obtained mixture is poured into a mold and polymerized, thus obtaining the objective moldings.

Description

Detailed Description of the Invention a. Industrial Field of Application The present invention relates to bulk polymerization of a meta-cis polymerizable monomer in a mold in the coexistence of a metathesis polymerization catalyst system, and a polymer obtained by molding at the same time as the polymerization. This invention relates to the improvement of composite molded products.

More specifically, a method for producing a polymer molded product with improved impact resistance by adding a soluble low polymer having a metathesis polymerizable group at the end and consisting of flexible chains as a metasense 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 was proposed in which a meta-cis-polymerizable monomer, such as dicyclopentadiene, which can be obtained at low cost, is poured into a mold in its 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.

For these molded products, it is necessary to adapt the balance between stiffness and impact resistance, represented by bending modulus, over a wide range depending on the intended use.

In order to increase the rigidity as a method for adjusting this balance, a method has been proposed in which monomers having more rigid and larger residues or monomers having a higher crosslink density are copolymerized. In this case, the heat distortion temperature also becomes higher, but the impact resistance often decreases.

On the other hand, as a method of making the polymer softer, a method of adding an elastomer or a plasticizer has been proposed. However, the method of adding a plasticizer significantly lowers the softening point and may cause blooming of the plasticizer during long-term use. In order to overcome this problem, the present invention also proposed a method of copolymerizing meta-cis-polymerizable monomers having long side chains that can have plasticizing properties. Although this prevents the plasticizer from blooming, the softening point is still significantly lowered.

On the other hand, in the method of adding an elastomer, by selecting an appropriate elastomer, a small amount of addition can have a large effect on improving impact resistance. However, when attempting to obtain a more flexible resin, the addition of an elastomer increases the viscosity of the reactive solution too much, causing problems in moldability. In order to overcome this, the inventor has also proposed the addition of a non-telechelic liquid rubber with a low molecular weight. Although good effects are produced in this case as well, problems such as phase separation occur as the amount of rubber added becomes large.

Therefore, the inventor of the present invention has arrived at the present invention as a result of intensive studies on a method that can accommodate a wider range of balances.

C1 Structure of the invention, namely, the present inventor has developed a method that effectively combines the use of a reactive plasticizer and the use of liquid rubber as previously proposed, that is, without using a non-telescopic liquid rubber as the liquid rubber, We have reached the goal of using a telechelic liquid rubber that has a functional group at its end, and by utilizing the functional group, a group reactive for metathesis polymerization is introduced at the end.

That is, by copolymerizing a rubber component whose molecular weight is not as large as the terminal metathesis polymerization reactivity, it is possible to obtain a crosslinked polymer containing blocks of components having such flexible chains, and such a polymer has high stiffness and durability. We have found scales that provide a wide balance of impact resistance and rubber elastic properties.

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, the number average molecular distance is about 350 to 10
．． 000, the main chain is substantially composed of an aliphatic acyclic hydrocarbon chain or a combination thereof with an ester bond and/or an ether bond, and the low polymer (a) has a metathesis polymerizable group at the terminal. A crosslinked polymer molded product characterized by being added to a polymerizable monomer.

(2) In 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, the number average molecular weight is approximately 350 to 10.
．． 000, the main chain is substantially composed of an aliphatic acyclic hydrocarbon chain or a combination thereof with an ester bond and/or an ether bond, and the metathesis polymerizable monomer (a) has a metathesis polymerizable group at the terminal. A method for producing a cross-linked polymer molded product, characterized in that it is added to.

(3) Reaction of a) a reactive solution (solution A) of a meta-cis polymerizable monomer containing a catalyst component of a metathesis polymerization catalyst system and b) a meta-cis polymerizable monomer containing an active agent component of a metathesis polymerization catalyst system In the combination of reactive solutions consisting of at least the following, at least one of these solutions A and B has a number average molecular weight of about 350 to 10.000 and a main chain of an aliphatic acyclic hydrocarbon chain or A combination of reactive solutions, characterized in that a low polymer (a) consisting essentially of a combination of ester bonds and/or ether bonds and having a metathesis polymerizable group at the end is added thereto.

The above-mentioned low polymer (a) used in the present invention consists essentially of the following general formula.

n (Y X')+ (X" R+mRz -"
(Y-X-R++ R2(-R1-X”) ・
...(I)n m-n (I)-1 nY'+(Y" X-R1+mRz →(Y-X-
R++RzfR+-Y”) ...(I[)n
m-n (a)-2 However, in the formula, Y is a metathesis polymerization reactive group, X is a bonding group between the metathesis polymerization reactivity and the telekeric liquid rubber, RL
R2 essentially consists of a divalent and m-valent aliphatic acyclic hydrocarbon chain or a combination thereof from an ester bond and/or an ether bond, and the side chain includes a cyano group, a phenyl group, an ester group, and an ether group. etc. may be contained. There may also be cases where only R1 exists and R2 does not exist. m
is an integer of 2 to 4, n is an integer of 1 to 4, and m≧n.

X' and X' are functional groups that react with each other to form X.

Yo and Yo represent functional groups that react with each other to form Y.

In the above formula compound, n/m represents the ratio of metathesis polymerizable group terminals to all functional terminals, and ideally it is desirable to be 1, but in reality, the above reaction (I) to (II)
In many cases, unreacted ends inevitably remain. It is preferable that it is at least 0.5. X' and X'' represent functional groups that react with each other to form X. Yo and Yo represent functional groups that react with each other to form Y.

Y needs to be a cyclic olefin group having at least the same metathesis polymerizability as the metathesis polymerizable monomer used in the present invention. From the viewpoint of such reactivity, those having a norbornene structure represented by the following formula (d) are preferred.

R1 and R2 are: (i) a saturated aliphatic hydrocarbon chain obtained from a polymerized structural unit of α-olefin such as ethylene, propylene, butylene, or an unsaturated aliphatic hydrocarbon chain to be described later;

(ii) Unsaturated aliphatic hydrocarbon chains formed from polymerized units of conjugated dienes such as butadiene and isoprene.

(Machi) The above α-olefins and conjugated dienes, vinyl compounds containing polar groups such as crylonitrile, acrylic esters, methacrylic esters, maleic esters, vinyl ethers, vinyl carboxylates, vinylene compounds, etc.
Alternatively, a polar group such as a cyan group, an ester group, an ether group, a halogen group, or a cyclic group such as a phenyl group can be added to the side chain by copolymerization with a ring-containing vinyl compound such as styrene or by polymerization of a substituted conjugated diene such as chloroprene. Contains hydrocarbon chains.

(ivl Polyalkylene ether chain produced by ring-opening polymerization of 3- to 5-membered cyclic ethers such as oxirane, oxetane, and oxolane.

M A polyalkylene ester chain produced by a condensation reaction between an aliphatic diol and an aliphatic dicarboxylic acid or a functional derivative thereof or by ring-opening polymerization of a lactone.

(vQ Polyalkylene-ether-ester chains etc. obtained by ring-opening copolymerization of aliphatic dicarboxylic acid cyclic anhydride and cyclic ether, ring-opening copolymerization of lactone and cyclic ether, or ring-opening polymerization of lactone having an ether bond) can be given.

X ++ is a functional derivative such as -〇to1 or an ester thereof, -COOH or a functional derivative such as an ester or acid halide thereof.

-Nl-12 etc. can be mentioned.

In the case of X ++ 10H and its functional derivative group, -COOH, -Co(ffl, -COOR3(
However, R3 is a carboxyl group represented by a monovalent paid group) or a derivative thereof, or, for example, -C[]2C! A reactive group that reacts with the hydroxyl group represented by 2 to form an ether group.

When X ++ is 1000H and its functional derivative group -
A hydroxyl group represented by OH, -0CR4 (where R4 is a monovalent organic group) or a derivative thereof.

When X' is -NHz, a dicarboxylic acid cyclic anhydride group capable of forming a cyclic imide group, etc. can be mentioned.

On the other hand, y''-x- is an acrylic ester group.

Examples include groups that can act as a genophile in the Diels Alder reaction, such as a methacrylic acid ester group, an allyl ether group, and a furyl ester group.

Further, Yo is a cyclic conjugated diene that can react with Yo of genophile, ie, cyclopentadiene.

Examples include 1,3-cyclohexadiene, but cyclopentadiene is particularly preferred.

Preferred examples of the Y-X- group obtained by such a combination include the following groups.

(X"-R1')IIIR;!,(Y" -X-
The compound represented by R+-)mR2 is commercially available as a so-called telekeric liquid rubber, which covers a considerable amount of the above-mentioned compounds, and is converted into a terminal containing a metasense polymerization reactive group by the reaction described above. Obtained by conversion.

Kab1ru(X"-R+ +1llR2,(Y"X-
R+ +lTI Rz (D Preferred specific examples include the following compounds.

(A) Oligo-ethylene glycol dimethacrylate or diacrylate, oligo-propylene glycol dimethacrylate or acrylate (R represents at least one of H or -〇H3) (B
) Liquid polyoxypropylene [HOCH2CH20+ CHCHzO+T-+-m
R2CH3 HO(-CHz-CH2-CH2-Ct(z-0+pH
(D) Liquid polyolefin glycol HO(-Ct-1z -CH)-+Cl-12-CH2
+.・01-[p (E) Liquid polybutadiene X” (= CH2-CH+D H・HOOCmoCHz-CH2=C-CHz+pCool-
1 ([1) Liquid styrene-butadiene rubber CI) Liquid acrylonitrile-butadiene rubber X″÷CHz CH
= CHCR2+-T-fC82CH+X”N (J) Liquid poly-ε-caprolactone [(HOCH2CH2CH2CH2CH2C-0+T-
+IIIRzThe molecular weight of such a functionalized oligomer is approximately 15
0 to io, ooo can be used, and as the low polymer (a), about 350 to 10,000 can be used.

The molecular weight may be selected optimally depending on the properties of the intended crosslinked polymer molded product, but those of 100 to 5,000 are generally used.

Preferably, all of the terminal ends of the low polymer (a) are converted to metathesis polymerization reactive groups.

However, the reaction for introducing it as described above is difficult to carry out completely, and some unconverted functional groups may remain. In particular, if the functional group is a functional group containing active hydrogen, such as a hydroxyl group, amine group, or carboxyl group, it may react with the metathesis polymerization catalyst component and inhibit metathesis polymerization, and therefore cannot be converted into a metathesis polymerizable group. Even in this case, it is preferable to take measures to reduce the active hydrogen content as much as possible by a reaction that replaces active hydrogen.

In addition, the inhibitory effect of such active hydrogen-containing compounds is
The amount of low polymer (
The inhibitory effect can be minimized by considering how the addition of b) is distributed between solutions A and B.

Further, the proportion of the low polymer (A) to be added to the monomers can be determined appropriately depending on the structure of (A) used and the required properties of the molded product. Generally 1
The range used is 60% by weight, more preferably 3% to 40% by weight, and most preferably 5% to 30% by weight. It is not necessarily necessary to add the low polymer (a) in equal amounts to solutions A and B, but considering the reasons mentioned above,
It can be increased or decreased appropriately.

The metathesis-polymerizable monomer used together with the low polymer (a) to form the molded product may be any monomer as long as it can be bulk-polymerized by metathesis polymerization to give a molded product, but in general, metathesis-polymerizable monomers Those containing 1 to 4 cycloalkene groups are used. Particularly preferred are those having norbornene type bonds. Hydrocarbons are particularly preferred, and specific examples include dicyclopentadiene (DCP), dihydrodicyclopentadiene, cyclopentadiene-methylcyclopentadiene codimer, 5-ethylidenenorbornene, 5-
Vinyl norbornene, norbornene.

5-cyclohexenylnorbornene, 1,4-methano-
1,4,4a, 5.6.7.8.8a-octahydronaphthalene, 1,4,5.8-dimethano-1,4,4
a, 5,6,7,8.8a -octahydronaphthalene, 6-methyl-1,4,5,8-dimethano-1,4,4
a, 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] ] tridecar 5,11-diennorbornadiene, 5-phenylnorbornene, ethylenebis(5-
norbornene), etc. Among these, dicyclopentadiene or a heptamer mixture containing 50% or more of dicyclopentadiene is particularly 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 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 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-methoxycarbonylnorbornene, 5-methoxycarbonyl-5-methyl-norbornene, 5[(2-ethylhexyloxy)carbonyl]norbornene.

Ethylene-bis(5-norbornenecarboxylate)
, 5-cyanonorbornene, 6-diatu 1.4,5.
8-dimethano-1,4,4a, 5.6.7.8.8a
-octahydronaphthalene, N-butylnadichimide, 5-(4-pyridyl)-norbornene, and the like.

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 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 produce 1 q of polymer molded products 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 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 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 within 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 molded polymer 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 meta-cis-polymerizable monomer containing such Lewis space, as described above. Alternatively, a method of injecting a pre-formed premix into the 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.

Such glass fiber mats can also be used in the mold in the RIM system.

Salts of halides such as tungsten, rhenium, tantalum, and molybdenum are used as catalyst components in the metathesis polymerization catalyst system, and tungsten and molybdenum are preferred, with tungsten compounds being particularly preferred. Such tungsten compounds include tungsten halide,
Tungsten oxyhalide and the like are preferred, and more specifically tungsten hexachloride, tungsten oxychloride and the like are preferred. 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 by suspending it in advance in chlorobenzene or the like and solubilizing it by adding a small amount of an alcoholic compound or a phenolic compound.

Further, in order to prevent undesirable polymerization as described above, it is preferable to add about 1 to 5 moles of Lewis base or chelating agent per mole 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 itself be a Lewis base as described above, and may have its effect even without the addition of any of the above compounds.

Thus, the 7mer solution (solution A) 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 alkylaluminum halide compounds are preferred, and specific examples include salt or diethylaluminum, di-salt or ethylaluminum, trioctylaluminum, dioctylaluminum iodide, tetrabutyltin, tributylhydrogentin, etc. By dissolving these organometallic compounds as activator components in the raw material monomer, the other solution (
Corresponding to solution B) is formed.

In the present invention, a crosslinked polymer molded product can basically be obtained by mixing the above solution with solution B8, but if the above composition remains as it is, the polymerization reaction will start very quickly. Curing may occur before it flows sufficiently into the 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, and the like. Such regulators are generally added to the solution of the organometallic compound activator component. When a copolymerizable polymer having a Lewis space group is used as described above, it can also serve as the 1q-th 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.

Furthermore, regarding masking agents and regulating agents, such as those mentioned above,
The amount 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,! These include antioxidants, light stabilizers, flame retardants, polymer modifiers, residual monomer reducers, etc. 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 agent components to a practical extent and must not inhibit polymerization. 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. Glass fiber, mica, and carbon black are used as materials.

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) comethane, and the like.

By adding the metathesis-polymerizable terminal low polymer (a) to the polymer molded product of the present invention, the flexibility and impact resistance are improved, and the metathesis-polymerizable group participates in metathesis polymerization so that the terminal ends It is characterized by introducing flexible chains into the block type and maintaining other polarities by participating in crosslinking. However, ordinary elastomers are also used in appropriate amounts, generally 15% by weight, for the purpose of adjusting viscosity and further improving flexibility.
The following amounts, generally up to 8% by weight, can be used in combination. Elastomers used for this purpose include styrene-butadiene-styrene triblock rubber, styrene-isoprene-styrene triblock rubber, polybutadiene, polyisoprene, butyl rubber,
Examples include ethylene-propylene rubber and ethylene-propylene diene terpolymer. Furthermore, in the present invention, if a large amount of residual monomer is present 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 monomer is as small as possible. As an additive to reduce such residual upper
,α,α-trichlorotoluene.

ω, ω-dichlorodiphenylmethane, phthalic acid chloride, benzoic anhydride, penganesulfonic 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 mentioned above, such a molding method includes a resin injection method in which a premix of the catalyst system and a 50% polymer mixture is flowed into a mold, and a resin injection method in which the catalyst system is divided into two parts, solution A and solution B, into a head part. It is possible to use the RIM method, in which the mixture is mixed by collision and 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 product obtained in this way has particularly improved plasticity and can cover a wide range of impact resistance-synthesis balances compared to conventional products, and can be used as parts for various transportation equipment, including automobiles, and electrical and electronic equipment. It can be used for a wide range of applications, including large molded products such as housings.

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 1-11. Comparative example [Preparation of low-handed polymer (a) having a metathesis polymerizable group at the end] Commercially available telekeric rubber (A-H) was dissolved in toluene, and 5-chlorocarbonylnorbornene and pyridine were added in the proportions shown in Table 2. A low polymer (A) having a metathesis polymerizable group at the terminal is prepared by adding and reacting with stirring at 20°C.
"~H') was 1q.

The mixture was steamed under reduced pressure to remove pyridine and unreacted 5-chlorocarbonylnorbornene, and then subjected to polymerization.

The degree of esterification was measured by the pyridine-acetic anhydride method. The structures and trade names of the telekeric rubbers A-H used are shown in Table 1.
It was shown to.

[Preparation of main catalyst concentrate] High purity tungsten hexachloride 19.80 (J (0,05
mol) was added to 90 ml of dry toluene under a nitrogen stream,
Add 0.925 mol of t-butanol (J dissolved in 5 d of toluene and stir for 1 hour, then add 11.05 mol of nonylphenol and 5 ml of toluene.
Add the solution and stir for 1 hour under a nitrogen purge.

10 () of acetylacetone was added to the mixture, stirring was continued overnight under a nitrogen purge while expelling the by-product hydrogen chloride gas, and then some of the toluene distilled out was made up and 0.5
A catalyst concentrate containing H tungsten was prepared.

[Preparation of active inhibitor concentrate] D-n-octyl aluminum iodide 5.70 (
1. Mix 31.17 g of tri-n-octylaluminium (13.42 g of 1° diglyme under a nitrogen stream, then add dicyclopentadiene (DCP) to give a total of 100 g
Dilute to ml 1. An activated concentrate containing OH aluminum was obtained.

[Preparation of reactive solution] Purified DCP obtained by distilling a commercially available product, monomers to which ethylidenenorbornene and vinylnorbornene were added as necessary, the low polymer (a) prepared above, and in the case of solution A, The above main catalyst concentrate has a tungsten concentration of o, o
In the case of solution B, the aluminum concentration was adjusted to ensure polymerizability, and a concentrated solution of activator was added to the concentration shown in Table 3.

[Preparation of crosslinked polymer molded product] After bringing the above solution to a predetermined temperature, 10 ml of catalyst component solution (solution A > 10 d, activator component solution (solution B)) was taken out into a syringe that had been sufficiently replaced with nitrogen. .

Both liquids were simultaneously extruded from the syringe at a constant speed into an IOO Y glass flask equipped with a stirrer under rapid stirring, and mixed rapidly to obtain a molded product in the form of a crosslinked resin flask with a thickness of about 1 cm.

It was confirmed that the obtained resin was softer and exhibited more rubber-elastic properties than the comparative example.

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, the number average molecular weight is approximately 350 to 10.
. A cross-linked polymer molded product characterized by being added to a monomer. (2) In 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, the number average molecular weight is about 350 to 10.
. A method for producing a crosslinked polymer molded product, characterized in that the crosslinked polymer is added to a monomer. (3) 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 activator component of the metathesis polymerization catalyst system (solution B) In a combination of reactive solutions consisting of at least one of the following, at least one of these solutions A and B has a number average molecular weight of about 350 to 10,000 and a main chain of an aliphatic acyclic hydrocarbon chain or an ester bond and an aliphatic acyclic hydrocarbon chain. A combination of reactive solutions characterized by adding a low polymer (a) consisting essentially of a combination of / or ether bonds and having a metathesis polymerizable group at the end.