JPH0222324A - Molded article of crosslinked polymer, production thereof and combination of reactive solution - Google Patents

Abstract

PURPOSE:To obtain the title molded article having a small amount of residual monomer, a slight smell and excellent heat resistance by subjecting a monomer having metathetically polymerizable cycloolefin structure and containing a specific hetero atom to bulk polymerization in the presence of a metathetic polymerization catalyst in a mold. CONSTITUTION:A hetero atom-containing metathetically polymerizable monomer [e.g., 5-(trichloroacetoxymethyl)-norbornene] which simultaneously has at least one metathetically polymerizable cycloolefin structure and at least one group selected from a group containing a bond between carbon with SP3 type orbit and a halogen wherein carbon linked to the carbon is activated by taking SP2 type orbit and/or a trihalomethyl group, a group containing a bond between carbon having SP2 type orbit and being deficient in electron and a halogen, carboxylic acid anhydride group, a group containing phosphorus and a halogen and a group containing a bond between silicon and a halogen, etc., is simultaneously polymerized and molded in the presence of a metathetic polymerization catalyst system (e.g., tungsten tetrachloride) to give the aimed molded article.

Description

Detailed Description of the Invention: a. Industrial Application Field The present invention provides a method of pouring a metathesis-polymerizable monomer into a mold in the presence of a metathesis-polymerization catalyst system, and performing molding simultaneously with bulk polymerization in the mold; The present invention relates to a combination of a polymer molded product obtained thereby and a reactive solution therefor.

More specifically, it relates to an improvement that uses a metathesis-polymerizable monomer with a specific structure as part of the monomer to reduce residual monomer, reduce odor of molded products, and improve heat resistance.

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 various improvements are necessary in order for these polymer molded products to be used with high practicality. Among these improvements, an important one is the reduction of residual monomers.

Generally, when polymerization and molding are performed at the same time to directly obtain a molded product, residual monomers are present when a chain polymerization type reaction is used, and such residual monomers remain in the molded product as is. Become. Such residual monomers are, for example, dicyclopentadiene (DC
In the case of P), DCP and its dissociated cyclopentadiene are formed, but such metathesis-polymerizable monomers, including these, generally have a unique strong and unpleasant odor, so they cannot be used in molded products. However, emitting such an odor is a major problem for molded products as products.

Furthermore, it has been found that when there is a large amount of residual monomer, the heat resistance expressed by heat distortion temperature (HDT) 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 often happens and in that case, not only the depth 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 both improving the depth and heat resistance.

As a method for reducing such residual monomers, US Pat.
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 reducing monomers 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, they do not appear to have any effect on polymerization. It is thought that its action is initiated by reacting with the catalyst system after the reaction has started or after the completion of the reaction.

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 believed that the compound forms a redox system and oxidizes transition metal ions, and at the same time reduces itself by abstracting halide ions and generates 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 has been confirmed that similar effects can be achieved with carboxylic acid halides, carboxylic acid anhydrides, and halogenated compounds such as phosphorus, sulfur, and the like.

As can be deduced from the assumed mechanism of action as described above, such a residual monomer reducing agent exerts its action in the latter half of the polymerization, that is, after the reaction system has gelled. Therefore, in theory, it is sufficient that the equivalent ratio of reduced heavy metal ions be present, but in reality, a sufficient and satisfactory effect of reducing residual monomers cannot be achieved unless they are present in a considerably excess amount. It turns out. However, the excess residual monomer reducing agent ends up remaining unreacted in the polymer molding, but it exhibits a plasticizing effect that offsets the effect of reducing the residual monomer and lowers the heat distortion temperature. It has been known that if the material is allowed to cool or, conversely, freezes at low temperatures, problems such as deterioration of impact resistance may occur. Therefore, the inventors of the present invention have arrived at the present invention as a result of intensive studies to find a residual monomer reducing agent that can sufficiently reduce the residual monomer and does not cause the above-mentioned disadvantages even when used.

The structure of the invention C1, that is, the present inventor considered the use of a residual monomer reducing agent having a functional group capable of reducing residual monomers as described above and a metathesis-polymerizable cyclic olefin in the same molecule. That is, even if such a residual monomer reducing agent is used in excess of the theoretically required amount, it acts as a metathesis polymerizable monomer and polymerizes, so it does not remain in the molded product as a low molecular weight compound. Therefore, it has been found that the above-mentioned inconvenience does not occur.

That is, the present invention includes the following inventions.

(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, the product has at least one metathesis-polymerizable cycloolefin structure (Il SP3 type orbital). A group having a bond between a carbon and a halogen, and the carbon bonded to that carbon is S22
A group that is activated by taking a Se2-type orbit and/or a triheromethyl group, a group that has an electron-deficient carbon-halogen bond and has an Se2-type orbit. , (c) carboxylic acid anhydride group, (n) group having at least one bond between phosphorus and halogen, (e) group having at least one bond between sulfur and halogen, and (N) group having at least one bond between silicon and halogen. 1. A crosslinked polymer molded article, characterized in that at least one metathesis polymerizable monomer (I) containing a heteroatom containing at least one group selected from the above groups is used as a part of the metathesis polymerizable monomer.

(2) 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, at least one metathesis-polymerizable cycloolefin structure and (a) sp, the orbit of the mold are SPZ is a group that has a bond between a carbon and a halogen, and the carbon that bonds with
f) A group that is activated by taking an SP2-type orbit and/or a triheromethyl group, f) A group that is activated by taking an SP2-type orbit and a bond between a carbon and a halogen that is electron-deficient. a group having at least 61 all sulfur and halogen bonds; Crosslinked polymer molding characterized in that at least one metathesis-polymerizable monomer (I) containing a heteroatom, which simultaneously has at least one group selected from at least one group, is used as a part of the metathesis-polymerizable monomer. How things are manufactured.

(3a) 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 these solutions A and B, at least one metathesis-polymerizable cycloolefin ellipse and (a) a bond with a halogen and a carbon having an sp type orbital are added. The group that has SPZ and the carbon bonded to it are SPZ
(b) A group that is activated by taking a Se2-type orbit and/or a triheromethyl group; (Kawa: Carboxylic anhydride group, Naka) Group having at least one bond between phosphorus and halogen, (e) Group having at least one bond between yellow and halogen, and (f) Group having at least one bond between silicon and halogen. A combination of reactive solutions containing at least one heteroatom-containing metathesis-polymerizable monomer (I) which simultaneously has at least one group selected from at least one group.

The metathesis-polymerizable cycloolefin group in the above-mentioned heteroatom-containing metathesis-polymerizable monomer (I) used in the present invention is one having at least the same level of metathesis-polymerizability as other metathesis-polymerizable monomers used at the same time. From that point of view, a norbornene structure as represented by the following formula (II) is preferred.

On the other hand, the monomer (I[) has at least one of the above (a) to (f) as a group capable of exhibiting the effect of reducing the residual monomer in the monomer (I[).

When the group corresponding to (a) is expressed as a partial structural formula, it becomes as follows.

The carbon atom taking the SP2 orbit in (III) and (V> is preferably introduced in the form of a carbon atom of an aromatic ring such as a benzene ring or a carbonyl carbon in a broad sense because it is easily available.

When considering obtaining a structure having both a norbornene structure and its #I structure, industrial methods include a method based on the Diels-Alder reaction between substituted styrene and cyclopentadiene, and a method derived from halo-substituted acetic acid, especially trichloroacetic acid. It is advantageous from a viewpoint.

As specific examples of such compounds, particularly preferred ones include:
First of all, the following formula (V), in which X represents halogen and satisfies the definitions of (■) and (IV) at the same time, is particularly preferred.

/1 5-(trichloroacetoxymethyl)-norbornene 5.6-bis(trichloroacetoxymethyl)-norbornene, etc. can be mentioned. Such a compound is allyl trichloroacetate or 1,4-trichloroacetoxy-
Direct Diels reaction between butene-2 and cyclopentadiene
Although it can also be obtained by Alder reaction, hydroxymethylnorbornenes are obtained by Diels-Alder reaction of allyl alcohol or butynediol with cyclopentadiene, and functional derivatives such as trichloroacetic acid ester and chloride are added to this. It can also be produced by trichloroacetylation method.

On the other hand, among those obtained from heromethylated styrenes, 5(P-ri-tetramethylphenyl)norbornene is the most easily obtained industrially. That is, styrene
It can be easily obtained by a Diels-Alder reaction between P-chloromethylstyrene obtained by chloromethylation and cyclopentadiene. When the group corresponding to (b) is expressed as a substructural formula, it becomes as follows.

(However, in the formula, X represents a halogen.) In such a structure, the SPz type carbon to which the halogen is bonded must be in an electron-deficient state due to a very strong electron-withdrawing group. Typical functional groups that realize such properties include carboxylic acid halide groups and perhaloolefin groups, and carboxylic acid chloride groups are particularly preferred because of their structural ease.

As specific preferred examples of such monomers (I), such cyclic anhydride groups may be either cyclic or chain-like, but cyclic ones are easier to obtain, but the cyclic anhydride group is less effective as a monomer reducing agent. It is thought that the chain-like ones are large.

Specific preferred examples of such monomer g(I) include: 5-chloroformylnorbornene 5-(P-chloroformylphenyl)norbornene etc. can be given.

(The group corresponding to Nori is expressed as a partial structural formula as follows.

Nadic anhydride, (norbornenyl)phthalic anhydride, specific examples of such monomers (I) include (norbornene-5-carboxylic acid) anhydride, (P-norbornenylbenzoic acid) anhydride, etc. I can do it.

(The group corresponding to the gradient is expressed as a partial structural formula as follows.

(However, in the formula, X represents a halogen.) Specific functional groups belonging to this group include partially esterified products of phosphorus oxychloride, partially esterified products of phosphorous trichloride, phosphonic acid chlorides, etc. .

etc. can be given.

When the group corresponding to (e) is expressed as a substructural formula, it becomes as follows.

+1 (However, in the formula, X represents a halogen.) Specific functional groups belonging to this group include a sulfonic acid chloride group, a chlorosulfide group, and the like. As a specific example of such monomers (I), the group corresponding to (f) is expressed as a partial structural formula as follows.

5t-X(X) (However, in the formula, X represents a halogen.) Specific functional groups belonging to this group include chlorosilane-containing groups derived from vinylchlorosilane and phenylchlorosilanes.

Specific examples of such monomers (I) include the following.

etc. can be given.

The action of such monomers (I) as a monomer reducing agent is thought to be due to the interaction between the functional groups (a) to (f) of these monomers and the main catalyst component of the metathesis polymerization catalyst system. The necessary amount of addition is such that equivalent functional groups are added to the number of moles of the transition metal element used as the main catalyst component, but as mentioned above, this generally does not provide sufficient effect. Generally, an amount several times that amount is used.

That is, the amount of monomers (I) generally used is 1 to 1 molar number of the transition metal element as the main catalyst component used in the polymerization system.
A range of 10 times equivalents is used.

Therefore, the proportion of the above monomers (I) to be used in the total monomers varies depending on the molecular weight of the monomer and the concentration of the main catalyst component used, so it cannot be determined with certainty, but it is generally 1% by weight or less, and at most 5% by weight or less. It is. What does it cost? - Group (I) is preferably one with as high purity as possible, particularly one with few impurities that inhibit metathesis polymerization.

Low molecular weight compounds conventionally used as monomer reducing agents can be used together with the monomers (I) according to the invention. That is, since the monomer reducing agent involved in the monomer reducing effect participates in a chemical reaction and is converted into another compound, the above-mentioned disadvantages will not occur if it is added in a small amount. Therefore, by using a small amount of a highly efficient low-molecular non-polymerizable residual monomer reducing agent, it may be possible to more efficiently reduce the residual monomer.

The specific molding method of the method for producing the polymer molded product of the present invention is to mix the reactive solution with a static mixer or the like, or to prepare a premix in advance and inject it into the mold to form the molded product. Resin injection methods and similar molding methods can also be used to obtain this, but in general, the reaction after mixing is quick, so reaction injection molding (RIM molding) involves injecting the mixed reaction solution into the mold immediately after impact mixing. is the most suitable.

In the present invention, as a preferred specific example of the metathesis-polymerizable main monomer used together with the monomers (I), a metathesis-polymerizable main monomer having a norbornene structure of 1
Preferably, those having ~2 are dicyclopentadiene, tricyclopentadiene, cyclopecitadiene-methylcyclopentadiene codimer, 5-ethylidenenorbornene, 5-vinylnorbornene, norbornene, norbornadiene, 5 -cyclohexenylnorbornene,
1,4,5.8-dimethano-1,4,4a, 5.6
．． 7.8.8a octahydronaphthalene, 1,4-methano-1,4°4a, 5.6.7.8.8a-octahydronaphthalene, 6-ethylidene-1,4,5,8-dimethano-1 , 4, 4a, 5.7. F3゜8a-hebutahydro-naphthalene, 1,4,5,8-dimethano-
Examples include one or a mixture of two or more of 1,4,4a,5,8.8a-hexahydronaphthaleneethylenebis(5-norbornene), and especially dicyclopentadiene, or mainly dicyclopentadiene. Monomer mixtures are preferably used.

Further, if necessary, a metathesis polymerizable cyclic compound containing a different element such as oxygen or nitrogen can also be used.

Such polar monomers are often used in copolymerization with dicyclopentadiene and the like.

Such a polar monomer also preferably has a norbornene structural unit, and the polar group is preferably an ester group, an ether group, a cyano group, N-ff substituted imide, or the like.

Specific examples of such copolymerizable monomers include 5-methoxycarbonylnorbornene, 5-(2-ethylhexyloxy)carbonyl-5-methylnorbornene, and 5-phenylokimethylnorbornene.

5-cyanonorbornene, 6-diatu 1.4, 5.8
Examples include dimethanol-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, and N-butylnadic acid imide.

As mentioned above, the metathesis polymerizable monomer is required to contain as few impurities as possible that would inactivate the metathesis polymerization catalyst.

As the catalyst component in the metathesis polymerization catalyst system used in the present invention, salts such as halides such as tungsten, rhenium, tantalum, and molybdenum are used, and tungsten compounds are particularly preferred.

As such a tungsten compound, tungsten halide, tungsten oxyhalide, etc. are preferable, and more specifically, tungsten hexachloride, tungsten oxychloride, etc. are preferable, and organic ammonium tungstate and the like can also be used.

It is known that when such a tungsten halide compound is added directly to a monomer, it immediately starts cationic polymerization, which is not preferable. Therefore, the tungsten halide compound is suspended in an inert solvent such as benzene, toluene, chlorobenzene, etc. It is preferable to use it after solubilizing it by adding 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 mol of a Lewis base or a chelating agent to 1 mol of the tungsten compound. Such additives include acetylacetone, alkyl acetoacetate, etc. Esters.

Tetrahydrofuran, benzonitrile, etc. can be used.

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

On the other hand, the active 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 activated components in the raw material monomer.

In the present invention, a crosslinked polymer molded article 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 often poses a problem, and as mentioned above, it is preferable to use an activity regulator for this purpose.

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 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.

Further, as described above, the masking agent and the regulating agent can be appropriately adjusted and used depending on the amount of the catalyst system to be used through experiments.

In the improved method of the present invention, the monomers (I) are added to at least one of the above-mentioned solutions A and B, preferably solution A, according to the usage conditions such as the amount added as described above, and the reaction is carried out. A polymer molded product can be obtained by simultaneously performing polymerization and molding by injection molding or the like. Due to the use of such monomers, such a molded product has a much smaller amount of residual monomer than in the case where such monomers are not used. In particular, compared to conventional residual monomer reducing agents, it can be used in large quantities without any side effects, so it is possible to easily obtain a product with a very small amount of residual monomer. That is, in general, when a residual monomer reducing agent is not used, residual monomers often remain as much as 2 to 4% by weight, but by using the monomers of the present invention, there are no side effects and in good cases 0.5% of residual monomer remains.
It can be reduced to less than % by weight.

In practical use, various additives may 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, and the like. Since it is impossible to add such additives after the crosslinked polymer of the present invention is molded, it is necessary to add them to the above-mentioned raw material solution in advance when adding them.

The easiest method is to
One method is to add it to either or both of the above in advance, but in that case, the amount of material that may interfere with the highly reactive catalyst components, activator components, or organic halogenated silicones in the liquid may be a practical problem. The monomer must not react with the monomer and must not inhibit the polymerization.If the reaction cannot be avoided, but the coexistence of the monomer does not substantially inhibit the polymerization, the monomer must be mixed with the monomer. It is also possible to prepare a third liquid and use the mixture immediately before polymerization.

Also, in the case of solid fillers, when both components are mixed and immediately before starting the polymerization reaction or during polymerization,
If the shape is such that the void can be filled sufficiently, it is also possible to fill it into the mold for molding.

Reinforcements or fillers as additives are effective in improving the flexural modulus. Examples of such materials include glass fiber, mica, carbon black, and wollastonite. Those that have been surface-treated with a so-called silane coupler can be preferably used.

In addition, it is preferable to add an antioxidant to the crosslinked polymer molded product of the present invention, and it is preferable to add a phenol-based or amine-based antioxidant to the solution in advance. Specific examples of agents include 2.6-
t-Butyl-P-cresol, N,N'-diphenyl-
P-phenylenediamine 1tetrakis[methylene(3,
Examples include 5-dibutyl-4-hydroxycinnamate)]methane.

Furthermore, other polymers can be added to the polymer molded article according to the present invention when it is in a monomer solution state. As such a polymer additive, the addition of an elastomer is
It is effective in increasing the lil impact strength and adjusting the viscosity of the solution. Elastomers used for this purpose include styrene-butadiene-styrene triblock rubber, styrene-isoprene-styrene triblock rubber, polybutadiene, polyisoprene, butyl rubber, ethylene-propylene rubber, ethylene globylene-dienter polymer, nitrile rubber, etc. A wide range of elastomers can be mentioned.

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

As mentioned above, such molding methods include the resin injection method, in which a premix of the catalyst and raw material monomers is mixed with a static mixer, etc., is flowed into the mold, and the resin injection method, in which the catalyst system is divided into two parts: dissolved OA and solution B. It is possible to adopt the RIM method in which the mixture is collided in the head and poured directly into the mold.

In particular, the RIM method is commonly used.

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, demolding is easy and often does not require special keying agents.

Since the molded product has many double bonds, an oxidized layer is formed on the surface, so that it has good adhesion to commonly used paints such as epoxy and polyurethane.

d0 Effects of the Invention According to the present invention, it is possible to obtain a polymer molded product with a small amount of residual monomer, little odor, and good heat resistance.

Furthermore, the residual monomer reducing agent of the present invention improves the drawback of conventional residual monomer reducing agents, namely, that if too large an amount is added, the softening temperature of the polymer molded product is lowered.

Therefore, the molded product obtained by the present invention can be used in a wide range of applications, mainly large-sized molded products, such as members for various transportation equipment including automobiles, and housings for electrical and electronic devices.

e. Examples The present invention will be described in detail below with reference to Examples and Comparative Examples. Note that the examples are for illustrative purposes only, and are not limited thereto.

Examples 1-18. Comparative Examples 1 to 5 Commercially available DCP was purified by distillation under reduced pressure in a nitrogen stream to obtain purified dicyclopentadiene having a freezing point of 33.4°C.

Purity measurement using a gas chromatograph showed a purity of 99% or more.

The heteroatom-containing metathesis-polymerizable monomer (1) was synthesized and purified by the following method, and the one with a purity of 99% or more as determined by gas chromatography was used.

Synthesis of heteroatom-containing metathesis polymerizable monomer (I) (a) Synthesis of 5-(trichloroacetoxymethyl)-norbornene (V-1) Hydroxymethylnorbornene 5.00ir, trichloro#acid chloride 7.461r, and pyridine 1.62g n
After a stirring reaction in 25 ml of -hebutane at 25°C for hours, 8.3 t of 5(trichloroacetoxymethyl)-norbornene with a purity of 99% or higher was obtained by distillation purification.

Synthesis of fo15-(P-chloromethylphenyl)norbornene (1-1) Dicyclopentadiene in autoclave 11.22 t
, 5-(P-chloromethylphenyl)norbornene 22 with a purity of 99% or more was synthesized by adding 25.92 g of P-chloromethylstyrene and 100 μm of hydroquinone and heating and stirring at 150°C for 5 hours, and purified by distillation.
．． 4g was obtained.

(7S Synthesis of 5-chloroformylnorbornene (Vl-1) 5-chloroformylnorbornene (Vl-1) was synthesized by reacting cyclopentadiene with acrylic acid chloride and then purifying it by distillation.

(d) Purification of nadic acid anhydride (■-1) Commercially available nadic acid anhydride was recrystallized and purified with ether, and the melting point was 1.
It was used as nadic acid anhydride (■-1) at 64-165°C.

(E) Synthesis of dichlorophosphorylic acid 5-norbornenyl methyl ester (■-1) Diphosphoryl chloride 2.27. and 1°48 g of hydroxymethylnorbornene at -5 to 5°C.

Synthesis was carried out by stirring for 8 hours. The product is isolated and purified by thin layer chromatography, and dichlorophosphorylic acid methyl norbornenyl ester is isolated and purified at a concentration of 0.42%. Obtained.

(f) Synthesis of 5-norbornenylmethyl-m-talolosulfonylpenzoate (IX-3>) Reaction of 3.1 g of 5-hydroxymethylnorbornene and 7.2 g of m-chlorosulfonylbenzoyl chloride with stirring at room temperature. 1.2 g of 5-norbornenylmethyl m-talolosulfonyl penzoate (IX-3) was obtained by the method of isolation and purification by thin layer chromatography.

(15-Trichlorosilylnorbornene (X-1) was manufactured by Shin-Etsu Chemical Co., Ltd. and was used as it was.

[Preparation of catalyst component solution 1 20 g of tungsten hexachloride was added to 70 ml of dry toluene under a nitrogen stream, and then a solution consisting of 21 g of nonylphenol and 16 ml of toluene was added to prepare a 0.5 M tungsten-containing catalyst solution. For the solution,
Nitrogen gas was purged overnight to remove hydrogen chloride gas produced by the reaction of tungsten hexachloride and nonylphenol, which served as a polymerization catalyst.

Such melt 110ml1. Add 1.0 ml of acetylacetone and a metathesis-polymerizable monomer (I) containing a heteroatom in an amount corresponding to the example to 6 wt% of the total amount of rubber 5tere.
It was added to 500 ml of a monomer mixture containing on702 and mixed to prepare a solution A having a tungsten content of 0.001 M.

[Preparation of activator component solution] Trioctylaluminium, dioctylaluminum iodide, and diglyme in a molar ratio of 85=15:1
00, 6 wt% of 5tereon70 was used based on the total amount.
A 0.003 M solution B was prepared by mixing it with 500 ml of a monomer containing 2 to prepare the aluminum content.

The amount of DCP and metathesis polymerizable monomer rubber component added to the monomer mixture in the solution, the type and molar ratio of the metathesis polymerizable monomer (I) containing a different atom were as shown in Table 1 below.

The above solution was added to 1 part of the catalyst component solution (solution A).
After bringing 10 ml of the activator component solution (solution B) to a predetermined temperature, it was taken out into a syringe that had been sufficiently replaced with nitrogen.

The liquid was mechanically extruded from the syringe at a constant speed, guided into a nozzle, and then molded using an ultra-compact RI Mfi that could be mixed by collision and poured into a mold, resulting in a brown, durable plate.

A 1 g sample was cut out from this plate-shaped cross-linked molded product.
After thoroughly extracting the residual monomer by immersing it in 0 onl of toluene, unreacted monomer components were discovered using a gas chromatograph, and the amount of residual monomer (% by weight relative to the molded product) was determined.
was measured.

Furthermore, take out the solidified cross-linked resin, cut out a section, and measure the softening point in the TMA needle penetration mode in a nitrogen stream.
The swelling ratio was also measured on another sample, and the results are summarized in Table 2.

It can be seen that the residual monomer, which is the cause of odor, decreases as the amount of the metathesis-polymerizable monomer containing a different atom increases. Furthermore, in the case of a metathesis-polymerizable monomer containing a heteroatom, even if the amount added is increased, only the amount of residual monomer is reduced and the softening temperature is not lowered, whereas in the case of a non-metathesis-polymerizable residual monomer reducing agent, the amount added is It can be seen that as the amount increases, the amount of residual monomer decreases, but the softening temperature nevertheless decreases.

Claims (3)

[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, it has at least one metathesis-polymerizable cycloolefin structure and (a) an SP_3 type orbital. SP_2
A group that is activated by having a type orbital and/or a trihalomethyl group; (b) A group that has a SP_2 type orbital and a bond between a carbon and a halogen that lacks an electron. (3) a carboxylic acid anhydride group, (d) a group having at least one bond between phosphorus and halogen, (e) a group having at least one bond between sulfur and halogen, and (f) a group having at least one bond between silicon and halogen. Cross-linked polymer molding characterized in that at least one metathesis-polymerizable monomer (I) containing a heteroatom, which simultaneously has at least one group selected from at least one group, is used as a part of the metathesis-polymerizable monomer. thing. (2) 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, at least one metathesis-polymerizable cycloolefin structure and (a) SP_3 type orbit are formed. A group having a bond between carbon and halogen, and the carbon bonded to that carbon is SP_2
A group that is activated by having a type orbital and/or a trihalomethyl group; (b) A group that has a SP_2 type orbital and a bond between a carbon and a halogen that lacks an electron. (3) a carboxylic acid anhydride group, (d) a group having at least one bond between phosphorus and halogen, (e) a group having at least one bond between sulfur and halogen, and (f) a group having at least one bond between silicon and halogen. Cross-linked polymer molding characterized in that at least one metathesis-polymerizable monomer (I) containing a heteroatom, which simultaneously has at least one group selected from at least one group, is used as a part of the metathesis-polymerizable monomer. How things are manufactured. (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 these solutions A and B, at least one metathesis-polymerizable cycloolefin structure and (a) a bond between a carbon and a halogen having an SP_3 type orbital are present. The group that has SP_2 and the carbon bonded to that carbon
A group that is activated by having a type orbital and/or a trihalomethyl group; (b) A group that has a SP_2 type orbital and a bond between a carbon and a halogen that lacks an electron. (3) a carboxylic acid anhydride group, (d) a group having at least one bond between phosphorus and halogen, (e) a group having at least one bond between sulfur and halogen, and (f) a group having at least one bond between silicon and halogen. A combination of reactive solutions containing at least one heteroatom-containing metathesis polymerizable monomer (I) which simultaneously has at least one group selected from at least one group.