JPH0739472B2 - Method for producing crosslinked polymer molding - Google Patents

Description

TECHNICAL FIELD The present invention relates to a process for producing a novel polymer molded product of an improved cyclopentadiene polymer. More specifically, it relates to a method for producing a crosslinked polymer molded article by bulk-polymerizing a monomer containing dicyclopentadiene using a metathesis polymerization catalyst.

b. Conventional technology Dicyclopentadiene (hereinafter sometimes abbreviated as “DCP”) is a thermodynamically-determined cyclopentadiene, which is one of the main components of the C ₅ fraction when ethylene is produced by naphtha cooking. It is obtained as a stable dimer and can be said to be a rich petrochemical raw material.

Conventionally, DCP has been used as a raw material for obtaining petroleum resin by thermal radical polymerization or cationic polymerization. But recently
A technique has been developed in which two double bonds in the ring of DCP are subjected to ring-opening polymerization by an olefin metathesis polymerization catalyst system to obtain a crosslinked polymer molded body from DCP at once (for example, Japanese Patent Laid-Open Publication No. Sho.
(See JP 58-129013). This technology is that a large-scale molded product can be easily obtained from the above-mentioned rich petrochemical raw materials by the reaction molding method, and the molded product has excellent physical properties with a good balance between synthesis and impact resistance. Is industrially valuable in that

By the way, the metathesis catalyst system used in the reaction molding method is generally active as a catalyst system by a combination of a transition metal salt catalyst such as tungsten, rhenium, or tantalum and an organometallic compound such as aluminum or tin for activating it. Expressed. The above method utilizes this point, in the state where both the catalyst component and the activator component are mixed in the DCP separately separated, the polymerization is not initiated, but by rapidly mixing the two, Metathesis polymerization is disclosed and devised so that the reaction proceeds and molded articles are obtained all at once.

Such a metathesis catalyst system is very reactive with both of the above components, and even if the reaction injection molding method as described above is adopted, the reaction rate after mixing both components is too fast,
It has been found that in some cases gelling may start before a sufficient molded product is obtained before it is sufficiently poured into the mold.

Furthermore, depending on the application, it may be advantageous in some cases that the apparatus is simpler and easier to cure by inflow heating and curing after a certain period of time in a premixed state in which both solutions are mixed, rather than reaction injection molding. I understand.

It is known that the activity of such a metathesis polymerization catalyst can be controlled by adding a Lewis base compound. However, when such a Lewis base is added in order to sufficiently control the activation degree, it remains in the polymer, and there is a problem that the properties of the polymer are impaired and a volatile component is generated. . Therefore, the present inventor has arrived at the present invention as a result of earnest research on a method for overcoming such inconvenience.

c. Structure of the invention That is, the present inventor, when the specific Lewis base is contained in a monomer having metathesis polymerizability and polymerized together, the low-molecular weight Lewis base does not remain and the above-mentioned inconvenience disappears. Moreover, it is thought that if the copolymerized Lewis base group can give useful properties to the polymer, it would be advantageous to obtain both of them. Therefore, as a result of the research on a specific Lewis base group-containing monomer, 1 The present invention has been completed by finding that the norbornene derivative containing 2 to 2 thereof is extremely suitable for the above purpose.

That is, the present invention, a metathesis polymerizable cyclic olefin compound containing dicyclopentadiene, in the presence of a metathesis polymerization catalyst system, in the method for obtaining a cross-linked polymer molded product by performing bulk polymerization and molding at the same time, a raw material monomer As a metathesis-polymerizable cycloalkene containing at least 30 mol% of dicyclopentadiene, the majority contains 99.5 mol% and the balance has 1 to 2 pendant cyano groups in the molecule.
A method for producing a cross-linked polymer molded article, which comprises using a monomer mixture consisting essentially of at least one norbornene derivative having two or more.

In the present invention, (a) a reaction solution of a metathesis-polymerizable cyclic olefin containing a catalyst of a metathesis polymerization catalyst system (solution A), (b) a reaction of a metathesis-polymerizable cyclic olefin containing an activator of a metathesis polymerization catalyst system A reactive solution (solution B), which comprises at least a reactive solution consisting of
The composition of the metathesis-polymerizable cyclic olefins in the solution A and the solution B is such that the combined composition of the metathesis-polymerizable cycloalkenes containing at least 30 mol% of dicyclopentadiene is more than half mol to 99.5 mol% and the balance is in the molecule. It is possible to use a combination of reactive solutions which is characterized in that it is a monomer mixture consisting essentially of at least one norbornene derivative having 1-2 pendant cyano groups.

The DCP used in the present invention is preferably highly purified. The DCP used in the present invention generally has a DCP purity of 95% or more, more preferably 97% or more, and impurities are
As a matter of course, it does not inhibit the activity of the metathesis catalyst system, but it is preferably one having metathesis polymerizability. The content of polar compounds such as alcohols, carboxylic acids, and carbonyl compounds that inhibit metathesis polymerization is preferably as low as possible.

As the metathesis-polymerizable cycloalkene used as a minor component together with DCP, those containing 1 to 2 metathesis-polymerizable cycloalkene groups are generally used.
Those having a norbornene-type bond are particularly preferable. Hydrocarbons are particularly preferable, and specific examples include cyclopentadiene-methylcyclopentadiene co-dimer,
5-ethylidene norbornene, 5-vinyl norbornene, 5-phenyl norbornene, 5-isobutyl norbornene, 1,4,5,8-dimethano-1,4,4a, 5,8,8a-hexahydronaphthalene, tricyclo [5, 2,1,0] deca-5-ene, tricyclopentadiene, 1,4,5,8-dimethano-1,
4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-ethylidene-1,4,5,8-dimethano-1,4,4a, 5,6,8,8a-heptahydronaphthalene, etc. Can be raised. The cycloalkenes containing a hetero atom are also preferably those containing a norbornene group, and examples thereof include 5-methoxycarbonyl-norbornene, 5-methoxycarbonylmethylnorbornene, and hexamethylene-bis-nadimide.

The norbornene derivative having 1 to 2 pendant cyano groups used in the present invention includes those having at least one norbornene structural unit represented by the following formula.

(However, in the formula, the valence may form a ring through another atom.) Therefore, in addition to the norbornene ring having a bicyclo structure, a tricyclo body or tetracyclo, for example, 1,4,5,8-dimethano-1, 4,4
a5,6,7,8,8a-octahydronaphthalene ring (However, the valence in the formula may form a ring through another atom), 1,4-methano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene ring And the like are included.

1 to 2 pendant cyano groups are added to the polycyclic olefin.
Although a compound having an individual compound can be used as the monomer of the present invention, compounds having a liquid state at 50 ° C or lower are generally preferable.

The following can be mentioned as specific examples.

5-cyano-norbornene 5-cyano-5-methylnorbornene 5,6-dicyano-norbornene 6-Cyano-1,4,5,8-dimethano-1,4,4a, 5,6,7,8,8a-
Octahydronaphthalene 6,7-Dicyano-1,4,5,8-dimethano-1,4,4a, 5,6,7,8,8
a-octahydronaphthalene 6-cyano-1,4-methano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene The cyano group-containing norbornene derivatives include cyclopentadiene (which can be used in the reaction in any form of cyclopentadiene and dicyclopentadiene), acrylonitrile, malonitrile, fumaronitrile, 5-
It can be obtained in an extremely high yield by the Diels-Alder reaction of cyanonorbornene, 5,6-dicyanonorbornene, cyanocyclohexene and the like. As a matter of course, such cyano group-containing norbornene derivatives need to be sufficiently purified before use.

Among the metathesis-polymerizable cycloalkenes in the present invention,
The proportion of DCP used is at least 30 mol%, but preferably 50 mol% or more.

On the other hand, with respect to the ratio of the cycloalkenes and the cyano group-containing norbornene derivative used, the preferable range varies depending on the molding method. As described above, when a crosslinked polymer molded product is to be obtained by the reaction injection molding method, the time from the mixing of the solution A and the solution B to the start of polymerization is a time sufficient for the liquid to flow into the mold. Therefore, the regulatory action of the cyano group-containing norbornene derivative may be small,
Therefore, the range of 0.5 to 25 mol% is preferable. On the other hand, in the molding method which goes through the premixed state, stability in the premixed state is required to some extent, and therefore, the range of 30 to 45 mol% is preferable.

The composition of these monomer mixtures is Solution A and Solution B.
In the above, it is not necessary that they are the same, and they can be appropriately adjusted and used according to the purpose, and it is sufficient that the combination of both is within the above range.

The copolymerization effect of the cyano group-containing norbornenes is that, in addition to the above-mentioned action of adjusting the polymerization initiation time, the cyano group has a high polarity, so that the crosslinked polymer obtained also has a high polarity and a large intermolecular force. In some cases, the secondary transition point is not lowered, and chemical resistance can be improved. Further, since it is highly polar even in the monomer state, it has an advantage that other monomers and additives which are solid at room temperature and do not dissolve in hydrocarbon type cycloalkenes can be well dissolved.

Salts such as halides of tungsten, rhenium, tantalum, etc. are used as the catalyst component in the metathesis polymerization catalyst system in the above-mentioned molding method, but tungsten compounds are particularly preferable. As such a tungsten compound, tungsten halide, tungsten oxyhalide and the like are preferable, and more specifically, tungsten hexachloride, tungsten oxychloride and the like are preferable. It has been found that such a tungsten compound immediately starts cationic polymerization when directly added to dicyclopentadiene, which is not preferable. Therefore, such tungsten compounds are insoluble solvents such as benzene, toluene,
It is preferable to suspend in chlorobenzene or the like in advance and solubilize it by adding a small amount of an alcohol compound or a phenol compound before use.

Further, 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 in order to prevent undesired polymerization. Examples of such additives include acetylacetone, acetoacetic acid alkyl esters, tetrahydrofuran and benzonitrile. As described above, the cyano group-containing norbornenes used in the present invention are themselves Lewis bases, and in many cases, they have the action even without the addition of the above compounds.

Thus, a monomer solution containing the main catalyst component (Solution A)
Has practically sufficient stability.

On the other hand, the activator component in the metathesis polymerization catalyst system is preferably an organometallic compound centered on an alkylated compound of a metal of Group I to Group III of the Periodic Table, particularly tetraalkyltin, an alkylaluminum compound, an alkylaluminum halide compound, Specifically, diethylaluminum chloride, diethylaluminum chloride, trioctylaluminum, tetrabutyltin, etc. can be mentioned. By dissolving the organometallic compound as the activator component in the mixed monomer, the other solution (corresponding to the solution B) is formed.

In the present invention, basically, a crosslinked polymer molded product can be obtained by mixing the solution A and the solution B, but the cyano group-containing norbornenes have a regulating effect on the reaction rate. Therefore, it can be cured under stable conditions, but if it is desired to further adjust the polymerization rate, another Lewis base can be added.

The amount of the metathesis polymerization catalyst system used is, for example, when a tungsten compound is used as the catalyst component, the ratio of the tungsten compound to the mixed monomer is about 10 on a molar basis.
If the activator component is an alkylaluminum, and the ratio of the aluminum compound to the DCP mixed monomer is on a molar basis, the ratio is from 00: 1 to about 15000: 1, preferably about 2000: 1. About 100 to 1 to about 2000 to 1,
Preferably, about 200: 1 to about 500: 1 is used.
Further, as described above, the masking agent and the adjusting agent can be appropriately adjusted and used depending on the amount of the catalyst system used by experiments.

The crosslinked polymer molded product according to the present invention may contain various additives in order to improve or maintain its properties in practical use. Such additives include fillers, pigments, antioxidants, light stabilizers, polymer modifiers and the like.
Since such an additive cannot be added after the crosslinked polymer of the present invention is molded, when it is added, it is necessary to add it to the above-mentioned raw material solution in advance.

The easiest method is to add it to either or both of the solution A and the solution B in advance, and in that case, a catalyst component having strong reactivity in the solution or activation It must be a substance that does not react with the components of the agent for practical purposes and does not hinder the polymerization. In any case, if the reaction is unavoidable but coexistence does not substantially inhibit the polymerization, it can be mixed with the monomer to prepare the third liquid, and mixed and used immediately before the polymerization. . Further, in the case of a solid filler, when the two components are mixed and the shape is such that the voids can be sufficiently filled immediately before starting the polymerization reaction or during the polymerization, it is filled in the molding mold. It is also possible to keep it.

The reinforcing material or filler as an additive is effective in improving the bending modulus. Examples thereof include glass fiber, mica, carbon black, wollastonite and the like. Those obtained by surface-treating these with a so-called silane coupler can also be suitably used.

In addition, it is preferable to add an antioxidant to the crosslinked polymer molded product of the present invention, and therefore it is desirable to add a phenol-based or amine-based antioxidant to the solution in advance. Specific examples of these antioxidants include 2,6-di-t-butyl-p-cresol and N, N'-diphenyl-
p-phenylenediamine, tetrakis [methylene (3,5
-Di-t-butyl-4-hydroxycinnamate)] methane and the like.

Further, the polymer molded product according to the present invention may be added with another polymer in a monomer solution state. As such a polymer additive, the addition of an elastomer is effective in enhancing the impact resistance of the molded product and controlling the viscosity of the solution. As the elastomer used for this purpose,
A wide range of elastomers such as styrene-butadiene-styrene triblock rubber, styrene-isoprene-styrene triblock rubber, polybutadiene, polyisoprene, butyl rubber, ethylene propylene-diene terpolymer, nitrile rubber can be mentioned.

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

As the molding method, as described above, the resin injection method in which the catalyst system and the monomer mixture are mixed in advance into the mold, the solution A and the solution B in which the catalyst system is divided into two are collided at the head portion. It is possible to adopt the RIM method in which it is mixed and poured into the mold as it is. In either case, the injection pressure into the mold can be relatively low, and thus inexpensive molds can be used.

Further, when the polymerization reaction in the mold starts, the temperature in the mold rapidly rises due to the reaction heat, and the polymerization reaction ends in a short time. Unlike the case of polyurethane-RIM, it is easy to release from the mold, and a special release agent is often unnecessary.

The molded product has an oxide layer on the surface and has good adhesion to commonly used paints such as epoxy and polyurethane due to the polarity of the cyano group.

d. Effect of the Invention According to the present invention, a reaction delay due to a cyano group can be achieved, and a molded product having excellent physical properties and the like can be obtained.

The molded product thus obtained can be used for a wide range of applications, mainly for large molded products such as members of various transportation equipment including automobiles, housings of electric and electronic devices.

e. Examples Hereinafter, the present invention will be described in detail with reference to Examples. It should be noted that the embodiment is for the purpose of explanation, and the present invention is not limited to this.

Examples 1 to 6 and Comparative Example Commercially available DCP was purified by distillation in a nitrogen stream under reduced pressure to give a freezing point of 3
Purified dicyclopentadiene having a temperature of 3.4 ° C. was obtained. Purity measurement by gas chromatography showed a purity of 99% or higher.

On the other hand, commercially available dicyclopentadiene was thermally dissociated to obtain cyclopentadiene, and 5-cyanonorbornene was synthesized by a method of reacting this with acrylonitrile. Purification by distillation and purity measurement by gas chromatography also showed a purity of 90% or higher.

[Preparation of catalyst component solution] 20 g of tungsten hexachloride was added to 70 ml of dry toluene under a nitrogen stream, and then 21 g of nonylphenol and 1 part of toluene.
A 0.5M tungsten-containing catalyst solution was prepared by adding a 6 ml solution, and the solution was purged with nitrogen gas overnight to remove the hydrogen chloride gas produced by the reaction of tungsten hexachloride and nonylphenol. This was used as a polymerization catalyst.

10 ml of this solution, 1.0 ml of acetylacetone mixed monomer 500
ml was mixed to prepare a solution A having a tungsten content of 0.01M.

[Preparation of activator component solution] Diethyl aluminum chloride 1.8g Mixed monomer 500ml
Was mixed to prepare an aluminum component, and a 0.03 M solution B was prepared.

The molar ratios of DCP and 5-cyanonorbornene used as the monomer mixture in the solution were as follows.

After 10 ml of the catalyst component solution (Solution A) and 10 ml of the activator component solution (Solution B) were heated to a predetermined temperature, the above solution was sufficiently replaced with nitrogen and taken out into a syringe. Both liquids are simultaneously extruded from the syringe at a constant speed under rapid agitation in a glass flask with a stirrer and rapidly mixed, then a thermocouple is inserted by raising the stirrer, and 100 ° C from the time when the injection of the liquid is completed from the syringe. The time to reach was measured.

In addition, take out the solidified crosslinked resin and cut out the section TM
Method A-Softening point and swelling rate were measured in needle entry mode.
The results are summarized in the table below.

It can be seen that the copolymerization of 5-cyanonorbornene extends the time from the mixing to the time when the polymerization sufficiently occurs to reach the temperature of 100 ° C., and the initiation of the polymerization can be controlled.

With respect to the liquids having the compositions of Examples 3 and 4, the microminiature RIMs in which the liquids A and B were taken out into syringes and mechanically guided at a constant speed into an extrusion nozzle, where they were collision-mixed and poured into a mold. When it was molded using a machine, it was possible to mold a sturdy brown plate.

Then, 5 ml of each of the compositions of Examples 4 and 5 was taken and stirred under a nitrogen stream to prepare a premix, which was poured into a mold kept at 60 ° C. Got

Examples 7 to 8 Fumaronitrile and cyclopentadiene were reacted in diethyl ether, and purified 5,6-dicyanonorbornene (DCN) was recrystallized and purified to obtain a compound having a melting point of 98 to 99 ° C.

A catalyst component solution (solution A) and an activating component solution (solution B) were prepared in the same manner as in Example 1 except that the composition of the monomer was changed as shown in the following table. A resin molded product was obtained from these solutions A and B in the same manner as in Example 1. The mixing temperature and polymerization time at that time are also shown in the following table. From the table, it can be seen that the polymerization time becomes longer and the delay effect due to the cyano group appears.

Examples 9 to 16-Cyano-1,4,5,8-dimethano by reacting 5-cyanonorbornene with cyclopentadiene obtained by thermally dissociating commercially available dicyclopentadiene by a conventional method and further purifying by distillation. -1,4,4a, 5,6,7,8,8a-octahydronaphthalene (CDMON) was synthesized. Purity measurement by gas chromatography showed a purity of 99% or higher.

The composition of the monomers was changed as shown in the following table, and the activator component diethylaluminum chloride was used except that a mixture of equimolar concentrations of trioctylaluminum and dioctylaluminium iodide of 85:15 was used. 1
In the same manner as above, a catalyst component solution (solution A) and an activator component solution (solution B) having the compositions shown in the following table were prepared.

The solutions A and B were treated in the same manner as in Example 1 to obtain a cured resin molding in the flask. In the same manner as in Example 1, a sample was cut from the mixing temperature, the polymerization time and the molded product.
The results of softening point measurement and swelling ratio measurement by TMA are shown in the table below.

It can be seen that the softening point is improved as compared with the case of using the corresponding 5-cyanonorbornene.

Then, in the same manner as in Example 4, 5 ml each of the solutions A and B in Examples 11 to 14 was taken, stirred in a nitrogen stream to prepare a premix, which was poured into a mold kept at 90 ° C., Similarly, a brown cured molded product was obtained.

For the liquids having the compositions of Examples 9, 10, 15, and 16, Example 3 was used.
In the same manner as above, the liquid was taken out into the syringes A and B respectively, and it was mechanically extruded at a constant speed and guided into the nozzle, where it was cast into an ultra-compact RIM machine that can be poured into the collision mixed mold. A plate-like material could be molded.

Claims (1)

[Claims] 1. A method for obtaining a crosslinked polymer molded product by simultaneously performing bulk polymerization and molding of a metathesis polymerizable cyclic olefin compound containing dicyclopentadiene in the presence of a metathesis polymerization catalyst system, as a raw material monomer. Metathesis-polymerizable cycloalkenes containing at least 30 mol% of dicyclopentadiene, containing at most 9 mol% to 99.5 mol% and the balance consisting essentially of at least one norbornene derivative having 1 to 2 pendant cyano groups in the molecule A method for producing a crosslinked polymer molded article, which comprises using a monomer mixture.