JPH0778114B2 - Method for producing crosslinked polymer molding and combination of reactive solution - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a novel crosslinked polymer molded article obtained by metathesis polymerization and a combination of reactive solutions. More specifically, a polycyclic metathesis polymerizable monomer having a norbornene structure and an aryl substituent in one molecule is
The present invention relates to a method for producing a crosslinked polymer molded product by simultaneously performing polymerization and molding by bulk polymerization using a metathesis polymerization catalyst system, and a combination of reactive solutions therefor.

b. Prior Art It is known that cyclic olefins give polymers by means of metathesis polymerization catalysts. By the way, cyclopentadiene, which is one of the main components of the C ₅ fraction during naphtha cracking, is inexpensively separated as a thermodynamically more stable dimeric dicyclopentadiene (hereinafter abbreviated as “DCP”). It

Therefore, there have been many attempts to obtain useful polymers by applying a metathesis polymerization catalyst system to this DCP, but DCP has two rings capable of metathesis polymerization with different reactivity. Therefore, since the polymer inevitably undergoes cross-linking, a useful thermoplastic material was not obtained. Therefore, polymerization is performed in bulk and liquid DCP is used.
It was proposed that a crosslinked polymer molded product be obtained in a single step by pouring it into a mold as it is and carrying out polymerization and molding in a single step (see, for example, JP-A-58-129013).

However, the cross-linked polymer molded product obtained by this method has a softening point of 100 ° C. or lower, and it has been found that one having higher heat resistance is desirable for use in a wide range of applications including automobile applications. I came. Further, it has been found that it is desirable that the above-mentioned monomer is improved in fluidity at the time of molding since gelation is initiated in the initial stage of polymerization.

Therefore, the present inventor arrived at the present invention as a result of earnest research to obtain a polymer molded article having a wider application range by using easily available raw materials.

C. Structure of the Invention That is, the present inventor exists in the structural unit of DCP,
Focusing on the norbornene structure, which is a group that facilitates metathesis polymerization, a polycyclic metathesis polymerizable monomer having one such norbornene structure and one or two aryl (aromatic) rings that are rigid substituents in the molecule It has been found that an excellent polymer can be obtained by using it as at least all or part thereof.

Since such a polycyclic metathesis polymerizable monomer can be easily obtained by a Diels Alder addition reaction of an unsaturated compound having an aromatic group, for example, styrene and cyclopentadiene, it is a compound which is very easy to industrially utilize.

The present invention has been achieved based on such findings and includes the following inventions.

(1) In the method of bulk-polymerizing a metathesis-polymerizable monomer in the presence of a metathesis polymerization catalyst system to obtain a crosslinked polymer molded product, in a molecule, one norbornene structure and an aryl substituent are used as raw material monomers. Using a monomer consisting essentially of at least one polycyclic metathesis polymerizable monomer having 1 or 2 or a mixture of said monomer and at least one other metathesis polymerizable monomer,
Moreover, a method for producing a crosslinked polymer molded article, characterized in that polymerization and molding are carried out simultaneously.

(2) a) a reactive solution of a metathesis polymerizable monomer containing at least a catalyst component of a metathesis polymerization catalyst system (solution A); and b) reaction of a metathesis polymerizable monomer containing at least an activator component of a metathesis polymerization catalyst system. A solution (solution B) in a combination of at least a reactive solution, as the metathesis polymerizable monomer in the solution A and the solution B,
Both liquids are combined and at least one polycyclic metathesis polymerizable monomer having one norbornene structure and one or two aryl substituents in one molecule or at least one of the monomer and another metathesis polymerizable monomer. A combination of reactive solutions for the production of a crosslinked polymer molding, characterized in that a raw material monomer consisting essentially of a mixture of

The polycyclic metathesis polymerizable monomer used in the present invention can be represented by the following general formula (I).

Such a polycyclic metathesis-polymerizable monomer can be generally obtained by the Diels Alder reaction between cyclopentadiene and an aromatic adduct having a non-aromatic unsaturated bond as described above.

In order to obtain the polymer molded product of the present invention, it is necessary to react it in a liquid state, and as a monomer mixture, at least 80 ° C.
Hereafter, it is preferably liquid at 50 ° C. or lower.

Specific examples of such polycyclic metathesis polymerizable monomer include the following.

5-phenyl norbornene 5-phenyl-5-methylnorbornene 5-phenyl-6-methylnorbornene 5,6-diphenylnorbornene 5- (p-toluyl) norbornene 1,4-methano-1,1a, 4,4a-tetrahydrofluorene 6-phenyl-1,4,5,8-dimethano-1,4,4a, 5,6,7,8,8a
-Octahydronaphthalene 5- (1-naphthyl) norbornene 1,4,5,11-Dimethano-1,1, a, 4,4a, 5,5a, 10,10a-octahydrobenzofluorene These polycyclic metathesis-polymerizable monomers may have impurities having the same metathesis-polymerizability even if they exist to some extent, but it is preferable that they contain no other impurities as much as possible. In particular, a polar inhibitor that serves as a metathesis polymerization catalyst inhibitor is preferably as low as possible in content.

In the present invention, in addition to the above polycyclic metathesis polymerizable monomer, another metathesis polymerizable monomer may be copolymerized and used. Such other metathesis-polymerizable monomer has metathesis-polymerizable property, and is capable of performing metathesis polymerization as a monomer solution with the polycyclic metathesis-polymerizable monomer without any trouble and is miscible Anything can be used.
This monomer is generally added for the purpose of reducing the cost of the polymer molded product or improving the performance.

For the former purpose, dicyclopentadiene (DCP) is most suitable. Since DCP can be used as an inexpensive monomer as described above, a polymer molded product having excellent practicability can be obtained by combining it with the polycyclic metathesis polymerizable monomer.

Also, as an example of another metathesis polymerizable monomer, DCP
Other than that, specific examples include those having the following norbornene units.

Dihydrodicyclopentadiene, cyclopentadiene-
Methylcyclopentadiene co-dimer, 5-ethylidene norbornene, 1,4-methano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 1,4,5,8-dimethano-1 , 4,4a, 5,6,7,
8,8a-octahydronaphthalene, 6-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] trideca-5,11
-Diene, norbornadiene, tricyclopentadiene On the other hand, having a different element such as oxygen and nitrogen, and having polarity,
The metathesis-polymerizable monomer having an ether group, an ester group, a cyano group, or an N-substituted imide group has a function of controlling the initiation rate of the metathesis polymerization reaction, and a polar group is added to the formed polymer molded product. It has effects that can be introduced, and can be added when those effects are required.

Examples of such polar monomers include (5-norbornenyl)
Methyl-phenyl ether, bis [(5-norbornenyl) methyl] ether, 5-methoxycarbonylnorbornene, 5-methoxycarbonyl-5-methyl-norbornene, 5 [(2-ethylhexyloxy) carbonyl]
Norbornene, ethylene-bis (5-norbornenecarboxylate), 5-cyanonorbornene, 6-cyano-1,4,5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydro Naphthalene, N-butyl nadic acid imide, 5-
(4-pyridyl) -norbornene and the like can be mentioned.

Also in the above-mentioned metathesis polymerizable monomer for copolymerization, the content of impurities that inhibit the metathesis polymerization catalyst is preferably as small as possible.

The amount of the copolymerization monomer used is generally in the range of 0 to 97 mol%, that is, in the present invention, the polycyclic metathesis polymerizable monomer is used as a main component and, rather, as a minor component. Includes both.

As described above, the polycyclic metathesis-polymerizable monomer of the present invention has a norbornene ring having high metathesis polymerizability and a rigid aryl substituent, so that a rigid substituent is present in the polymer to be produced. Characterized by

Therefore, it is effective in adjusting the rigidity of other metathesis polymers to improve the heat resistance, and in that case, the use ratio of about 3 mol% may be sufficient.

For example, when used in combination with a hydrocarbon-based metathesis polymerizable monomer such as dicyclopentadiene, ethylidene norbornene, norbornene, the polycyclic metathesis polymerizable monomer is used in an amount of 3 to 50 mol%, more preferably 10 to A range of 30 mol% is practically used.

On the other hand, when the polar copolymerizable monomer is used for the purpose as described above, the range of 2 to 30 mol% in the total monomer is generally used. The use ratio is as described above, but it is necessary to determine the optimum point by a test for each suitable use range according to the purpose.

The metathesis polymerization catalyst system used to obtain polymer moldings in the present invention generally comprises two components, a catalyst component and an activator component, as is known.

In order to apply such a catalyst system to bulk polymerization, an activator component is first added to a monomer, and then a catalyst component is added and polymerization is initiated, and a process is performed until gelation occurs and a molded product is obtained. Inversely, a method of adding a catalyst component and an activator component at the same time to obtain a molded product can be employed.

However, the metathesis polymerization reaction is generally an exothermic reaction, and once the polymerization is started, the system is further heated to accelerate the reaction, and the reaction is completed at a very high speed. In many cases, it is difficult to shape large molded products.

Therefore, as described above, two solutions, that is, a solution mainly composed of a monomer and a catalyst component (solution A) and a solution mainly composed of a monomer and an activator component (solution B) are prepared in advance and subjected to collision mixing (RIM method). ) Or a static mixer, rapid mixing, immediate injection into a mold, shaping, and then curing in the mold can be suitably used.
In that case, the composition of the monomer does not have to be the same in both liquids, and can be arbitrarily changed depending on the function of the monomer. For example, when using the function as a polymerization initiation regulator by copolymerizing the polar copolymerization monomer, it is possible to add a large amount to the solution (B).

Salts such as halides of tungsten, rhenium, tantalum, molybdenum and the like are used as a catalyst component in the metathesis polymerization catalyst system, but a tungsten compound is 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. Further, organic ammonium tungstate or the like can also be used. It has been found that such a tungsten compound immediately starts cationic polymerization when added directly to the monomer, which is not preferable. Therefore, the tungsten compound is preferably suspended in an inert solvent such as benzene, toluene, chlorobenzene or the like in advance and solubilized by adding a small amount of an alcohol compound or a phenol compound before use.

Further, as described above, in order to prevent undesired polymerization, it is preferable to add about 1 to 5 mol of Lewis base or chelating agent to 1 mol 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 be a Lewis base itself as described above, and may have its action even if the above compound is not added.

Thus, the monomer solution containing the catalyst component (solution A) is
It 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, Specific examples include diethyl aluminum chloride, diethyl aluminum chloride, trioctyl aluminum, dioctyl aluminum iodide, and tetrabutyl tin. The other solution (corresponding to solution B) is formed by dissolving the organometallic compound as the activator component in the raw material monomer.

In the present invention, a crosslinked polymer molded article can be obtained basically by mixing the solution A and the solution B, but with the above composition as it is, the polymerization reaction is initiated very quickly, Since the curing sometimes occurs before it sufficiently flows into the casting mold, it often causes a problem, and therefore it is preferable to use the activity control agent.

As such a regulator, Lewis bases are generally used, and ethers, esters, nitriles and the like are used. Specific examples include ethyl benzoate, butyl ether, diglyme and the like. Such regulators are generally used by adding them to the solution side of the organic compound activator component. When a monomer having a Lewis base 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 the catalyst component, the ratio of the tungsten compound to the raw material monomer is about 10 on a molar basis.
The ratio is about 00: 1 to 15000: 1, preferably about 2000: 1, and when an alkylaluminum is used as the activator component, the ratio of the aluminum compound to the raw material monomer is approximately on a molar basis. Around 100: 1 to about 2000: 1, preferably about 200: 1 to about 500: 1 is used. Further, as described above, the masking agent and the regulator can be appropriately adjusted and used depending on the amount of the catalyst system used by experiments.

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

The easiest method is the solution A and the solution B.
It is possible to cite a method of adding it to either or both of them in advance, but in that case, it does not react to a certain extent with the catalyst component or the activator component having strong reactivity in the liquid, and to a certain extent, and It must not interfere with polymerization. In any case, if the reaction is unavoidable but coexistence does not substantially inhibit the polymerization, it can be mixed with a monomer to prepare a third liquid, and mixed and used immediately before the polymerization. . In the case of a solid filler,
It is also possible to fill the mold for molding in a shape in which the voids can be sufficiently filled just before the polymerization reaction is started or during the polymerization by mixing the two components.

Reinforcing agents or fillers as additives are effective in improving the bending modulus. Examples of such materials 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, 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. Examples of elastomers used for this purpose include a wide range of elastomers such as styrene-butadiene-styrene triblock rubber, styrene-isoprene-styrene triblock rubber, polybutadiene, polyisoprene, butyl rubber, ethylene propylene-dienta-polymer and nitrile rubber. Can be done.

The crosslinked 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.

Since the molded product has an oxide layer on the surface, it has good adhesion to commonly used paints such as epoxy and polyurethane.

d. Effect of the invention The molded product thus obtained has excellent heat resistance and can be used in a wide range of applications, mainly for large molded products such as parts 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 is not limited thereto.

Examples 1 to 10 and Comparative Example [Preparation of raw material monomer] Commercially available DCP was purified by distillation in a nitrogen stream under reduced pressure to give a freezing point of 3
Purified dicyclopentadiene showing 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-phenylnorbornene (PNB) was synthesized by a method of reacting styrene with this, and 5,6-diphenylnorbornene (DPNB) was synthesized by a method of reacting stilbene.

These compounds were purified by distillation, and the purity was 99% or more when measured by gas chromatography.

Further, (5-norbornenyl) methyl phenyl ether (NMPE) was obtained by the reaction of allyl phenyl ether and cyclopentadiene.

[Preparation of Catalyst Component Solution] 20 g of tungsten hexachloride was added to 70 ml of dry toluene under a nitrogen stream, and then a solution of 21 g of nonylphenol and 16 ml of toluene was added to prepare a 0.5 M tungsten-containing catalyst solution. On the other hand, nitrogen gas was purged overnight to remove hydrogen chloride gas generated by the reaction between tungsten hexachloride and nonylphenol, to obtain a polymerization catalyst.

10 ml of such solution, 1.0 ml of acetylacetone monomer mixture 50
0 ml was mixed to prepare a solution A having a tungsten content of 0.01M.

[Preparation of Activator Component Solution] Trioctylaluminum 85, dioctylaluminum iodide 15, and diglyme 300 were prepared at a ratio of 500 ml, and 500 ml of a mixed monomer was mixed to prepare a 0.03 M solution B as an aluminum component.

The molar ratios of DCP, ethylidene norbornene, cyclopentadiene-methylcyclopentadiene co-dimer, 5-phenylnorbornene and 5,6-diphenylnorbornene used in the monomer mixture in this solution were as follows.

The above solution was heated to a predetermined temperature with 10 ml of the catalyst component solution (solution A) and 10 ml of the activator component solution (solution B), and the contents of the syringe were sufficiently replaced with nitrogen and taken out. Both liquids are simultaneously extruded into the glass flask with a stirrer at a constant speed from such a syringe under rapid stirring, and after rapid mixing, the stirrer is raised and a thermocouple is pushed in. The time reached was measured.

Further, the solidified cross-linked resin was taken out and cut into pieces to measure the softening point in a nitrogen stream in the TMA method-needle penetration mode.
The swelling rate was measured with another sample. The results are summarized in Table 2.

Copolymers of PNB with 10 to 30 mol% of DCP have been obtained as a polymer having improved heat resistance and well-balanced performance. It can be seen that a polymer having an excellent chain-like property was obtained in the portion where PNB was abundant. Further, by using a copolymerizable monomer of a norbornene derivative having a polar group such as an ether group as in Example 10, the start of the polymerization reaction is delayed,
It turns out that molding via premix is possible.

With respect to the liquids having the compositions of Examples 1 to 9, a microminiature RIM in which the liquids are taken out into each of A and B syridines, mechanically guided at a constant speed into an extrusion nozzle, where they are 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 each of the liquid of the composition of Example 10 was stirred under a nitrogen stream to prepare a premix, which was poured into a mold kept at 90 ° C. to obtain a similarly strong brown plate. .

Examples 11-23 By the reaction of indene with cyclopentadiene, 1,4-
Methano-1,1a, 4,4a-tetrahydrofluorene (MTHF)
And cyclopentadiene-added 1,4-5,11-
Dimethano-1,1a, 4,4a, 5,5a, 10,10a-octahydrobenzofluorene (DMBF) was synthesized.

After distilling and purifying these compounds, a monomer mixture as shown in Table 3 was prepared, and a catalyst component solution and an activator component solution were prepared in the same manner as in Example 1 and polymerized in the same manner to give a crosslinked polymer molded product. Obtained. Table 4 shows the measurement results of the polymerization rate and the softening point and swelling ratio of the crosslinked polymer molded product.

It can be seen that the polymers from MTHF and DMBF show excellent heat resistance, and they do not fall even when copolymerized with DCP, and have high heat resistance in a very wide range.

A liquid having the composition of Example 15 was added to A, B as in Example 1.
The solution was molded by an ultra-compact RIM machine capable of collision mixing, and a brown, tough, plate-like crosslinked polymer molded product was obtained.

Claims (2)

[Claims] 1. A method for bulk-polymerizing a metathesis-polymerizable monomer in the presence of a metathesis polymerization catalyst system to obtain a crosslinked polymer molding, wherein as a raw material monomer, one norbornene structure is substituted with aryl in a molecule. Group 1 or 2
Of at least one polycyclic metathesis polymerizable monomer having 1
Of a cross-linked polymer molded article, characterized in that a monomer substantially consisting of a seed or a mixture of the monomer and at least one other metathesis polymerizable monomer is used, and the polymerization and the molding are simultaneously carried out. Method. 2. A reactive solution (solution A) of a metathesis polymerizable monomer containing at least a catalyst component of a metathesis polymerization catalyst system, and b) a metathesis polymerizable monomer containing at least an activator component of a metathesis polymerization catalyst system. In the combination of at least the reactive solution consisting of the reactive solution (solution B), as a metathesis polymerizable monomer in the solution A and the solution B, both solutions are combined and one norbornene structure is substituted in one molecule with an aryl group. A raw material monomer which is substantially composed of at least one polycyclic metathesis polymerizable monomer having one or two groups or a mixture of the monomer and at least one other metathesis polymerizable monomer. A combination of reactive solutions for the production of crosslinked polymer moldings.