JPS6399206A - Molded article of crosslinked polymer, production thereof and combination of reactive solutions - Google Patents

Abstract

PURPOSE:To produce a molded article having excellent properties free from residual norbornene derivative in a polymer, by polymerizing a monomer mixture of a metathetic polymerizable cycloalkene and a pyridyl group-containing norbornene derivative in the presence of a catalyst. CONSTITUTION:A monomer mixture consisting of 90-99.9mol% metathetic polymerizable cycloalkene (e.g. 5-ethylidene norbornene, 5-polymerizable cycloalkene (e.g. 5-ethylidene norbornene, 5-methoxycarbonylnorbornene, etc.) containing >=30mol% dicyclopentadiene and 10-0.1mol% pyridyl group- containing norbornene derivative [e.g. 5-(4-pyridyl)norbornene, etc.] is polymerized in the presence of a metathetic polymerization catalyst system (e.g. catalyst consisting of tungsten compound, Lewis base and tetraalkyltin, etc.) to give the aimed molded article. A combination of (A) a solution of a cyclic olefin compound containing a catalyst of metathetic polymerization catalyst system and (B) a solution of a cyclic olefin compound containing an activator for the catalyst system is used as a reactive solution. In the cyclic olefins in the solutions, both the solutions are blended to give a composition equal to that of the monomer mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention relates to a new and improved crosslinked polymer molded product of a cyclopentadiene polymer, a method for producing the same, and a reactive solution therefor. More specifically, the present invention relates to a crosslinked polymer molded product obtained by bulk-combining dicyclopentadiene-containing monomers using a metathesis polymerization catalyst, a method for producing the same, and a reactive solution used therefor.

b. Conventional technology [Copentadiene (hereinafter sometimes abbreviated as "D CP") is prepared by cracking] -
Cyclopentadiene, which is one of the main components of the C5 fraction used to produce tyrene, etc., is obtained in the form of a thermodynamically more stable dimer, and can be said to be an abundant petrochemical raw material. .

Conventionally, DCP has been used as a raw material for obtaining petroleum resins and the like through thermal radical polymerization and cationic polymerization. but,
Recently, a technique has been developed in which the two dicar bonds in the ring of DCP are subjected to ring-opening polymerization using an A-lefin metathesis polymerization catalyst system, and a molded product of a crosslinked polymer is produced from DCP at once (for example, in JP-A-58 (Refer to Publication No.-129013). This technology uses the reaction molding method to easily produce large molded products in one step from the abundant petrochemical raw materials, and the molded products have excellent physical properties with a good balance of rigidity and impact resistance. It has industrial value in that it is

By the way, the metathesis catalyst system used in the reaction molding method described above is generally made of a combination of a transition metal salt catalyst such as tungsten, rhenium, tantalum, or molybdenum and an organometallic compound such as aluminum or tin to activate it. Activity is expressed. The above method takes advantage of this point, and polymerization does not start when both the catalyst component and the activator component are mixed together in separately separated DCP, but by rapidly mixing them. , metathesis polymerization is disclosed and devised so that reaction molding proceeds and molded products are obtained all at once.

In such a metathesis vehicle system, both of the above components are highly reactive, and even if the reaction injection molding method described above is adopted, the reaction rate after mixing the two components is too fast, resulting in insufficient molding. It has been found that gelation may begin before pouring into the mold, making it impossible to obtain a good molded product.

Furthermore, depending on the application, it may be more advantageous to mix the two liquids in a premix state, hold it for a certain period of time, and then flow it into the mold and heat it to harden, rather than reaction injection molding, since the equipment is inside the cylinder. I knew that there were many.

It is known that the activity of such a metathesis polymerization catalyst can be adjusted by adding a Lewis space compound. However, if such Lewis space is added in order to sufficiently control the degree of activation, it may remain in the polymer, causing problems such as impairing the properties of the polymer and generating volatile components. there were. Therefore, the inventor of the present invention has arrived at the present invention as a result of intensive research into methods for overcoming such disadvantages.

C9 The structure of the invention, that is, the present inventor has discovered that when such Lewis space is contained in a monomer having metathesis polymerizability and polymerized together, low molecular weight Lewis space does not remain in the polymer. The above inconvenience will disappear. Moreover, it would be a win-win situation if such a copolymerized Lewis space group could impart useful properties to the polymer.

Therefore, as a result of conducting research on such monomers containing a Lewis space group, it was found that a pyridyl group is suitable for this purpose as a Lewis space group.In other words, even a small amount of a norbornene derivative containing a pyridyl group has a large polymerization retardation effect. The present invention has been completed by discovering that it is extremely suitable for the above purpose.

That is, the present invention includes the following inventions (1) to (3).

(1) Metathesis-polymerizable cycloalkynes containing at least 30 mol% of dicyclopentadiene 90-99.
Norbornene derivative 10 having 9 mol% and pyridyl group
A cross-braided composite molded product obtained by polymerizing a monomer mixture consisting essentially of ~0.1 mol % in the presence of a metathesis polymerization catalyst system.

(2) In a method for obtaining a crosslinked polymer molded product by polymerizing a meta-12-cis-meritable cyclic olefin compound containing dicyclopentadiene in the presence of a metathesis polymerization catalyst system, dicyclopentadiene is used as a raw material monomer. characterized by using a monomer mixture consisting essentially of 90 to 99.9 mol% of metathesis-polymerizable cycloalkenes containing at least 30% of A method for producing a crosslinked polymer molded product.

(3) Consists of at least a) a reactive solution of a cyclic olefin compound containing a catalyst of a metathesis polymerization catalyst system (solution A) b) a reactive solution of a cyclic olefin compound containing an activator of a metathesis polymerization catalyst system (solution B) In the combination of reactive solutions, the cyclic olefin compounds in Solution A and Solution B have a combined composition of 90 to 99.9 mol of metathesis-polymerizable cycloalkenes containing at least 30 mol% of dicyclopentadiene. % and a monomer mixture consisting essentially of 10-0.1 mol % of norbornene derivatives having pyridyl groups.

The DCP used in the present invention is preferably highly purified. The DCP used in the present invention is generally DCPI
IT! It is preferred that the impurity is 95% or more, more preferably 97% or more, and that impurities do not inhibit the activity of the metathesis catalyst system, but have metathesis polymerizability. The content of polar compounds such as alcohols, carboxylic acids, and carbonyl compounds that inhibit metathesis polymerization is preferably as small as possible.

As the metathesis-polymerizable cycloalkenes used as a minor component together with DCP, those containing 1 to 2 metathesis-polymerizable cycloalkene groups are generally used. Particularly preferred are those having norbornene type bonds. Particularly preferred are hydrocarbons, and specific examples include cyclopentadiene-methylcyclopentadiene codimers.

5-ethylidenenorbornene, 5-vinylnorbornene, 5-phenylnorbornene, 5-isobutylnorbornene, 1,4,5.8-dimethano-1,4,4a,5
, 8.8a-hexahydro-naphthalene, 6-nitylidene-1.4,5.8-dimethano-1,4,4a,5,7,
8,8a-heptahydronaphthalene, tricyclo[5
, 2,1,Oldec-5-ene and the like. Among the cycloalkenes containing a hetero atom, those containing a norbornene group are preferred, and examples include 5-methoxycarbonyl-norbornene, 5-methoxycarbonyl-methylnorbornene, and 5-cyanonorbornene.

The norbornene derivative having a pyridyl group used in the present invention has a pyridyl group and a norbornene group at the same time, and has a bond that is otherwise inactive with respect to the metathesis polymerization catalyst system, and the above-mentioned metathesis polymerizable cycloalkene Any material can be used as long as it is miscible with 0.1% by mole or more.

Specific examples of this can include the following.

2.6-bis(5-norbornenyl)pyridine Such norbornene 11 can be obtained by a Diels-Alden reaction between cyclopentadiene and 4-vinylpyridine, 2-vinylpyridine, 2,6-dipynylpyridine, or the like. Naturally, such pyridyl group-containing norbornene derivatives require sufficient purification before use.

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

On the other hand, the preferred range of the ratio of the cycloalkenes to the pyridyl group-containing norbornene derivative varies depending on the molding method. As mentioned above, when attempting to obtain a crosslinked molded product by reaction injection molding, the time from mixing solution A and solution B to the start of polymerization should be sufficient for the liquid to flow into the mold. Therefore, the regulating effect on the norbornene derivative having a pyridyl group may be small, and therefore, in that case, the range of 0.1 to 0.5 mol% is preferable. On the other hand, in a molding method that involves a premix state, stability in the premix state is required to a certain extent or more, and therefore, in this case, the range of 0.5 mol % to 5 mol % is particularly preferable. In any case, an extremely large polymerization retardation effect can be exerted by using a very small amount.

The composition of these seven-mer mixtures does not necessarily have to be the same in solution A and solution B, and can be adjusted as appropriate depending on the purpose, and the composition of both solutions falls within the above range. It is good if there is.

As the catalyst component in the metathesis polymerization catalyst system in the above-described molding method, salts such as halides such as tungsten, rhenium, and tantalum are used, and tungsten compounds are particularly preferred. As such a tungsten compound, tungsten halide, tungsten oxyhalide, etc. are preferable, and more specifically, tungsten hekiliku[2]rite, tungsten oxyf[1-ride, etc.] are preferable. Such a tungsten compound is known to immediately start cationic polymerization when directly added to dicyclopentadiene, which is not preferable.

Therefore, such a tungsten compound is presuspended in an inert solvent such as benzene, toluene, chlorobenzene, etc.
It is preferable to solubilize it by adding a small amount of an alcoholic compound or a phenolic compound before use.

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 1 mole of the tungsten compound. Such converted products include acetylacetone and aceto acid-resistant alkyl esters.

Can be used to remove tetradidrofuran, benzonitrile, etc. The pyridyl group-containing norbornene derivative used in the present invention is itself a Lewis base as described above, and often has its effect even without the addition of any of the above compounds.

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

On the other hand, the activation inhibitor component in the metathesis polymerization catalyst system is preferably an organometallic compound centered on a fullylated metal of Groups 1 to 2 of the periodic table, particularly a tetraalkyl tin, an alkyl aluminum compound, or an alkyl aluminum halide compound. Specifically, salt or diethylaluminum, di-salt or ethylaluminum, tri-Aquadylaluminum, tetrabutyltin, etc. can be mentioned. The other solution (corresponding to solution B) is formed by dissolving these organometallic compounds as active inhibitor components in the monomer mixture.

In the present invention, the crosslinked vehicle is basically assembled by mixing the solution A and the JD solution B. ! 1!71, but since the pyridyl group-containing norbornene derivative has a regulating effect on the reaction rate, it is possible to cure with stable streaking.

The amount of the metathesis polymerization catalyst system to be used is, for example, when a tungsten compound is used as a catalyst component, the ratio of the tungsten compound to the monomer mixture is about 1,000:1 to about 15,000:1, preferably 2,000:1 on a molar basis.
When the activator component is an alkyl aluminum, the ratio of the aluminum compound to the monomer mixture is about 100:1 on a molar basis.
~about 2000:1, preferably about 200:1 to about 500
A value around 1 to 1 is used. Furthermore, the masking agent and regulating agent as described in (e) above can be appropriately adjusted and used depending on the use of the above-mentioned catalyst system through experiments.

In order to improve or maintain the properties of the crosslinked polymer molded product according to the present invention, various (f additives n1) can be added to the crosslinked polymer molded product according to the present invention. Examples of such additives include fillers, pigments, Antioxidants, light stabilizers.

There are 1v1 molecule improvers, etc. This J: eel additive is
Since it is impossible to add it after one polymer of the present invention has been formed, it is necessary to add it to the above-mentioned raw material +21 solution in advance when adding it.

The easiest method is to use the solution A and solution B.
Is there a method in which it is added in advance to either or both of the following? In that case, it does not react with the highly reactive catalyst component or deactivator component in the liquid to a practical extent, and It must not inhibit polymerization. If the reaction cannot be avoided, but coexistence does not substantially inhibit polymerization, it is also possible to mix it with the monomer to prepare a third liquid and use it immediately before polymerization. . In addition, in the case of a solid filler, when both components are mixed and the shape is such that the voids can be sufficiently filled immediately before starting the polymerization reaction or during polymerization, it is necessary to It is also possible to fill it up.

Additive reinforcements or fillers are effective in improving the flexural modulus. Examples of such materials include glass fiber, mica, carbon black, and wollastonite. Those surface-treated with a so-called silane coupler 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-phenylenecyamine, tetrakis[methylene (3,
5-di-t-ablu 4-hydroxycinnamate)]
Examples include methane.

Furthermore, the polymer molded product according to the present invention can be prepared by adding the same polymer in the form of a monomer solution. The addition of an elastomer as such a polymer additive is effective in increasing the impact resistance of the molded product and in controlling the viscosity of the solution. Elastomers used for this purpose include styrene-butadiene-methylene triblock rubber,
Styrene-isoprene-styrene rib [Tsuku rubber,
A wide range of elastomers can be mentioned, including polybutadiene, polyisoprene, butyl rubber, ethylene propylene-genterpolymer, and nitrile rubber.

The 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 uses a catalyst system and a single FF1K.
There is a resin injection method in which a premix containing the ff compound is flowed into the mold, and a RIM method in which the catalyst system is divided into two parts (solution A and solution B are collision-mixed in the head and poured directly into the mold). You can take it.

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 and the polarity of the pyridyl group.

The molded product thus produced can be used in a wide range of applications, mainly large-sized molded products, such as parts for various transportation equipment including automobiles, and housings for electrical and electronic devices.

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 limited thereto.

Examples 1-5. Comparative Example Commercially available DCP was purified by distillation under reduced pressure in a nitrogen stream to obtain purified dicyclopentadiene 17, which had a freezing point of 33.4°C. Gas chroma 1 - 99 in l114 measurement by graph
% or more purity.

On the other hand, 5-(4-pyridyl)norbornene was synthesized by thermally dissociating commercially available dicyclopentadiene to obtain cyclopentadiene, which was then reacted with 4-vinylpyridine. It was purified by distillation and measured once every second using a gas chromatograph, and similarly showed a purity of 99% or more.

[Preparation of catalyst component solution] 20 g of hexasalt or tungsten was added to dry toluene 7 (7) under a nitrogen stream, and then a solution consisting of nonylphenol 21 (J) and toluene 161 dl was added to give a 0.5M solution.
A tungsten-containing catalyst solution was prepared, and this solution was purged with nitrogen gas overnight to remove the hydrogen chloride gas purified by the reaction between hexasalt or tungsten and nonylphenol, thereby obtaining a polymerization catalyst.

10 d of such solution, 1.0 d of acepulacetone and 500 d of monomer mixture were mixed, and the tungsten content was 0.00.
A 1 M solution A was prepared.

[Preparation of activator component solution] 0018 g of diethyl aluminum chloride and 500 m of mixed human body were mixed to give an aluminum content of 0.0
03M solution B was prepared.

The ratio of DCP and pyridyl group-containing norbornene in the monomer mixture in this solution was as follows.

10 d of the catalyst component solution (solution A) and 10 d of the activator component solution (solution B) were brought to a predetermined temperature, and then taken out into a syringe which had been sufficiently purged with nitrogen. Both liquids were simultaneously extruded from the syringe at a constant speed into a glass flask with a stirrer under rapid stirring, and after rapid mixing, the stirrer was raised and a thermocouple was inserted, and the temperature was raised to 100 °C from the time the liquid was injected from the syringe. The time reached was measured.

Furthermore, the solidified crosslinked resin was taken out, cut into sections, rapidly heated to 280°C in a nitrogen stream, and then treated.
The softening point was measured in the Chisel immersion mode. The swelling ratio was also measured on another sample. The results are summarized in Table 1.

It can be seen that due to the copolymerization of 5-(4-pyridyl)norbornene, the time from the time of mixing until the polymerization sufficiently occurs and the temperature reaches 100° C. is extended, and the initiation of polymerization can be controlled.

Regarding the liquid having the composition of Example 1, the liquid was taken out into syringes A and B, and mechanically extruded at a constant speed (
When the mixture was molded using an ultra-compact RIM machine that introduced it into a nozzle, mixed it by collision, and then poured it into a mold, a brown, durable plate-like product was molded.

Next, 5 d each of the liquids having the compositions of Examples 2 and 3 were taken and stirred under airflow on the chamber floor to create a premix, which was poured into a mold kept at 90°C, and a similarly strong brown plate was formed. I got it.

Table 1 Measurements were taken after immersion in this toluene.

Claims (1)

[Scope of Claims] 1. Metathesis-polymerizable cycloalkenes containing at least 30 mol% of dicyclopentadiene 90-99.9
Norbornene derivative with mol% and pyridyl group 10~
A crosslinked polymer molded product obtained by polymerizing a monomer mixture that is more practical than 0.1 mol % in the presence of a metathesis polymerization catalyst system. 2. A method for obtaining a crosslinked polymer molded product by polymerizing a metathesis-polymerizable cyclic olefin compound containing dicyclopentadiene in the presence of a metathesis polymerization catalyst system, which contains at least 30% dicyclopentadiene as a raw material monomer. Metathesis-polymerizable cycloalkenes 90
A method for producing a crosslinked polymer molded article, characterized in that a monomer mixture consisting essentially of 99.9 mol % and 10 to 0.1 mol % of a norbornene derivative having a pyridyl group is used. 3. A reaction consisting of at least a) a reactive solution of a cyclic olefin compound containing a catalyst of a metathesis polymerization catalyst system (solution A); and b) a reactive solution of a cyclic olefin compound containing an activator of a metathesis polymerization catalyst system (solution B). In the combination of the cyclic olefin compounds in solution A and solution B, the combined composition of both solutions is 90 to 99.9 mol % of metathesis-polymerizable cycloalkenes containing at least 30 mol % of dicyclopentadiene. A reactive solution combination characterized in that it is a monomer mixture consisting essentially of 10 to 0.1 mol % of a norbornene derivative having a pyridyl group.