JPS63152620A - Molded article of crosslinked polymer, production thereof and combination of reactive solution - Google Patents

Abstract

PURPOSE:To moderately control polymerization starting time and improve quality of molded articles, by the presence of a cyano group-containing norbornene derivative in obtaining a molded dicyclopentadiene based polymer article using a metathetic polymerization catalyst system. CONSTITUTION:A blend consisting of (A) a metathetic polymerizable cycloalkane containing >=30mol% dicyclopentadiene in a predominant amount - 99.5mol% and (B) the remainder of a norbornene derivative having 1 or 2 pendant cyano groups, e.g. 5-cyano-norbornene, etc., is polymerized in the presence of (C) a metathetic polymerization catalyst system consisting of a catalyst component, e.g. tungsten compound, etc., and an activating component, e.g. oranometallic compound, etc., in a mold to afford the aimed molded article. Furthermore, the catalyst component and activating component of the catalyst system (C) are normally added separately to divided blends of the monomers (A) and (B) and both are mixed in polymerization.

Description

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

b. Prior art Dicyclopentadiene (hereinafter sometimes abbreviated as "D CP") is a thermodynamically produced cyclopentadiene, which is one of the main components of the C5 fraction used to produce ethylene etc. by naphtha cracking. It can be obtained in the form of a dimer, which is more stable than before, and can be said to be an abundant petrochemical raw material.

DCP has conventionally been used as a raw material for obtaining petroleum resins and the like through thermal radical polymerization or cationic polymerization. However, recently, a technique has been developed in which two double bonds in the ring of DCP are subjected to open-roll polymerization using an olefin metasense polymerization catalyst system to obtain a molded body of a crosslinked polymer from DCP at once. reference). This technology uses the reaction molding method to easily obtain large molded products in one step from the aforementioned 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 metasense catalyst system used in the above reaction molding method is generally activated as a catalyst system by a combination of a transition metal salt catalyst such as tungsten, rhenium, or tantalum, and an organic total bending compound such as aluminum or tin to activate it. 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 in separately separated DCP, but by rapidly mixing them, the metasensitivity Polymerization is disclosed, reaction molding proceeds and molded products are obtained all at once.

In such a metasense catalyst system, both of the above components are highly reactive, and even if the reaction injection molding method described above is used, the reaction rate after mixing the two components is too fast.
It has been found that gelation may begin before the mixture is sufficiently poured 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 for a certain period of time, then pour it into the mold and heat it to harden, as the equipment is simpler, rather than reaction injection molding. I've come to understand.

It is known that the activity of such a metasense polymerization catalyst can be controlled by adding a Lewis space compound. However, when Lewis space is added to sufficiently adjust the degree of activation, it remains in the polymer, causing problems such as impairing the properties of the polymer and generating volatile components. . Therefore, the present inventor has arrived at the present invention as a result of intensive research into a method for overcoming such disadvantages.

The structure of the C3 invention, that is, the present inventor has discovered that when such Lewis space is contained in a monomer having metasense polymerizability and polymerized together, low molecular weight Lewis space does not remain, and the above-mentioned disadvantages are eliminated. We believe that it would be a win-win situation if the copolymerized Lewis space group could impart useful properties to the polymer, and as a result of research on such Lewis space group-containing monomers, we found that the cyano group was used as Lewis space. The present invention was completed by discovering that a norbornene derivative containing 1 to 2 is extremely suitable for the above purpose.

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

1. Majority of metasense polymerizable cycloalkenes containing at least 30 mol% of dicyclopentadiene - 9
A monomer mixture containing 9.5 mol % and the remainder consisting essentially of at least one norbornene derivative having 1 to 2 pendant cyano groups in the molecule is polymerized in the presence of a metasense polymerization catalyst system. A cross-linked polymer molded product.

2. A method for obtaining a crosslinked polymer molded product by polymerizing a metasense polymerizable cyclic olefin compound containing disilone pentadiene in the presence of a metasense polymerization catalyst system, the method comprising at least 30 mol% of dicyclopentadiene as a raw material monomer. Use a monomer mixture containing the majority of metasense polymerizable cycloalkanes to 99.5 mol%, with the remainder 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, characterized by:

3. (ω A reactive solution of a metasense polymerizable cyclic olefin containing a catalyst of a metasense polymerization catalyst system (solution A), mountain) A reactive solution of a metasense polymerizable cyclic olefin containing an activator of a metasense polymerization catalyst system (solution B) ), the metasense polymerizable cyclic olefins in solution A and solution B are metasense polymerizable dichloroflucanes whose combined composition contains at least 30 mol% of dicyclopentadiene. A reactive solution characterized in that it is a monomer mixture comprising a majority of 99.5 mol % and the remainder consisting essentially of at least one norbornene derivative having 1 to 2 pendant cyano groups in the molecule. combination.

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 do not inhibit the activity of the metasense catalyst system, and have metasense polymerizability. Preferably. The content of polar compounds such as alcohols, carboxylic acids, and carbonyl compounds that inhibit metasense polymerization is preferably as small as possible.

As the metasense polymerizable cycloalkenes used as a minor component together with DCP, those containing 1 to 2 metasense polymerizable cycloalkenes are generally used. Particularly preferred are those having norbornene type bonds.

Hydrocarbons are particularly preferred, and specific examples include cyclopentadiene-methylcyclopentadiene, 5-ethylidenenorbornene, 5-vinylnorbornene, 5-phenylnorbornene, 5-isobutylnorbornene, 1,4 , 5.8-dimethano-1,4,4a,
5゜8.8a-hexahydronaphthalene, tricyclo[
5,2,1,0]dec-5-ene, tricyclopentadiene, 1,4,5.8-dimethano-1,4,4a,5,
6,7,8゜8a-octahydomnaphthalene, 6-nitylidene-1,4,5,8-dimethano-1,4,4a,5
, 6,8.8a-hebutahydronaphthalene and the like. Regarding the cycloalkenes containing a petero atom, those containing a norbornene group are also preferable, and 5-
Examples include methoxycarbonyl-norbornenerubonylmethylnorbornene, hexamethylene-sunadiquimide, and the like.

The norbornene derivatives having one or two pendant cyano groups used in the present invention include those having at least one norbornene structural unit represented by the following formula.

(However, the valence in the formula may form a ring via another atom.) Therefore, in addition to the norbornene ring of the bicyclo structure, tricyclo and tetracyclo, for example, 1,4,5.8-dimethano-1.4 , 4a,5,6,7,8,8a-octahydrona may form a ring via other atoms), 1.4
-Methane-1.4.4a,5,6,7,8.8a-Octahydronaf A compound having 1 to 2 pendant cyano groups in the polycyclic olefin can be used as the 7mer of the present invention. Generally, those exhibiting a liquid state at 50° C. or lower are preferred.

Specific examples include the following.

5-cyano-norbornene 5-cyano-5-methylnorbornene 5.6-diatu norbornene 6-diatu 1.4,5,8. -dimethano-1,4,4
a, 5,6°7.8.8a-octahydronaphthalene 6
．． 7-dicyano-1,4,5,8-dimethano-1,4,
4a.

5.6,7,8.8a-Octahydronaphthalene 6-diatu 1,4-methano-1,4,4a,5,6,7,
8.8a-Octahydronaphthalene Such cyano group-containing norbornene derivatives are cyclopentadiene (which can be used in the reactor in the form of either cyclopentadiene or dicyclopentadiene) S
1 Acrylonitrile, malonitrile, fumaronitrile,
D 1els-A with 5-cyanonorbornene, 5,6-dicyanonorbornene, cyanedichlorohexene, etc.
It can be obtained in extremely high yield by a 1der reaction. Naturally, such cyano group-containing norbornene derivatives need to be sufficiently purified before use.

The proportion of DCP used in the metasense 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 cyano group-containing norbornene derivative varies depending on the molding method. As mentioned above, when trying to obtain a crosslinked molded product by reaction injection molding, the time from mixing solution A and solution B until the start of polymerization is sufficient for the liquid to flow into the mold. Therefore, the regulating effect of the cyano group-containing norbornene derivative may be small, and therefore, the range of 0.5 to 25 mol % is preferable. On the other hand, in the molding method that goes through a premix state, stability in the premix state is required to a certain extent, and therefore, 30 mol% to
A range of 45 mol% is preferred.

The composition of these seven-mer mixtures is solution A and solution B.
They do not necessarily have to be the same, and can be appropriately adjusted and used depending on the purpose, and it is sufficient that the combination of both falls within the above range.

The copolymerization effect of cyanogen-containing norbornenes is that in addition to the above-mentioned effect of adjusting the polymerization initiation time, the polarity of the crosslinked polymer obtained is also increased because the cyano group is highly polar, which increases the intermolecular force. In some cases, the secondary transition point is less likely to be lowered, and chemical resistance can also be improved. Also,
Since it is highly polar even in the monomer state, it has the advantage of being able to easily dissolve other monomers and additives that are solid at room temperature and do not dissolve in hydrocarbon cycloalkenes.

Salts such as halides such as tungsten, rhenium, and tantalum are used as catalyst components in the metasense polymerization catalyst system in the above-described molding method, 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. It is known that when such a tungsten compound is directly added to dicyclopentadiene, cationic polymerization starts immediately, which is not preferable.

Therefore, it is preferable to use such a tungsten compound by first suspending it in an inert solvent such as benzene, toluene, chlorobenzene, etc., and solubilizing it by adding a small amount of an alcoholic compound or a phenolic compound.

Furthermore, in order to prevent undesirable polymerization as described above, it is preferable to add about 1 to 5 moles of a Lewis base or a chelating agent per mole of the tankzusten compound. Such additives include acetylacetone and acetoacetic acid alkyl esters.

Examples include tetrahydrofuran and benzonitrile. As mentioned above, the cyano group-containing norbornenes used in the present invention are Lewis bases themselves, and often have this 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 active component in the metasense polymerization catalyst system is preferably an organometallic compound centered on alkylated metals of Groups 1 to Ⅰ of the Periodic Table, particularly tetraalkyltin, alkylaluminum compounds, and alkylalmonium halide compounds. Specifically, diethylaluminum chloride, ethylaluminum dichloride, trioctylaluminum, tetrabutyltin, etc. can be mentioned. The other solution (corresponding to solution B) is formed by dissolving the organometallic compound as the active ingredient in the mixed monomer.

In the present invention, a crosslinked polymer molded article can basically be obtained by mixing the solutions A and 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, other Lewis bases can be added.

For example, when a tungsten compound is used as a catalyst component, the ratio of the tungsten compound to the above-mentioned mixed monomers is about 1 on a molar basis.
000:1 to about 15,000:1, preferably around 2,000:1, and when an alkylaluminum is used as the active agent component, the ratio of the aluminum compound to the DCP mixed monomer is on a molar basis. about 100:1 to about 2000:1, preferably about 200:1 to about 50
A value around 0:1 is used. 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.

Rack 1 according to the present invention! In practical use, polymer molded products have
Various additives can be added to improve or maintain its properties. Such additives include fillers,
Pigments, antioxidants, light stabilizers.

Examples include polymer modifiers. Such additives cannot be added after the crosslinked polymer of the present invention has been molded, so if they are added, they must be added to the above-mentioned raw material solution in advance.

The easiest method is to use the solution A and solution B.
One method is to add it to either or both of them in advance, but in that case, it will not react with the highly reactive catalyst components or other active agent components in the liquid to a practical extent. In addition, it must not inhibit polymerization. If the reaction cannot be avoided, but coexistence does not substantially inhibit polymerization, it can be mixed with the monomer to prepare a third liquid and mixed and used immediately before polymerization. . In the case of a solid filler, in the case of a filler in a shape that can sufficiently fill the voids immediately before starting the polymerization reaction or during polymerization when both components are mixed, in the mold for forming, It is also possible to fill it.

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 surface-treated with so-called silane gobbler can also be suitably used.

Further, it is preferable to add an antioxidant to the cross-monopolymer molded article of the present invention, and therefore it is desirable to add a phenolic or amine antioxidant to the solution in advance. Specific examples of these antioxidants include 2.6-
t-Butyl-P-cresol, N,N'-diphenyl-P-phenylenediamine, tetrakis[methylene(
Examples include 3,5-di-butyl-4-hydroxycinnamate)]methane.

Moreover, the polymer molded article according to the present invention contains 1f of other polymers.
It can be added when the fi body is in a solution state. As a bending polymer additive, the addition of an elastomer is effective in increasing the impact resistance of the molded product and controlling the viscosity of the solution. Elastomers used for this purpose include styrene-butadiene-styrene. Triblock rubber, styrene-isoprene-styrene triblock rubber,
A wide range of elastomers can be mentioned, including polybutadiene, polyisoprene, butyl rubber, ethylene brobylene-dienter polymer, and nitrile rubber.

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 the catalyst system and monomer mixture are prepared in advance and the mixed premix is flowed into the mold, and the catalyst system is divided into two parts, solution Δ and solution B, into the head part. It is possible to use the RIM method, in which the mixture is mixed by collision and then poured directly into a mold. In either case, the injection pressure into the mold can be relatively low, so it is possible to use inexpensive molds.

Furthermore, although the polymerization reaction inside the mold is started, 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 easily released from molds 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 removability of the cyano group.

The molded product thus obtained can be used in various vehicles including automobiles.
It can be used in a wide range of applications, mainly large molded items, such as parts for pottery tools, housings for electrical and electronic wire types, etc.

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 1-6. Comparative Example Commercially available DCP was purified by distillation under reduced pressure in a nitrogen stream to obtain purified diclopentadiene without lowering its freezing point to 33.4°C.

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

On the other hand, heat the commercially available dicyclopentadiene! ! let me,
5-Cyanonorbornene was synthesized by reacting schifpentadiene (q) with acrylonitrile. It was purified by distillation, and the purity measurement by gas chromatography similarly showed a purity of 99% or more.

[Preparation of M medium component solution 1 20 g of tungsten hexachloride was added to 70 d of dry toluene under a nitrogen stream IIOL, then nonylphenol 21
g and 16 d of toluene to make 0.5 M
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 tungsten hexachloride and nonylphenol, thereby obtaining a polymerization catalyst.

10d of such solution, acetylacetone 1. Mix 500d of Ome mixed monomer, containing tungsten m 0.001
M solution A solution was prepared.

[Preparation of active ingredient solution 1 500d of diethyl aluminum chloride 0.189 mixed single Φ body was mixed to give an aluminum content of 0.003
Solution B of M was prepared.

The molar ratio of the mixed monomers DCP and 5-cyanonorbornene in this solution was as follows.

After bringing the above-mentioned solution to a predetermined temperature, 10 d of the catalyst component solution (solution A) and 10 m of the active agent component solution (solution B) were taken out into a syringe which was sufficiently replaced with nitrogen.

Both liquids were simultaneously extruded from the syringe at a constant speed into a glass flask equipped with a stirrer under rapid stirring, and after rapid mixing, the stirrer was raised, a thermocouple was inserted, and the temperature was 100°C from the time the liquid was injected from the syringe. The time it took to reach was measured.

Furthermore, the solidified crosslinked resin was taken out, a section was cut out, and the softening point and swelling rate were measured using the TMA method - needle penetration mode. The results are summarized in the table below.

It can be seen that the copolymerization of 5-cyanonorbornene lengthens the time from the time of mixing until polymerization sufficiently occurs and the temperature reaches 100°C, indicating that the initiation of polymerization can be controlled.

For the liquid having the composition of Example 3.4, use liquid A.

Each of B was taken out into a syringe, mechanically introduced at a constant speed into an extrusion nozzle, and molded by an ultra-compact RIMi that could be mixed by collision and poured into a mold.A brown, durable plate-like product was molded.

Next, 5 portions each of the liquids having the compositions of Examples 4 and 5 were taken and stirred under a nitrogen stream to create a premix, which was heated at 60°C.
When the mixture was poured into a mold held at a temperature, a similarly strong brown plate was obtained.

Example 7-8 Fumaronitrile and cyclopentadiene were reacted in diethyl ether, and purified 5,6-dicyazunorbornene (DCN) was purified by recrystallization to obtain a product with a melting point of 98 to 99°C.

A catalyst component solution (solution A) and an active agent component solution (solution B) were prepared in the same manner as in Example 1, with the composition of the monolayer body being changed as shown in the following table. Such solution A.

A resin molded product was obtained using B in the same manner as in Example 1, and the mixing temperature and polymerization time are also listed in the table below.

From the same table, it can be seen that as the polymerization time becomes longer, the retardation effect due to the cyano group appears.

Example 9-16 5-cyanonorbornene and cyclopentadiene obtained by thermally dissociating commercially available dicyclopentadiene were reacted in a conventional manner and further purified by distillation to produce 6-dia2-1.4,5.8- Dimethano-1,4゜4a,5,6,7
,8.8a-octahydronaphthalene (CDMON) was synthesized. Purity can be measured by gas chromatography 99
% or more purity.

Example 1 except that the composition of the single matrix was changed as shown in the table below, and the active ingredient diethylaluminum chloride was a mixture of equimolar concentrations of trioctylaluminum and dioctylaluminum iodide in a molar ratio of 85:15. In the same manner as above, a catalyst component solution (solution A) and an active agent component solution (solution B) having the compositions shown in the table below were prepared.

These solutions A and B were treated in the same manner as in Example 1 to obtain a cured resin molded product in a flask. In the same manner as in Example 1, the temperature during mixing was 1 polymerization time, and the sample was cut out from the molded product and the softening point was measured by TMA.

The results of measuring the swelling ratio are shown in the table below.

It can be seen that the softening point is improved compared to when the corresponding 5-cyanonorbornene is used.

Next, in the same manner as in Example 4, 5 d of each solution A and B in Examples 11-14 were taken and stirred in a nitrogen stream to create a premix, which was poured into a mold maintained at 90°C. Similarly, a brown cured molded product was prepared (q).

Regarding the liquid having the composition of Example 9.10.15.16, take out the liquid into each syringe of A and B in the same manner as in Example 3,
It was mechanically guided at a constant speed into an extrusion nozzle, where it was molded using an ultra-compact RIM machine that allowed it to be poured into a mold where it was collided and mixed, resulting in a brown, durable plate.

Claims (1)

[Scope of Claims] 1. Metasense polymerizable cycloalkenes containing at least 30 mol % of dicyclopentadiene with a majority of 99 to 99 mol %
．． obtained by polymerizing a monomer mixture containing 5 mol % and the remainder consisting essentially of at least one norbornene derivative having 1 to 2 pendant cyano groups in the molecule in the presence of a metasense polymerization catalyst system. Cross-linked polymer molded product. 2. A method for obtaining a crosslinked polymer molded product by polymerizing a metasense polymerizable cyclic olefin compound containing disilone pentadiene in the presence of a metasense polymerization catalyst system,
At least 3 dicyclopentadiene as a single raw material
A monomer containing a majority of metasense polymerizable cycloalkanes containing 0 mol% to 99.5 mol%, with the remainder 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, the method comprising using a mixture. 3. (a) A reactive solution of a metasense polymerizable cyclic olefin containing a catalyst of a metasense polymerization catalyst system (solution A), (b) A reactive solution of a metasense polymerizable cyclic olefin containing an activator of a metasense polymerization catalyst system ( Solution B), wherein the metasense polymerizable cyclic olefin in solution A and solution B is a metasense polymerizable cycloolefin whose combined composition contains at least 30 mol% dicyclopentadiene. Reactivity characterized by being a monomer mixture containing a majority of alkanes to 99.5 mol % and the remainder consisting essentially of at least one norbornene derivative having 1 to 2 pendant cyano groups in the molecule. Combination of solutions.