JPS633017A - Molded article of crosslinked polymer, production thereof and combination of reactive solution - Google Patents

Abstract

PURPOSE:To obtain a molded article of a crosslinked polymer suitable as an automobile part, etc., by mixing dicyclopentadiene with 5- alkylidenebicyclo[2,2,1]hept-2-ene at a specific ratio and polymerizing the obtained monomer mixture in the presence of a metathesis polymerization catalyst. CONSTITUTION:A monomer mixture composed of 99-50mol% dicyclopentadiene (preferably purified to >=97% purity) and 1-50mol% 5- alkylidenebicyclo[2,2,1]hept-2-ene {preferably highly purified 5- ethylidenebicyclo[2,2,1]hept-2-ene} is divided into two portions at an arbitrary ratio and the portions are dissolved in a solution containing a catalyst of metathesis polymerization catalyst system (preferably tungsten hexachloride, etc.) and a solution containing an activation agent for the metathesis polymerization catalyst system (preferably diethylaluminum chloride, etc.), respectively. Both solutions are quickly mixed together, poured into a mold and formed by polymerization to obtain the objective molded article of crosslinked polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an improved new 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 polymerization of a monomer containing dicyclopentadiene using a metathesis polymerization catalyst, a method for producing the same, and a reactive solution used therefor.

Conventional technology Dicyclopentadiene (hereinafter sometimes abbreviated as "D CP") is a thermodynamic compound of cyclopentadiene, which is one of the main components of the C5 fraction when producing ethylene etc. by naphtha clubking. It is obtained in the form of a more stable dimer, 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 ring-opening polymerization using an olefin metathesis 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 metathesis catalyst system used in the reaction molding method described above is generally made by combining a transition metal salt catalyst such as tungsten, rhenium, or tantalum with a specific metal compound such as aluminum or tin to activate the catalyst. The activity is expressed as The above method utilizes this point, and although polymerization does not start when both the catalyst component and the activator component are mixed in separately separated DCP, metathesis can be carried out by rapidly mixing the two components. Polymerization is disclosed, reaction molding proceeds and molded products are obtained all at once.

In such a metathesis catalyst system, both of the above-mentioned components are highly reactive, easily reacting not only with oxygen and water but also with other polar components in the hexamer, making them highly reactive as catalysts. It is known to cause loss of ability. Therefore, DCP used as a monomer in such a reaction molding method is
It is necessary to remove impurities that inhibit such metathesis catalyst systems, and since it is extremely difficult to selectively remove only such catalysts, DCP with a higher degree of purification is generally used. It will be done. By the way, as the degree of purification of DCP is increased, the freezing point becomes higher than 33°C. Although the freezing point is lowered to some extent by dissolving the catalyst system components as a polymerization reaction liquid for reaction molding, the freezing point as a liquid often reaches 20°C or higher, and when it reaches the freezing point or slightly lower. It has been found that there is a problem in that the reaction solution freezes and cannot be used as it is as a liquid reaction solution.

On the other hand, in the polymerization reaction solution, each component is extremely active even when the catalyst system components are separated into two solutions, and it has been found that the activity decreases within a relatively short period of time at temperatures above 30°C. It has also become clear that it is difficult to constantly warm the polymerization reaction solution and keep it in a liquid state so that it can be used immediately. In other words, when preparing the reaction liquid for reaction molding, it is not necessary to dissolve it at h0 temperature immediately before use, which is a very troublesome problem in practice. found.

As a countermeasure, it is possible to add a component that does not inhibit the activity of the catalyst system in order to lower the freezing point of DCP, but if the component does not polymerize and remains in the crosslinked polymer molded product as a low molecular component, This may impair the properties of the polymer molded product, make it more likely to catch fire, and cause various other problems.

Therefore, the present inventor discovered that the material is liquid at room temperature and can cause freezing point depression by mixing with DCP, and
We conducted intensive research to find a compound that has metathesis polymerizability and can be copolymerized with DCP.

Furthermore, in the case of the metathesis polymerization of DCP mentioned above, the polymerizability is at a level that can be used for practical purposes, but depending on the conditions, monomers may remain and have a unique depth. It is desired that the above-mentioned copolymerization compound has stronger polymerizability.

The present inventor conducted extensive research in order to find a compound for copolymerization with DCP that can satisfy this requirement in addition to the above requirements.

Structure of the invention That is, the present inventor has discovered that 5-alkylidenebicyclo[2,2,1]hept-2-
We focused on E (hereinafter sometimes abbreviated as "A B H").

R+ [However, in the formula, R+ and R2 represent a hydrogen atom or an alkyl group having 3 or less carbon atoms, but R+ and R2 are never hydrogen atoms at the same time. j The compound represented by the general formula [I] has a 5-fulkiritan norbornene ring that is more strained than a normal norbornene ring, and is expected to have strong metathesis polymerizability. However, it has a -direction acyclic olefin group, and if this group were to participate in the metathesis reaction, it would act as a terminal capping agent, and there was a fear that it would be difficult to obtain a sufficiently high polymer.

However, when the present inventors actually carried out metathesis polymerization, they found that most of the metathesis reaction did not occur, although this is thought to be due to steric hindrance because the acyclic olefin group is substituted with at least three alkyl groups. It has been found that the norbornene ring does not participate in the above and yet exhibits strong polymerizability as expected, leading to the present invention. Moreover, the ABHs are Diels-Alder (D 1
It can be easily obtained by isomerization reaction of 5-alkenylnorbornene produced by els A 1der) reaction, and some of these are produced industrially and are easily available.

Furthermore, the resulting copolymer not only has performance comparable to that of a DCP homopolymer, but also has ABH chain portions that are chain-like without any crosslinks and have post-reactivity. It was also discovered that since it contains an acyclic olefin, it has the potential to develop superior performance depending on the usage.

The present invention has been achieved based on these findings. (1) 99 to 50 mol% of dicyclopentadiene and 5-alkylidenebicyclo[2,2,1]hept-2-
Another invention is a crosslinked polymer molded product obtained by polymerizing a monomer mixture consisting essentially of 1 to 50 mol% of ene in the presence of a metathesis polymerization catalyst system. In the method of obtaining a crosslinked polymer molded product by polymerizing in the presence of a metathesis polymerization catalyst system, dicyclopentadiene 99-5 is used as a raw material single omega substance.
0 mol% and 5-alkylidenebicyclo[2,2,1]
A method for producing a crosslinked polymer molded article characterized in that a monomer mixture consisting essentially of 1 to 50 mol% of hept-2-ene is used, and yet another invention comprises: (3) a. Metathesis polymerization. A reactive solution of a cyclic olefin compound containing at least one compound having two cyclic olefin groups in one molecule containing a catalyst-based catalyst (solution A); b. A cyclic olefin containing an activator for a metathesis polymerization catalyst system. At least one compound having two groups in one molecule
The reactivity of the species-containing cyclic olefin compound is as follows:
), in which the cyclic olefin compounds in solution A and solution B are both:
The combined composition is 99 to 50 mol% dicyclopentazine and 5-alkylidenebicyclo[2,2,1]hept-
A reactive solution combination characterized by a monomer mixture consisting essentially of 1 to 50 mole percent of 2-ene.

The DCP used in the present invention is preferably highly purified as described above. DCP is generally separated and purified from 1 q of Cs produced by naphtha crab king.
It will be done. More specifically, a common method is to heat-treat the separated C5 fraction to dimerize cyclopentadiene to create a boiling point difference from other C5 fractions, and then purify it by distillation.

However, with this method alone, the Diels-Alder reaction of cyclopentadiene with dienes having 4 to 6 carbon atoms other than cyclopentadiene, such as butadiene, isoprene, piperylene, etc. Norbornene and the like are produced as by-products, and since these do not have much difference in boiling point from DCP, their contamination is unavoidable.

Then, the obtained OCP is dissociated into monomers by heating, and the difference in dissociation reaction rate of the adducts at that time is utilized to preferentially recover cyclopentadiene, which is further re-dissolved and purified. This is also done.

The DCP used in the present invention is generally DCP IIi degree 9
The content of impurities should preferably be 5% or more, more preferably 97% or more, and should not inhibit the activity of the metathesis catalyst system, but should preferably have metathesis polymerizability. Alcohols and carboxylic acids that inhibit metathesis polymerization.

It is preferable that the content of polar compounds such as carbonyl compounds is as small as possible.

Preferably, the ABHs used in the present invention are similarly purified. ABHs include 5-ethylidene bicyclo[
2,2,1]hept-2-ene (ENB), 5-isopropylidenebicyclo[2,2,1]hept-2-ene (
PNB) is preferred, and ENB is particularly preferred.

The monomers of the crosslinked polymer of the present invention include the above-mentioned monomers.
Although a mixture consisting mainly of p and AB)-1 is used, other metathesis-polymerizable monomers may be added as a third component.

Such a third component monolayer may generally be present as a contaminant in DCP or ABH, but it is generally added to the crosslinked polymer of the present invention to the extent that it does not impair the characteristics of the present invention. can be copolymerized and used, preferably within a range not exceeding 20 mol % based on the DCP and ASH mixture, and a crosslinked polymer copolymerized with such a third component monomer is also naturally included in the scope of the present invention. It is something that will be done.

Such third components include cyclopentadiene-methycyclopentadiene codimer, norbornene, dihydrodicyclopentadiene, 5-phenylnorbornene, 5-
Hydrocarbon-based cycloarthine such as isobutylnorbornene,
Examples include cycloarthines containing different elements such as 5-cyanonorbornene, 5-methyl-methoxycarbonylnorbornene, and nylnorbornene.

In the present invention, the usage ratio of DCP and ASH is 99:
1 to so: The range of so (mol%) is used, but for the purpose of lowering the melting point of DCP, ABH3 to 1 is used.
0 mol% is preferable, and if you try to take advantage of the characteristics of ABH such as increasing the polymerization rate, A B H 20 ~
A range of 45 mol% is preferred. A major feature is that even if a large amount of ABH is copolymerized, the thermal properties, such as the secondary rearrangement point, will not be significantly impaired, and if post-reactivity is utilized, it may even be possible to improve them depending on the treatment method. There is.

As is generally known, a metathesis polymerization catalyst system is composed of a two-component system consisting of a main catalyst component and an active agent component.

Therefore, the active ingredient is first added to the monomer mixture;
Next, the main catalyst component is added, and the mold is placed until polymerization starts and gelation occurs to obtain a crosslinked molded product. Alternatively, the main catalyst component and other active agent components are added to the monomer mixture at the same time, and crosslinking is generated in the same way. There are also ways to obtain things. However, metathesis polymerization reactions are generally exothermic reactions, and once polymerization has started, the system is further heated and the reaction accelerates, completing the reaction very quickly. It is often difficult to shape the gel before gelation using the methods described above.

Therefore, as described above, two solutions, a solution containing the main catalyst component of the metathesis catalyst system (solution A) and a solution containing other active agent components (solution B), are prepared in advance and mixed together with the monomer mixture. (RIM system) or a static mixer or the like, a method of rapidly mixing the mixture, immediately pouring it into a mold, shaping it, and then curing it in the mold to obtain a formed product can be suitably applied. In that case, the composition of the monomer mixture does not necessarily have to be the same in both liquids, and can be changed as desired. In particular, when attempting to utilize melting point depression, the freezing point of the activator solution (solution A) may generally be higher than that of the catalyst solution (solution B) when monomers of the same composition are used. Therefore, it is possible to use a method in which the mixing ratio of ASH is increased in this solution.

A method for manufacturing a molded article using a two-component mixing method for a shell mainly composed of CP is basically disclosed in, for example, Japanese Unexamined Patent Publication No. 129013/1983.

Salts such as halides such as tungsten, rhenium, and tantalum are used as catalyst components in the metathesis 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. Such tungsten compounds are known to immediately start cationic polymerization when added directly to monomers, which is not preferred. 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 the above-mentioned undesirable polymerization, it is preferable to add about 1 to 5 moles of a Lewis base or a chelating agent to 1 mole of the tungsten compound. Such additives include acetylacetone and acetoacetic acid alkyl esters.

Examples include tetrahydrofuran and benzonitrile. By doing so, the DCP solution containing the tungsten compound (corresponding to solution A) will have sufficient stability when used in practical use.

On the other hand, the active component in the metathesis polymerization catalyst system is preferably an organometallic compound mainly consisting of alkylated products of metals from Groups 1 to 2 of the periodic table, particularly tetraalkyl tin, alkyl aluminum compounds, and alkyl aluminum halide compounds. Specifically, diethylaluminum chloride, ethylaluminum dichloride, trioctylaluminum, itbutyltin, etc. can be mentioned. The other solution (corresponding to solution B) is formed by dissolving these organometallic compounds as active ingredients in DCP or a mixture containing DCP.

In the present invention, a crosslinked polymer molded article can basically be obtained by mixing the solutions A and B, but depending on the temperature of the mold, etc., the polymerization reaction may start very quickly. As a result, hardening may occur before sufficient flow into the mold, for which activity modifiers can be used.

As such regulators, Lewis bases are generally used, among which ethers, esters, nitriles, etc. are used. Specific examples include ethyl benzoate, butyl ether, diglyme, etc. Such regulators are generally added to the solution of the activator component of the metal compound.

When using a metathesis polymerization catalyst system, for example, when a tungsten compound is used as a catalyst component, the ratio of the tungsten compound to the DCPD mixed monomer is about 1000:1 to about 1 so on a molar basis.

On the other hand, the ratio is preferably around 2000:1, and when the active ingredient is an alkyl aluminum,
The ratio of the aluminum compound to the DCP mixed monomer is about 100:1 to about 2000:1, preferably about 200:1 to about 500:1 on a molar basis. Furthermore, as mentioned above, masking agents and regulating agents are determined as appropriate depending on the amount of the catalyst system used through experiments.
It can be adjusted and used.

In practical use, various additives can be added to the cross-linked polymer molded article according to the present invention in order 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 in advance to either or both of the above, 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, and And it must not inhibit polymerization.
It won't happen. 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 solid fillers, 1
It is also possible to fill a mold with a shape that can sufficiently fill the voids immediately before starting the polymerization reaction or during polymerization after the image components are mixed.

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 that an antioxidant is added to the crosslinked polymer molded article 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-phenylenediamine, tetrakis[methylene(3,5-di-t-butyl-4-hydroxycinnamate)]]methane methylene-4,4'-bis3 .5-G-
t-butylphenol), etc.

Further, other polymers can be added to the polymer molded article according to the present invention when it is in the form of a single-unit solution. As such polymer additives, the addition of elastomers is effective in increasing the impact resistance of molded articles and in controlling the viscosity of solutions. Elastomers used for this purpose include:
A wide variety of elastomers can be mentioned, such as styrene-butadiene-styrene triblock rubber, styrene-isoprene-styrene triblock rubber, polybutadiene, polyisoprene, butyl rubber, and ethylene brobylene-dienter polymer.

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

Therefore, it is preferable to make a bequest using the so-called RIM method. In molding using the RIM method, as mentioned above, a single α solution (
That is, a common method is to rapidly mix solution A and solution B) in the mixing head of RIMBIN, inject into a mold, polymerize and mold, and obtain a molded product.

The injection pressure into the mold can be relatively low, thus making it possible to use inexpensive molds.

The injection pressure into the mold can be used at a relatively low pressure, so it is possible to use an inexpensive mold. Also,
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 the case of polyurethane-RIM, it is easy to release from the mold and often does not require a special mold release agent.

The molded product has a polar surface, probably due to the formation of an oxidized layer on the surface, and has good adhesion to commonly used paints such as epoxy and polyurethane.

As mentioned above, the polymer molded product according to the present invention has improved workability in terms of liquid melting point dual polymerizability, etc., compared to the case of a DCP homopolymer, and can advantageously be used in various molded products. can be manufactured. Furthermore, it is also possible to raise the softening point by post-treatment or the like by utilizing the reactivity of chain unsaturated bonds remaining in the system. Therefore, it can be said that the combination of an improved crosslinked polymer molded product, its manufacturing method, and a reactive solution is extremely industrially advantageous.

The molded product thus obtained can be used in a wide range of applications, mainly large-sized molded products, such as parts for various transportation vehicles 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 to 7 Comparative Example 1 Commercially available dicyclopentadiene was purified by distillation under reduced pressure in a nitrogen stream to obtain purified dicyclopentadiene 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, commercially available 5-ethylidenebicyclo[2,2,1]hept-2-ene was similarly distilled to obtain a product with a purity of 98.5% or more as determined by gas chromatography.

In order to examine the melting point lowering effect of 5-ethylidenebicyclo[2,2,1]hept-2-ene (ENB), DCP
When mixed monomer liquids were prepared with 2.5 mol%, 5 mol%, and 10 mol% of ENB added, and the freezing points of each were measured, the results were as shown in the table below, and the freezing point decreased in proportion to the amount of addition. It turned out that.

Table 1 Freezing point depression [Preparation of catalyst component solution 1 20 g of tungsten hexachloride was added to 70 Inl of dry toluene under a nitrogen stream, and then 21 g of nonylphenol
and 16 m of toluene to prepare a 0.5 M tungsten-containing catalyst solution, and to this solution,
Nitrogen gas was purged overnight to remove hydrogen chloride gas purified by the reaction of tungsten hexachloride and nonylphenol, which was used as a polymerization catalyst.

Such a solution io, g, acetylacetone 1. 500d of Od-containing monomers are mixed, and tungsten-containing m o, oo+
M solution A was prepared.

[Preparation of activator component solution] 0.18 g of diethylaluminum chloride, 0.375 d of isopropyl ether, and 500 d of mixed monomer were mixed to prepare a 0.003 M solution B as the aluminum content.

When the prepared solution was kept at 25°C, both the activator component solution and the catalyst component solution were frozen in the solution prepared only from pure dicyclopentadiene, but the solution state was not found in the solution prepared from mixed monomers. I kept it.

In addition, cold 1 with a temperature inside the mixed monomer liquid storage of 7°C, which corresponds to Example 3.
Both solutions did not freeze when stored in liu. The effect of lowering the freezing point is evident, and it can be seen that it is very easy to use in practical use.

Rough ENB content 20 mol% (Example 4), 30 mol%
(Example 5), 40 mol% (Example 5), 48 mol% (
Solution A and solution B were prepared using the mixed monomers of Example 7).

The above solution was mixed with 10 In of catalyst component solution (solution A).
l 10 ml of activator component solution (solution B) at an internal temperature of 25°C.
It was then taken out into a syringe that had been thoroughly replaced with nitrogen. The syringe was extruded at a constant speed, liquid was injected, mixed in a nozzle, and then poured into a mold using an ultra-small RIM system to obtain a plate-shaped, extremely durable three-dimensional polymer molding.

The time after the solution is heated until heat generation suddenly starts in the system and the maximum temperature in the system are indicators for determining whether polymerization has been carried out without being inhibited. , E
As the proportion of NB increases, the initiation time tends to be shorter and the maximum temperature reached tends to be higher, indicating the high metathesis polymerizability of ENB.

This is probably due to the good polymerizability, but there is also a tendency for the depth to decrease, which is thought to be due to residual monomer from the molded product, demonstrating the excellent properties of the crosslinked copolymer of the present invention.

Furthermore, the softening point by TMA method and 1 m a', j ratio using toluene, which are indicators of heat resistance and chemical resistance, were measured, and the results are summarized in Tables 2 and 3. Although the swelling rate tends to increase as the copolymerization ratio of ENB increases compared to when pure DCP is used, it does not increase so much and is within a range that does not cause any problem in practical use. - On the other hand, even at the softening point due to T fvl A, pure D
Compared to the case where CP is used, the softening point is almost the same (sometimes larger and sometimes smaller), and when the softening point of the sample moistened to 280°C is measured again, the softening point is slightly higher in all cases. As shown in No. 5, the apparent softening point was no longer observed, indicating the possibility of improving the softening point by post-processing using the ENB component.

Table 2 Softening point needle penetration mode Kimoto - re-measured after heating up to 280°C Table 3 Swelling rate 1, gravity ratio in swollen state

Claims (3)

[Claims] (1) Dicyclopentadiene 99-50 mol% and 5-
A crosslinked polymer formed by polymerizing a monomer mixture consisting essentially of 1 to 50 mol% of alkylidene bicyclo[2,2,1]hept-2-ene in the presence of a metathesis polymerization catalyst system. thing. (2) In a method for obtaining a crosslinked polymer molded product by polymerizing cycloalkenes in the presence of a metathesis polymerization catalyst system, 99 to 50 mol% of dicyclopentadiene and 5-alkylidene bicyclo[2,2 , 1] A method for producing a crosslinked polymer molded article, characterized in that a monomer mixture consisting essentially of 1 to 50 mol % of hept-2-ene is used. (3) a, at least one compound having two cyclic olefin groups in one molecule containing a metathesis polymerization catalyst system;
A reactive solution of a cyclic olefin compound containing species (solution A
), b, a reactive solution of a cyclic olefin compound containing at least one compound containing two cyclic olefin groups in one molecule (solution B) containing an activator for a metathesis polymerization catalyst system; In the combination, both the cyclic olefin compounds in solution A and solution B have a combined composition of 99 to 50 mol% dicyclopentazine and,
5-Alkylidenebicyclo[2,2,1]hept-2-
A reactive solution combination characterized in that it is a monomer mixture consisting essentially of 1 to 50 mole % of enene.