JPH01304113A - Polymer molded item, preparation thereof and combination of reactive solutions - Google Patents

Abstract

PURPOSE:To facilitate the control of a polymn. reaction and to improve impact resistance and heat resistance by performing simultaneously polymn. and molding of a metathesis-polymerizable monomer in the presence of a metathesis polymn. catalyst system and a specified polymer. CONSTITUTION:After a polymer (D) substantially consisting of 70-95mol% ethylene and 30-5mol% vinyl acetate or a lower alkyl acrylate and being substantially dissolved by 5wt.% or more at 30 deg.C in a mixed soln. consisting of 90wt.% dicyclopentadiene and 10wt.% ethylidenenorbornene is added to at least one of the component (a) and (b) in a combination (C) of a reactive soln. consisting of a reactive soln. (a) of the component of a metathesis-polymerizable monomer (A) contg. a catalytic component among a metathesis polymn. catalyst system consisting of a catalytic component and an activating component and a reactive soln. (b) of the component A contg. an activating component of the component B, the components A-D are cast in a mold and bulk polymn. and molding are simultaneously performed therein.

Description

DETAILED DESCRIPTION OF THE INVENTION a. Industrial Application Field The present invention relates to a method of pouring a metathesis-polymerizable monomer into a mold in the coexistence of a metathesis-polymerization catalyst system, and performing molding simultaneously with bulk polymerization in the mold; This invention relates to a combination of a polymer molded product obtained by the method and a reactive Fg liquid therefor.

More specifically, the present invention relates to a method of significantly improving the wI impact resistance and heat resistance of a crosslinked polymer molded product by coexisting a specific polymer in the above technique, and advantageously controlling the bulk polymerization reaction.

b. Prior Art It is known that cyclic olefins can be ring-opened by metathesis polymerization catalyst systems to give crosslinked polymers.

Therefore, there is a method in which a monomer such as dicyclopentadiene, which can be obtained at low cost and has two metathesis-polymerizable groups, is poured into a mold in a liquid state, bulk polymerized in the mold, and molded simultaneously with polymerization in one step. proposed (for example, see Japanese Patent Laid-Open No. 129013/1983).

According to this method, a large-sized molded product can be obtained using an inexpensive mold, so it has the possibility of being used in a wide range of applications.

However, it has been found that some improvements are necessary in putting polymer moldings into practical use, especially in large-sized moldings. Among these, the major ones are impact resistance, heat resistance, and adjustment of polymerization reaction rate.

That is, large-sized molded products need to have good impact resistance while maintaining their rigidity. In the case of a polymer molded product containing dicyclopentadiene alone, the notched Izot impact strength at room temperature is generally 10 kIrcz/(2) or less,
In the case of such molded products, at least 20 kg(2)/(2
) or more, preferably 40 kt/(2) or more. In addition, in terms of heat resistance, in the case of a polymer molded product containing only dicyclopentadiene, the softening point is around 90''C, but it is desirable that it be 100''C or higher.

On the other hand, when making large molded products, it would be a waste if the liquid monomer solidified before being filled into the mold, so it is preferable to have an induction period corresponding to the filling period. .

By the way, it has been found that adding a soluble elastomeric polymer to the monomer is effective in improving impact resistance while maintaining rigidity. However, it has been found that the heat resistance of the resulting molded product is greatly affected by the type of such polymer.

On the other hand, it has been found that addition of a polar compound such as ester or ether, which is a Lewis space, is effective in controlling the above-mentioned polymerization initiation time. However, such polar compounds
It has been found that since it remains as it is in the polymer molding, it causes problems such as impairing the heat resistance of the obtained polymer.

Therefore, the present inventors have developed an elastomer for improving impact resistance, which can improve not only impact resistance but also heat resistance, and can also add a polymerization initiation regulating effect by having a polar group. As a result of intensive research, we have arrived at the present invention.

C9 Structure of the Invention The present inventor has focused on ethylene-vinyl acetate copolymers and ethylene-acrylic acid ester copolymers. Such polymers can be industrially produced in a wide range of copolymerization ranges and degrees of polymerization for use in rubber, thermoplastic elastomers, or flexible thermoplastic plastics, and can be said to be readily available polymers.

The main chain of such polymers is composed of chemically stable saturated hydrocarbon chains, and the side chains contain ester groups, which are weak Lewis spaces. Therefore, we focused on the possibility that they could be used for the above-mentioned improvements. As a result of more detailed study, it was discovered that a specific ethylene content range [m] would most likely achieve the purpose.

That is, the present invention encompasses the following inventions.

(1) In a polymer molded product obtained by simultaneously polymerizing and molding a metathesis polymerizable monomer in the coexistence of a metathesis polymerization catalyst system, 70 to 95 mol% of ethylene,
A polymer consisting essentially of 30 to 5 mol% of vinyl acetate or lower alkyl acrylate, and at least 5% by weight at 30°C in a mixed solvent consisting of 90% by weight of dicyclopentadiene and 10% by weight of ethylidene norbornene. A polymer molded product obtained by adding at least one substance that is substantially soluble to the metathesis polymerizable monomer.

(2) In a method for producing a polymer molded product in which polymerization and molding of a metathesis polymerizable monomer are simultaneously performed in the coexistence of a metathesis polymerization catalyst system, 70 to 95 mol% of ethylene;
A polymer consisting essentially of 30 to 5 mol% of vinyl acetate or lower alkyl acrylate, and at least 5% by weight at 30°C in a mixed solvent consisting of 90% by weight of dicyclopentadiene and 10% by weight of ethylidene norbornene. A method for producing a polymer molded article, characterized in that at least one substance that is substantially soluble is added to the metathesis-polymerizable monomer.

(31a) A reactive solution of metathesis polymerizable monomers containing a catalyst component of a metathesis polymerization catalyst system (solution A) and b) A reactive solution of metathesis polymerizable monomers containing an activating component of a metathesis polymerization catalyst system (solution B) In the combination of at least one reactive solution, at least one of these solutions A and B contains ethylene 7
0 to 95 mol%, vinyl acetate or lower alkyl acrylate 30 to 5 mol%, and a mixed solvent consisting of 90% by weight of dicyclopentadiene and 10% by weight of ethylidene norbornene at 30°C.
A combination of reactive solutions containing at least 5% by weight of at least one substance that is substantially soluble in the combination.

A copolymer containing less than 70 mol% of ethylene and 30 mol% or more of vinyl acetate has good solubility, but the polymerization retardation effect becomes too large and the effect of improving the heat resistance of the obtained polymer is insufficient. Not.

Also, ethylene content is less than 70 mol%, acrylic acid ester 3
If the amount is 0 mol % or more, the solubility in the monomer tends to deteriorate, and the same tendency occurs due to polymerization retardation effects, etc., which is not preferable.

On the other hand, for both copolymerized monomers, ethylene is 95
If it exceeds mol%, the crystallinity becomes too large, the solubility becomes insufficient, and the improvement in impact resistance becomes insufficient.

Therefore, it has been found that those containing ethylene in the above-mentioned range are highly effective. In particular, ethylene 75~
Among the lower alkyl esters having 3 or less carbon atoms, ethyl ester is particularly preferred as the acrylic ester, which is preferably in the range of 95 mol%.

Ethylene copolymers having the above-mentioned composition are extruded as plastics and used in a wide range of applications, including injection molding, thermoplastic elastomers, rubber, hot melt adhesives, and pressure-sensitive adhesive blends. A wide range of ethylene compositions and degrees of polymerization can be used industrially depending on the requirements.

Regarding the degree of polymerization and the amount added of the copolymer used in the present invention, a suitable range can be selected depending on which of the above-mentioned three points of improvement is particularly focused on.

That is, when the main focus is on improving impact resistance, it is preferable to use a material with a low ethylene content and a high degree of polymerization; conversely, when the focus is on heat resistance, a material with a high ethylene content is preferable. In addition, the degree of polymerization and the amount added affect the viscosity of the reactive solution, but the viscosity is correlated with a suitable range depending on the relationship with the molding process.For example, when such a reactive solution is put into a reaction injection molding mold, When used, 200 to 1000 cps at the injection temperature, especially 30
A viscosity of about 0 to 500C1]S is preferred, and therefore,
Once a suitable composition and degree of polymerization are determined, the amount to be added is generally determined to provide a suitable viscosity.

Furthermore, since a material with a low degree of polymerization was used, if the viscosity is insufficient even after adding the required amount for performance improvement, soluble polymers such as other elastomers as described below may be added.

Generally, the amount added is in the range of 2 to 30 wt%,
In particular, a range of 3 to 20 wt% is preferably used.

The copolymer essentially consists of ethylene and vinyl acetate or acrylic acid ester, but other copolymer monomers may be added to the extent that the characteristics of the copolymer are not impaired.
Those containing the same can also be used in the present invention.

Furthermore, the metathesis-polymerizable monomer used to form a polymer molded product together with such a soluble copolymer may be any monomer as long as it can be bulk-polymerized by metathesis polymerization to give a molded product. Those containing 1 to 4 metathesis-polymerizable cycloalkene groups are used. Particularly preferred are those having a norbornene type bond, and particularly preferred are those having a hydrocarbon type bond. -ethylidenenorbornene, 5-vinylnorbornene.

Norbornene, 5-cyclohexenylnorbornene, 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, 5-phenylnorbornene, ethylene bis(5-norbornene), etc., among others, dicyclopentadiene or 50% or more, preferably 70% or more of dicyclopentadiene. Monomer mixtures containing are preferred.

Further, if necessary, a metathesis polymerizable monomer containing a polar group having a different element such as oxygen or nitrogen can also be used. Such a metathesis-heavy monomer preferably has a norbornene supplementary unit, and the polar group is preferably an ester group, an ether group, a cyano group, or an N-substituted imide group.

Such a polar group, as Lewis space, has the function of regulating the initiation of the metathesis polymerization reaction together with the ester group of the side chain of the copolymer in the present invention, and can also introduce a polar group into the formed polymer product. Depending on the type of norbornened polymer (wa), it may even have the effect of increasing its solubility, so it is suitably used depending on the necessity of the action.

Such polar monomers include (5-norbornenyl)
Methyl-phenyl ether, bis[(5-nornornenyl)methyl]ether, 5-methoxycarbonylnorbornene, 5-methoxycarbonyl-5-methyl-norbornene, 5[(2-ethylhexyloxy)carbonyl]
Norbornene, ethylene-bis(5-norbornenecarboxylate), 5-cyanonorbornene, 6-diatwo 1゜4.5.8-dimethano-1,4,4a, 5,6,
7,8.8a-Octahydronaphthalene, N-butylnadic imide.

Examples include 5-(4-pyridyl)-norbornene.

Furthermore, halogen-containing metathesis polymerizable monomers can also be used to improve flame retardancy and softening temperature. Specific examples of such monomers include 5-chloronorbornene,
5-bromonolbornene.

5.5.6-drichloronorbornene, 5,5,6.
Examples include 6-titrachlornorbornene, 5,6-dibromonorbornene, and 5-(2,4-dibromophenyl)norbornene.

All of the metathesis-polymerizable monomers mentioned above preferably have as low a content of impurities that inhibit the metathesis-polymerization catalyst as possible.

As is known, the metathesis polymerization catalyst system used to obtain the polymer molded product in the present invention generally consists of two components: a catalyst component and an activator component.

However, the metathesis polymerization reaction is generally an exothermic reaction, and once the polymerization starts, the system is further heated and the reaction is accelerated.

Therefore, as mentioned above, two solutions were prepared in advance: a solution consisting mainly of monomers and catalyst components (solution A), and a solution consisting mainly of monomers and other active agent components (solution B), and collisional mixing (RIM method) was carried out. ) or a static mixer, the mixture is immediately poured into a mold, shaped, and then hardened within the mold.

In that case, the composition of the monomers does not need to be the same in both liquids, and can be arbitrarily changed depending on the function of the monomers. Although the amount of the copolymer added can be varied depending on the two solutions, it is generally preferable in the reaction injection molding method that the two solutions have the same viscosity, since mixing can be performed more effectively.

Another method for obtaining a polymer molded product is to delay the initiation of polymerization by adding Lewis space, which acts as a regulator to delay the initiation of metathesis polymerization, or a metathesis-polymerizable monomer containing such Lewis space, as described above. A method of flowing the generated premix into a mold, that is, a resin injection method can also be used.As mentioned above, the ester chain of the copolymer of the present invention can also exhibit such a retarding effect. be. In this case, it is advantageous to place a glass fiber mat or the like in the mold in advance to obtain a fiber-reinforced molded product.

In the RIM method, such a glass fiber mat can also be used in the mold.

Salts such as halides such as tungsten, rhenium, tantalum, and molybdenum are used as catalyst components in the metathesis polymerization catalyst system, and tungsten compounds are particularly preferred.Tungsten halides are particularly preferred as such tungsten compounds.

Tungsten oxyhalide is preferable, and more specifically, tungsten hexachloride, tungsten oxychloride, etc. are preferable, and organic ammonium tungstates, molybdates, etc. can also be used. It is known that when a tungsten halide compound is added directly to a monomer, it immediately starts cationic polymerization, which is undesirable. It is preferable to use it by solubilizing it by adding a small amount of an alcoholic compound or a phenolic compound.

Furthermore, in order to prevent undesirable polymerization as mentioned above, it is preferable to add about 1 to 5 mol of a Lewis base or a chelating agent to 1 mol of the tungsten compound. Examples of such additives include acetylacetone, alkyl acetoacetate, etc. As mentioned above, the polar monomer for copolymerization used in the present invention may include esters, tetrahydrofuran, benzonitrile, etc., and may itself be a Lewis base. In some cases, it has that effect.

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

On the other hand, the active component in the metathesis polymerization catalyst system is an organometallic compound mainly containing alkylated products of metals of Groups 1 to 2 of the Periodic Table, especially tetraalkyltin, trialkylhydrogentin, triarylhydrogentin, and alkyltin. Aluminum compounds and alkyl aluminum halide compounds are preferred, and specific examples include diethyl aluminum chloride, ethyl aluminum dichloride, trioctyl aluminum, dioctyl aluminum iodide, and tetrabutyl pot. The other solution (corresponding to solution B) is formed by dissolving the organometallic compound as the active ingredient in the raw material monomer.

In the present invention, a polymer molded product can basically be obtained by mixing the solutions A and B, but if the above composition is used as it is, the polymerization reaction will start very quickly. Curing may occur while the copolymer of the present invention does not flow sufficiently into the mold, which is often a problem, and the ester groups contained in the copolymer of the present invention are effective in preventing this. However, if this is still insufficient, it is preferable to use an activity modifier as described above.

As such regulators, Lewis bases are generally used, among which ethers, esters, nitriles, etc. are used. Specific examples include ethyl benzoate, butyl ether, and diglyme. As mentioned above, when a copolymerizable monomer having a Lewis space group is used, it may exhibit an effect as a regulator.

The amount of the metathesis polymerization catalyst system used is, for example, when a tungsten compound is used as a catalyst component, the ratio of the tungsten compound to the raw material monomer is about 1 on a molar basis.
000:1 to 15000:1, preferably 2000:1
In addition, when an alkyl aluminum is used as the active inhibitor component, the value is close to 1. The ratio of the aluminum compound to the raw material monomers in E is about 100:1 to about 2000:1, preferably about 200:1 to about 500:1 on a molar basis. 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.

In practical use, various additives can be added to the crosslinked polymer molded product of the present invention in order to improve or maintain its properties. Such additives include fillers, fillers, antioxidants, light stabilizers, B fumigants, polymer modifiers, TA residue monomer reducers, and the like. Since such additives cannot be added after the polymer of the present invention is formed, it is necessary to add them to the above-mentioned raw material solution in advance.

The easiest method is to use the solution MA and solution B.
One method is to add it in advance to either or both of the above, but 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 be something that does not inhibit polymerization. If the reaction cannot be avoided, but it does not substantially inhibit polymerization even if it coexists, mix it with the monomer and prepare the third liquid. They can also be 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 the filler, 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 a so-called silanga puller 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. As a specific example, 2.6-
t-Butyl-p-cresol, N,N'-diphenyl-
p-phenylenediamine, tetrakis[methylene (3,
5-di-t-butyl-4-hydroxycinnamate)]
Examples include methane.

In the present invention, as mentioned above, the purpose is to improve impact resistance and heat resistance and to adjust the polymerization initiation time by adding the ethylene copolymer. As such, general soluble elastomers can also be used in combination.

Examples of elastomers used for this purpose include styrene-butadiene-styrene triblock rubber, styrene-isoprene-styrene triblock rubber, polybutadiene, polyisoprene, butyl rubber, ethylene-propylene rubber, ethylene-propylene-genterpolymer, and the like. I can do it.

Furthermore, in the present invention, if the amount of residual monomer in the molded product increases, it not only lowers the softening point but also may emit a characteristic odor, so it is preferable to have as little residual monomer as possible. α, α as additives to reduce residual monomers.

Very small amounts of halides and acid anhydrides such as α-trichlorotoluene, LW-dichlorodiphenylmethane, phthalic chloride, benzoic anhydride, benzenesulfonic acid chloride, and phosphorus oxychloride can be added.

The crosslinked polymer molded product of the present invention is produced by simultaneously carrying out the polymerization process as described above.

As mentioned above, such molding methods include the resin injection method in which a premix of the catalyst system and monomer mixture is flowed into the mold, and the resin injection method in which the catalyst system is divided into two parts, solution A and solution B, collided at the head part. It is possible to use the RIM method in which the mixture is mixed and poured directly into a mold. 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.

The molded product thus obtained has improved impact resistance and heat resistance compared to conventional products, and the polymerization start time can be adjusted, making it suitable for use in various vehicles including automobiles.
It can be particularly suitably used for large-sized molded products, such as parts for electronic equipment 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 intended to be limiting.

Examples 1-5. Comparative Examples 1 to 2 [Preparation of main catalyst source liquid a] High purity tungsten hexachloride 19.80 kK (0.05
mol) was added to 90 ml of dry toluene under a nitrogen stream,
A solution of 0.925 g of t-butanol dissolved in 5 ml of toluene was added and stirred for 1 hour. Then, a solution consisting of 11.05 kg (0.05 mol) of nonylphenol and 51I11 of toluene was added and the mixture was kept under nitrogen purge for 1 hour. Stir. Add 10g of acetylacetone to the mixture;
Stirring was continued overnight under a nitrogen purge while purging by-produced hydrogen chloride gas, and then some of the toluene distilled off was supplemented to prepare a 0.5M tungsten-containing catalyst concentrate.

[Preparation of activated inhibitor concentrate] 5.70 g of di-n-octylaluminum idide, 31.17 f of tri-n-octylaluminium.

13.42 g of diglyme was mixed under nitrogen flow, then dicyclopentadiene (DCP) was added to make a total of 10 g.
The solution was diluted to 0ml to obtain an activated concentrate containing 1.0M aluminum.

[Preparation of Reactive Solutions] Reactive solutions A and B having the compositions shown in Table 2 were prepared by using purified DCP obtained by distilling and purifying commercially available DCP and ethylene copolymers shown in Table 1.

[Preparation of polymer molded product and measurement of its properties] 10 ml of the above catalyst component solution (solution A).

After the activator component solution (solution B) 101111 was brought to a predetermined temperature, it was taken out into a syringe which had been sufficiently replaced with nitrogen. The liquid from these two syringes is extruded simultaneously at a constant speed into a glass flask equipped with a stirrer under rapid stirring, and after rapid mixing, the stirrer is raised and a thermocouple is pushed in. When the injection of liquid from the syringe is finished, to 100℃
The time it took to reach was measured.

Furthermore, the solidified crosslinked resin was taken out, cut into sections, and the softening point was measured using the TMA method in the needle penetration mode in a nitrogen stream. The results are also listed in Table 2.

Table 1 Table 2 The ratio of the activator used was selected to be the concentration that would minimize the time required to reach 100°C depending on the ethylene copolymer used, but as the ester content of the copolymer increased, the time required to reach 100°C decreased. It can be seen that the copolymer of the present invention has a function of adjusting the polymerization initiation time. However, in the case of copolymer E (Comparative Example 2) in which the Nisnal content is outside the range of the present invention, it is found that it is difficult to initiate polymerization even if the aluminum concentration is increased considerably. The softening temperature is greatly improved compared to when such a copolymer is not used.
That is, it can be seen that the heat resistance is improved.

It can be seen that this is particularly noticeable when the ethylene content is 85 mol% or more.

The obtained polymer molding was cut into thin pieces and the degree of IL impact resistance was qualitatively judged. Compared to the polymer molding obtained in Comparative Example 1, it had a milky white color and had poor resistance. It was found that the impact resistance was improved.

Claims (3)

[Claims] (1) In a polymer molded product obtained by simultaneously polymerizing and molding a metathesis polymerizable monomer in the coexistence of a metathesis polymerization catalyst system, 70 to 95 mol% of ethylene,
A polymer consisting essentially of 30 to 5 mol% of vinyl acetate or lower alkyl acrylate, and at least 5% by weight at 30°C in a mixed solvent consisting of 90% by weight of dicyclopentadiene and 10% by weight of ethylidene norbornene. A polymer molded product obtained by adding at least one substance that is soluble in the metathesis polymerizable monomer to the metathesis polymerizable monomer. (2) In a method for producing a polymer molded product in which a metathesis polymerizable monomer is simultaneously polymerized and molded in the presence of a metathesis polymerization catalyst system, from 70 to 95 mol% of ethylene and 30 to 5 mol% of vinyl acetate or lower alkyl acrylate. A polymer consisting essentially of dicyclopentadiene 90% by weight and ethylidene norbornene 10% by weight
at 30°C for a mixed solvent consisting of at least 5
The method for producing a polymer molded article is characterized in that at least one substance that is substantially soluble in weight percent is added to the metathesis polymerizable monomer. (3) a) a reactive solution of metathesis polymerizable monomers containing the catalyst component of the metathesis polymerization catalyst system (solution A); and b) a reactive solution of metathesis polymerizable monomers containing the activating component of the metathesis polymerization catalyst system (solution B). ), in which at least one of these solutions A and B contains ethylene 7
0 to 95 mol%, 30 to 5 mol% of vinyl acetate or lower alkyl acrylate, and a mixed solvent of 90% by weight of dicyclopentadiene and 10% by weight of ethylidene norbornene at 30°C.
A combination of reactive solutions containing at least 5% by weight of at least one substance that is substantially soluble in the combination.