JPH03126731A - Production of molded article of metathesis polymer - Google Patents

Abstract

PURPOSE:To obtain the title inexpensive and strong molded article without causing crack, etc., of mold by using a mold comprising a specific skin material, polymerizing and molding a metathesis polymerization monomer in the presence of a metathesis polymerization catalyst system. CONSTITUTION:A metathesis polymerization monomer such as dicyclopentadiene or 5-ethylidenenorbornene is polymerized and molded in the presence of metathesis polymerization catalyst system such as tungsten (oxy)halide in a mold using a resin having >=3kg/cm<2> tensile strength at 150 deg.C or >=2kg/cm<2> flexural strength as a skin material to give the objective high quality molded article having excellent decoration.

Description

Detailed Description of the Invention: a. Industrial Application Field The present invention relates to a method for polymerizing and molding metathesis-polymerized bamboo seeds in a mold in the presence of a metathesis polymerization catalyst to obtain a cured polymer molded product. As a mold, it is possible to use an inexpensive and durable resin mold.

h. Prior Art It is known that cyclic olefins can be prepared by metathesis polymerization catalyst systems to give ring-opened polymers. Therefore, a method has been proposed in which a liquid metasense polymerizable cyclic olefin, which can be obtained at low cost, such as dicyclopentadiene (DCP), is polymerized and molded in one step in a mold using a metathesis polymerization catalyst to produce a polymerized molded product. Ta. That is, the metathesis polymerization catalyst system combines a catalyst component such as tungsten chloride with Al-1
- Utilizing the fact that it consists of an active inhibitor component such as aluminum and two components J, it is cured by reaction indexing (casting) molding method by impact mixing using two types of liquids consisting of these two components and a monomer. For example, a method for t9ing a polymer molded article has been proposed.
(Refer to Japanese Patent Application Laid-Open No. 58-129013@publication).

According to this method, a doll molded product with good performance can be obtained using an inexpensive low-pressure mold, so it can be said to be a very attractive method from an industrial standpoint. However, when applied to actual molding, It has become clear that there are some points that require improvement.

For one thing, it is true that using such a method makes it possible to use inexpensive molds such as electroforming molds and molten metal molds, but even so, molds that use ordinary epoxy resin for the surface cannot be used. , cracks in the mold after several to thousands of times of molding,
It has been found that defects such as peeling occur.

C3 Object of the Invention The object of the present invention is to provide an excellent method for producing cured polymer moldings using a metathesis-polymerizable septamer using a mold that can withstand repeated use.

d1 Structure of the Invention The present invention involves polymerizing and molding a metathesis-polymerizable monomer in a mold in the presence of a metathesis polymerization catalyst system to obtain a cured polymer molded product. The tensile strength is 3 K'J/
This is a method for producing a cured polymer molded article, characterized in that a resin having a bending strength of 2 Kg/ci or more or a bending strength of 2 Kg/ci or more is used.

The present inventor has conducted various studies on the material of the mold in a method for producing a cured polymer molded article by polymerizing and molding a metasense polymerizable monomer in a mold in the presence of a metathesis polymerization catalyst system. Molding molds whose skin is made of epoxy resin A131 develop defects such as cracking and peeling in the mold after being molded several to several thousand times, but this is mainly due to the heat generated by this reaction and the mold We discovered that this is due to the pressure generated within the mold, and the compression and tension between the molded product and the mold due to expansion and contraction during molding, and as a result of studying countermeasures, we arrived at the present invention.

That is, in this molding, a maximum of 150
℃ and a pressure of 2 to 51 VI/cm culm is applied, and at this time the mold is subjected to tension, compression, etc. At this temperature, the tensile strength is 3 Ky/cI.
If a resin with a bending strength of +1 or more or a bending strength of 2 Kg/cr/r or more is used as III, it becomes possible to perform molding far more than several thousand times. Preferably, the tensile strength is 3
Kg/c#! or more and bending strength is 2K9/cm
m or more (a mold using material A is preferable).

In the present invention, tensile strength is a value measured according to JIS K7113°, and bending strength is a value measured according to JIS K7203.

The molding temperature is generally raised to allow the curing reaction to occur smoothly. In the case of curing in the present invention, the mold temperature is generally in the range of 50 to 110°C. Although blowing nitrogen into the mold in advance is effective in improving the surface properties of the molded product and in reducing the temperature of the mold, it is not always necessary to carry out the blowing.

Specific examples of the metathesis-polymerizable salts used in the present invention include dicyclopentadiene, tricyclopentadiene, cyclopentadiene, methylcyclopentadiene, 5-ethylidene norbornene, norbornene,
norbornagene, 5-cyclohexenylnorbornene, 1,4,5. B dimethanol-1,44a,5,6,7,
8,8.8a-octahydronaphthalene, 1,4. -methanol-1,4,4a, 5,6,7,8,8゜8a-octahydronaphthalene, 6-ethylidene 1.4,5.8-
Dimethano-1,4,4a,5,7,8.8a-hexahydronaphthalene, 1,4,5.8-dimethano-1,4°4a,5,8.8a-hexahydronaphthalene1. Examples include ethylene bis(5-norbornene). Especially dicyclopentazine or more than 50 mol%
A mixture containing two is preferably used.

Further, if necessary, a metathesis-polymerizable heptamer having a polar group containing a different element such as oxygen or nitrogen can be used for copolymerization. It is preferable that such a J (small merging hexamer) has a norbornene structural unit, and the polar group is an ester group, an ether group, a cyano group, an N-
Preferred are substituted imide monomers, halogen groups, and the like. Specific examples of such copolymerizable monomers include 5-methoxycarbonylnorbornene, 5-(2-ethylhexy[1xy]carbonyl-5-methylnorbornene, 5-phenyloxymethylnorbornene, 5-cyanonorbornene, 6- Diatu 4,4,5.8-dimethano-1,4,4a.

5.6,7,8.8a-octahydronaphthalene, N-
Butylnadic acid imide, 5-chloronorbornene In the present invention, it is preferable to carry out the polymerization and molding by a reaction molding method.

In the reaction-cutting (casting) molding method used in the present invention, a monomer solution (solute/
A method is often used in which two solutions, i.e., IA) and monomer solution 'fj, (solution B) containing an activator component, are mixed and then press-fitted into a mold, but this is not necessarily the only method. There are also methods of mixing with stirring, static mixing, etc., and methods of dividing the solution into three or more parts. C1 can have various lengths depending on the time from start to completion, use, and purpose.

For such molding, 1' is added to the metathesis polymerization catalyst system.
The catalyst components include tungsden and rhenium.

Salts such as metal halides such as tantalum and molybdenum are used, 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. Maiko, 41
Ammonium tungstate and the like can also be used. It is known that when such a tungsten compound is added directly to a monomer, cationic polymerization immediately starts, which is not preferable. Accordingly, such tungsten compounds are contained in inert solvents such as benzene, toluene.

It is preferable to use it by suspending it in advance in chlorobenzene or the like and solubilizing it by adding a small amount of an alcohol compound and/or a phenol compound.

Further, as mentioned above, in order to prevent undesirable polymerization, it is preferable to add about 1 to 5 mol of a Lewis base or a gyrating agent per 1 mol of the tungsten compound. What kind of additive is Acedylua I? l-one, ahitoacetic acid alkyl esters, detrahydrofuran, benzoni 1
~You can give rills, etc. When a polar polar compound is used, as described above, it may itself be a Lewis base, and may have the effect even without the addition of the above-mentioned compounds.

Thus, the monomer solution containing the catalyst component (solution A) is
This results in a stability of "substantially".

The activating component in the metathesis polymerization catalyst system has a period tl! Organometallic compounds mainly consisting of alkylated products of metals in Groups ■ to ■ of the table are preferred, particularly tetraalkyltin, argylaluminum compounds, and alkylaluminum halide compounds, and specifically, diethylaluminum chloride and ethyl dichloride. Examples include aluminum, trioctylaluminum, dioctylaluminum iodide, and tetrabutyltin. By dissolving the organometallic compound of these activator components in a diluted solution,
Another solution (corresponding to solution B) is formed.

In the present invention, a crosslinked polymer molded article can basically be prepared by mixing the solutions A and B, but if the composition remains as it is, polymerization and anti-silting will start very quickly. However, hardening may occur before it flows sufficiently into the molded wall, which often poses a problem, and as mentioned above, it is preferable to use an activity regulator for this purpose.

As such regulators, Lewis bases are generally used, especially ethers and esters.

Nitriles etc. are used. Specific examples include edyl benzoate, butyl ether, and diglyme. Such regulators are generally added to the solution of the organometallic compound activator component. When a monomer having a Lewis base is used as described above, it can also serve as a regulator.

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 raw material monomer is about 1 on a molar basis.
000Kari 1 to 15000:1, preferably around 2000:1 'C', and in the case where the activating component is an alkyl aluminum, the ratio of the aluminum compound to the raw material monomer is: J to about 100 to 2000:1, preferably from about 200 to 1 to 50 on a molar basis.
An f4 neighborhood of 1 is used.

Furthermore, as described above, the masking agent and regulating agent can be appropriately adjusted and used depending on the amount of the catalyst system to be used through experiments.

In order to improve or maintain the properties of the cross-linked polymerized product obtained by the present invention in practical use,
Furthermore, various additives can be added.

Such additives include fillers, pigments, antioxidants, light stabilizers, N-smoking agents, polymer modifiers, and the like. Since such additives cannot be added after the crosslinked polymer of the present invention has been molded, when they are added, it is necessary to reduce the additive to the above-mentioned raw material solution in advance.

The easiest way to do this is to add the above solution and solution B.
One method is to add it in advance to either or both of the following: However, in this case, it is necessary to add a substance that 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 interfere with polymerization. Even if the reaction is unavoidable, if the polymerization does not substantially harm the rice fields, mix it with Nanatsuma to prepare a third liquid and use it immediately before polymerization. You can also do it. It is also possible to consider a method in which the polymerization catalyst or activator is used as a third liquid and the above-mentioned additives are added to solution A or solution B that does not contain this.

Furthermore, in the case of a solid filler, if it is in a shape that can sufficiently fill the voids immediately before starting the polymerization reaction or during polymerization when both components are mixed, it may be filled into the mold. It is also possible to keep it.

Reinforcements or fillers as additives are effective in improving the flexural modulus. Such materials include glass fiber, mica, and carbon black.

I can give you a raspite, etc. Those surface-treated with a so-called silane coupler can also be suitably used.

Further, it is preferable to add an antioxidant to the cured polymer molded article obtained by 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, detrakis [
Examples include styrene (3,5-di-t-butyl-4-hydroxycinnamate)]methane.

In addition, other polymers can be added to the polymer molded product obtained by the present invention when it is in a monomer solution state. As such a polymer additive, addition of an elastomer is effective in increasing the 1li-1 impact strength of the molded article and adjusting the viscosity of the solution. Elastomers used for this purpose include a wide range of elastomers such as styrene-butadiene-styrene triblock rubber, styrene-isoprene-styrene triblock rubber, polybutadiene, polyisoprene, butyl rubber, and ethylene-brobylene-dienter polymantrile rubber. I can give you.

Possible materials for the mold according to the present invention include epoxy resins, polyester resins, and modified versions of these resins, but the tensile strength at 150°C is 3 Kg/crd.
or, as long as the bending strength is 2 Kg/cta or more, there is no limitation to these.

e1 Effects of the Invention According to the present invention, it is possible to repeatedly obtain a good molded product 3 without causing troubles such as cracks in the mold. The cured polymer molded product obtained by the present invention has very few defects on its surface and is of high quality, has excellent cosmetic properties, and has little heat distortion and is less likely to be thermally deformed. It can be used for a wide range of purposes, including parts for various transportation equipment, housings for electrical and electronic equipment, and molded dolls.

f. Examples The present invention will be explained with reference to Examples below. Note that the examples are for illustrative purposes only, and the present invention is not limited thereto.

[Preparation of catalyst component solution] 20 parts by weight of tungsten hexachloride was added to 70 parts by volume of dry toluene under a nitrogen stream, and then 2 parts of nonylphenol was added to 70 parts by volume of dry toluene.
A 0.5M tungsten-containing catalyst solution was prepared by adding a solution consisting of a heavy part and 16 volumes of toluene, and the solution was purged with nitrogen gas overnight to produce a solution consisting of tungsten hexachloride and nonylphenol. The resulting hydrogen chloride gas was removed to obtain a polymerization catalyst solution.

4. 500 parts by volume of purified dicyclopentadiene were mixed with 10 parts by volume of the polymerization catalyst solution and 1 part by volume of acetylacetate to prepare a solution A of 0,001M tungsten Venus.

[Preparation of Activation Side Component Solution] 1-Li-A-di-A-di-A-di-A-dite and dio-di-A-di-A-di-A-dite were mixed with purified dicyclopentadiene in a molar ratio of 85:15, and the aluminum solution was 0.00.
If you want to prepare 3M solution B, please read the above (the corresponding letters are 1 mf! and 1 LJ, LQ and I Kg).

Using this solution and B, molding was carried out using a reaction index molding machine and a mold having a skin having the mold material number shown in the table below. Tensile strength (measured according to JISK 7113) is shown in the table.
, dill strength (measured according to JIS K7203) and the number of times of molding until molding trouble occurs.

As is clear from this table, when grinding wheels 1 and 2.5 having excellent tensile strength and/or bending strength are used, the number of times of molding from molding 1 to rubble light generation is greatly increased.

Claims (1)

[Claims] When polymerizing and molding a metathesis polymerizable monomer in a mold in the presence of a metathesis polymerization catalyst system to obtain a cured polymer molding, 15
A method for producing a cured polymer molded article, characterized in that a resin having a tensile strength at 0° C. of 3 Kg/cm^2 or more or a bending strength of 2 Kg/cm^2 or more is used.