JPH0819221B2 - Method for producing crosslinked polymer molding - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention relates to a method for producing a crosslinked polymer molded product by carrying out molding simultaneously with polymerization of a metathesis polymerizable monomer in the presence of a metathesis polymerization catalyst system. More specifically, it relates to an improved method for carrying out such metathesis polymerization in the presence of a silicon halide compound to reduce residual monomers in the crosslinked polymer molding.

b. Prior Art It is known that cyclic olefins give ring-opening polymers via metathesis polymerization catalyst systems. Therefore, a method has been proposed in which a metathesis-polymerizable cyclic olefin such as dicyclopentadiene (DCP), which is inexpensively obtained, is polymerized and molded in a single step in a mold with a metathesis polymerization catalyst to obtain a polymerized molded product. That is, the metathesis polymerization catalyst system,
Utilizing the fact that it consists of two components, a catalyst component such as tungsten chloride and an activator component such as alkylaluminum. Using two types of liquids, each of which is a component and a monomer, after rapid mixing during polymerization There has been proposed a method of obtaining a polymer molded product by pouring into the above (see, for example, JP-A-58-129013).

According to such a method, an inexpensive low-pressure mold can be used to obtain a large molded product having good mechanical performance, which can be said to be an industrially very attractive method, but as it is actually applied, some It has become clear that there are points that need improvement.

One of the major factors is the presence of unreacted residual monomer in the cured polymer molding. Such residual monomers volatilize from the molded product and give off a peculiar and often unpleasant odor, which is a serious problem in practical use.

Further, it has been found that when the amount of the residual monomer is large, not only the odor but also the plasticizing action lowers the apparent glass transition point and adversely affects the rigidity of the molded product upon heating. On the other hand, as described above, the monomer solution containing the catalyst component (Solution A) and the monomer solution containing the activator component (Solution B) are, from a practical point of view, as long as possible after the preparation until the polymerization. It is preferable that it can be stored for a long time,
In fact, it has been found that the polymerizability deteriorates with the lapse of time, and as a result, the amount of residual monomer increases, which causes the above-mentioned inconvenience to a greater extent. Such residual monomer does not decrease so much even if the amount of the catalyst system is increased, and the increase of the catalyst system makes the polymer expensive, and the residual amount of the catalyst metal increases, which may adversely affect the durability of the polymer. There is not preferable.

Therefore, if a compound that activates the activity of the catalyst system can be found by adding a small amount, especially in the latter half of the polymerization, this problem can be solved.

As such a catalyst activator, a hydrocarbon compound having a trihalogen substituent in US Pat. No. 4,481,344,
It is disclosed that a hydrocarbon compound having an activated halogen atom due to the double bond at the β-position can be used for such a purpose. Although it is true that some of these compounds are effective in reducing residual monomers, they are harmless and have a considerably high boiling point, and it is very difficult to select a compound that can be used safely and economically.

Therefore, the present inventor has arrived at the present invention as a result of earnest research to find out a group of compounds having a large number of compounds having such an effect and which can be practically and easily used.

c. Structure of Invention That is, the present inventors have surprisingly found that silicon halide compounds are compounds that can act as a very effective residual monomer reducing agent. As such a silicon halide compound, dichlorodiphenylsilane, trichlorophenylsilane and the like, which are commercially produced as an intermediate of a silicon resin, can be preferably used, and include easily available compounds.

 The present invention has been achieved based on the above findings.

That is, in the present invention, alcohol or phenol is added to a salt of tungsten, rhenium, tantalum or molybdenum as a catalyst component of the metathesis polymerization catalyst system, and 1 to 1 mol of the salt of tungsten, rhenium, tantalum or molybdenum is added thereto. A reactive solution (solution A) of a metathesis polymerizable monomer containing a catalyst to which 5 mol of a Lewis base or a chelating agent is added, and an organometal of Group I to III of the periodic table as an activator component of the metathesis polymerization catalyst system. A method for producing a crosslinked polymer molded article by mixing a combination of a reactive solution of a metathesis polymerizable monomer containing a compound (solution B) and a reactive solution consisting of at least At least one of the halogenated silicon compounds having a halogen-silicon bond is allowed to coexist. A method for producing a crosslinked polymer molded article that.

In the present invention, a reaction characterized by the addition of at least one halogenated silicon compound having a halogen-silicon bond to at least one of the combinations of reactive solutions consisting of solution A and solution B. Combinations of sex solutions can be used.

In the present invention, when the silicon halide compound is not added by adding 0.5 to 4 times the equivalent amount of the metal atom (for example, tungsten atom) of the catalyst component as the number equivalent of silicon atoms having at least one halogen-silicon bond. It is possible to reduce the amount of residual monomer to about 1/2 or less than that of, and the effect is extremely remarkable.

Bromine and chlorine are preferable as the halogen of the silicon halide compound used in the present invention. From the point of effect, bromine may be used, but chlorine is particularly preferable from an industrial viewpoint. Further, when silicon in the silicon halide compound is bonded to an organic group, examples of the organic group include an alkyl group and an aryl group, but an aryl group is generally preferable. Particularly, from the viewpoint of obtaining a commercial product, a phenyl group and a phenylene group are preferable.
Further, even if it has a siloxane bond corresponding to a form in which a part of the halogen of the silicon halide compound used in the present invention is hydrolyzed and further condensed, or an alkoxy bond or an aryloxy bond generated by the addition of alcohol or phenol, It doesn't matter. In this case, it may be chain-shaped or ring-shaped. Further, such a silicon halide compound does not have a very low boiling point (at least 60 ° C. or higher, preferably 100 ° C. or higher).
(° C or higher) and those which are well soluble in the above-mentioned monomer-containing reactive solution are preferable.

Specific examples of the organic halogenated silicon compound include phenyltrichlorosilane, diphenylchlorosilane, triphenylchlorosilane, P-phenylenebis (trichlorosilane), P-phenyldichlorosilane), dimethyldichlorosilane, methyltrichlorosilane and partial hydrolysis thereof. Examples thereof include those introduced with a siloxane bond, or those introduced with an alkoxy group or a phenyl group by decomposition with an alcohol or phenol.

Among the above examples, phenyltrichlorosilane and diphenyldichlorosilane are particularly preferable from the viewpoint of performance and easy availability.

As the method of using such a silicon halide, a method of adding it to at least one of the solutions A and B in advance or a method of adding it to at least one of the solutions A and B immediately before use is used. Either can be taken.

As a side to be added, it is generally preferable to add it to the liquid A side because it has strong reactivity with alkyl metals such as alkylaluminum which is an activator component. By adding it to the reaction solution from the beginning,
The effect of the catalyst activator can be expected at all times. Furthermore, it is possible to regenerate a liquid that has become unusable in general by preventing the increase of residual monomer due to the decrease of the polymerizability by adding it to the reactive solution whose polymerizability has dropped after a long time without addition. . Regeneration of the polymerizability of the reactive solution can also be achieved by adding a new catalyst system component, but this method is expensive and increases the metal content in the molded product, so that The use of the activator is more practical, and the residual monomer can be reduced to the extent that it is impossible only by adding the catalyst.

In addition, in order to evaluate the polymerizability of the reactive solution, solution A and solution B are used.
The effective ratio of the catalyst component and the activator component is adjusted so that the polymerizability becomes the highest, and the temperature in the reaction system is set by rapidly mixing and reacting in a flask from a constant temperature such as 30 ° C. A method of observing the length of time when the temperature reaches a certain temperature is defined as the polymerization time is used.

The catalyst activator according to the present invention does not significantly change the polymerization time and is effective in reducing the residual monomer, so that it does not participate in the initiation reaction of the polymerization but participates in the termination reaction, or Whether the deactivated catalyst is literally activated in the latter stage of the polymerization, or whether the metathesis polymerization and another polymerization occur in the latter stage of the polymerization, in any case, the effect is exhibited after the polymerization is started. It is thought that this is the case, but at present the clear mechanism is unknown.

As described above, the addition amount is 0.5 to 10 equivalents of the transition metal element in the catalyst component in terms of the number of silicon halide atoms equivalent.
A range of 4 equivalents, particularly preferably 0.9 to 2.5 equivalents, is generally used.

It is preferable that the silicon halide compounds used in the present invention do not have impurities that inhibit the polymerization reaction or remain in the polymer and cause harm.

As a specific molding method of the method for producing a polymer molded product of the present invention, the reactive solution is mixed with a static mixer or the like, or a premix is prepared in advance and injected into a mold to form a molded product. The resin injection method and the molding method similar to it can be used, but since the reaction after mixing is generally fast, the reaction injection molding method (RIM molding method) that injects the mixed reaction solution into the mold immediately after collision mixing is performed. Most suitable.

As a preferred specific example of the metathesis polymerizable monomer used in the present invention, one having 1 to 2 metathesis polymerizable high norbornene structures is preferable, and dicyclopentadiene, tricyclopentadiene, cyclopentadiene-methylcyclopentadiene. Co-dimer, 5-ethylidene norbornene, norbornene, norbornadiene, 5-cyclohexenyl norbornene, 1,4,5,8-dimethano-1,4,4a, 5,5,7,8,8a-octahydronaphthalene,
1,4-methano-1,1,4a, 5,6,7,8,8a-octahydronaphthalene, 6-ethylidene-1,4,5,8-dimethano-1,4,4a, 5,
One or more kinds of 7,8,8a-heptahydro-naphthalene, 1,4,5,8-dimethano-1,4,4a, 5,8,8a-hexahydronaphthalene ethylenebis (5-norbornene), etc. Although a mixture can be mentioned, dicyclopentadiene or a monomer mixture containing it as a main component is preferably used.

Further, if necessary, a metathesis-polymerizable cyclic compound having a different element such as oxygen or nitrogen can be used.
Such polar monomers are often used in copolymerization with dicyclopentadiene and the like.

The polar monomer also preferably has a norbornene structural unit, and the polar group is an ester group,
Ether group, cyano group N-substituted imide and the like are preferable.

Specific examples of the copolymerization monomer include 5-methoxycarbonylnorbornene, 5- (2-ethylhexyloxy) carbonyl-5-methylnorbornene, 5-phenyloxymethylnorbornene, 5-cyanonorbornene,
6-Cyano-1,4,5,8-dimethano-1,4,4a, 5,6,7,8,8a-
Octahydronaphthalene, N-butyl nadic acid imide and the like can be mentioned.

As described above, the metathesis-polymerizable monomer is required to have as few impurities as possible that deactivate the metathesis polymerization catalyst.

As the catalyst component in the metathesis polymerization catalyst system used in the present invention, salts such as tungsten, rhenium, tantalum, and a halide of molybdenum are used, and a tungsten compound is particularly preferable. As such a tungsten compound, tungsten halide, tungsten oxyhalide and the like are preferable, and more specifically, tungsten hexachloride, tungsten oxychloride and the like are preferable. Further, organic ammonium tungstate or the like can also be used. Such a tungsten compound,
If it is directly added to the monomer, cationic polymerization may start immediately, which is not preferable. Therefore, the tungsten compound or the like is suspended in an inert solvent such as benzene, toluene, or chlorobenzene in advance, and solubilized by adding a small amount of an alcohol compound or a phenol compound before use. Further, as described above, in order to prevent undesired polymerization, 1 to 5 mol of Lewis base or chelating agent is added to 1 mol of the tungsten compound or the like. Examples of such additives include acetylacetone, acetoacetic acid alkyl esters, tetrahydrofuran and benzonitrile. When a polar monomer is used, it may be a Lewis base as described above, and it may have the action even without adding the above-mentioned compound.

Thus, the monomer solution containing the catalyst component (Solution A)
Has practically sufficient stability.

On the other hand, the activator component in the metathesis polymerization catalyst system is
Organometallic compounds centered on alkylated metals of Group I to Group III of the Periodic Table, especially tetraalkyltin, alkylaluminum compounds, and alkylaluminum halide compounds are preferable, and specifically, diethylaluminum chloride, diethyl chloride. Examples thereof include aluminum, trioctylaluminum, dioctylaluminum iodide, tetrabutyltin and the like. The other solution (corresponding to solution B) is formed by dissolving the organometallic compound as the activator component in the raw material monomer.

In the present invention, basically, a crosslinked polymer molded product can be obtained by mixing the solution A and the solution B, but since the polymerization reaction is started very quickly with the above composition, Curing may occur before it is sufficiently poured into the mold, which often causes a problem. Therefore, it is preferable to use an activity modifier.

Lewis bases are generally used as such regulators, and ethers, esters, nitriles and the like are used among them. Specific examples thereof include ethyl benzoate, butyl ether, and diglyme. Such regulators are generally used by adding them to the solution side of the activator component of the organometallic compound. When a monomer having a Lewis base group is used as described above, it can also serve as a regulator.

The amount of the metathesis polymerization catalyst system used, for example, when using a tungsten compound for the catalyst component, the ratio of the tungsten compound to the raw material monomer, on a molar basis,
When the alkylaluminum is used as the activator component, the ratio of the aluminum compound to the raw material monomer is about 1000: 1 to 15000: 1, preferably 2000: 1. Around 100 to 1 to about 2000 to 1, preferably about 200 to 1 to about 500 to 1 is used. Further, as described above, the additives and regulators can be appropriately adjusted and used depending on the amount of the catalyst system used by experiments.

In the improved method of the present invention, the above solutions A and B
At least one of the above, preferably, the above-mentioned silicon halides are added to the solution A according to the use conditions such as the addition amount addition timing as described above, and polymerization and molding are simultaneously performed by reaction injection molding or the like to obtain a polymer molded product. You can
Such a molded product is obtained by using silicon halides.
The amount of residual monomer is very small as compared with the case where it is not used.

The crosslinked polymer molded article according to the present invention, in practical use,
Various additives can be further added in order to improve or maintain the characteristics. Such additives include fillers, pigments, antioxidants, light stabilizers, flame retardants, polymer modifiers and the like. Even with such an additive, it is impossible to add it after the crosslinked polymer of the present invention has been molded. Therefore, when it is added, it is necessary to add it to the above-mentioned raw material solution in advance.

The simplest method is to add it to either or both of the solution A and the solution B in advance. In that case, a catalyst component having a strong reactivity in the solution or activation It must be one that can be used practically with the agent components and silicon halides, does not react to some extent, and does not hinder the polymerization. When the reaction is unavoidable but the coexistence does not substantially inhibit the polymerization, it is possible to prepare a third liquid by mixing with the monomer and mix and use it immediately before the polymerization. Further, in the case of a solid filler, both components are mixed, and those having a shape capable of sufficiently filling the voids immediately before starting the polymerization reaction or during the polymerization, in the molding mold, It is also possible to fill it.

Reinforcing agents or fillers as additives are effective in improving flexural modulus. Examples thereof include glass fiber, mica, carbon black, wollastonite and the like. Those obtained by surface-treating these with a so-called silane coupler can also be suitably used.

In addition, it is preferable to add an antioxidant to the crosslinked polymer molded product of the present invention, and therefore it is desirable to add a phenol-based or amine-based antioxidant to the solution in advance. Specific examples of these antioxidants include 2,6-
t-butyl-P-cresol, N, N'-diphenyl-P
-Phenylenediamine, tetrakis [methylene (3,5-
Di-t-butyl-4-hydroxycinnamate)] methane and the like.

Further, the polymer molded product according to the present invention may be added with another polymer in a monomer solution state. As such a polymer additive, the addition of an elastomer is effective in enhancing the impact resistance of the molded product and adjusting the viscosity of the solution. Examples of the elastomer used for such a purpose include a wide range of elastomers such as styrene-butadiene-styrene triblock rubber, styrene-isoprene-styrene triblock rubber, polybutadiene, polyisoprene, butyl rubber, ethylene propylene-dienta-polymer and nitrile rubber. Can be done.

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

As the molding method, as described above, a resin injection method in which a premix in which a catalyst and a raw material monomer are mixed in advance is made to flow into a mold, and a solution A and a solution B in which a catalyst system is divided into two are used in a head portion. It is possible to use the RIM method in which collision mixing is performed and the mixture is directly poured into the mold. Especially R
The IM method is generally used.

In either case, the injection pressure into the mold can be relatively low, and thus inexpensive molds can be used. Further, when the polymerization reaction in the mold starts, the temperature in 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 a special release agent is often unnecessary.

Since the molded product has many double bonds, an oxide layer is formed on the surface of the molded product, so that it has good adhesion to commonly used paints such as epoxy and polyurethane.

d. Effects of the Invention According to the present invention, it is possible to obtain a crosslinked polymer molded product with a reduced residual monomer.

The molded product thus obtained can be used in a wide range of applications, mainly for large molded products such as members of various transportation equipment including automobiles, housings of electric and electronic devices.

e. Examples Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. It should be noted that the embodiment is for the purpose of explanation, and the present invention is not limited to this.

Examples 1 to 10 and Comparative Examples 1 and 2 Commercially available DCP was purified by distillation under a reduced pressure in a nitrogen stream to obtain purified dicyclopentadiene having a freezing point of 33.4 ° C. Purity measurement by gas chromatography showed a purity of 99% or higher.

Diphenyldichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, and trimethylchlorosilane also showed a purity of 99% or more when measured by a gas chromatograph.

[Preparation of Catalyst Component Solution] 20 g of tungsten hexachloride was added to 70 ml of dry toluene under a nitrogen stream, and then a solution of 21 g of nonylphenol and 16 ml of toluene was added to prepare a 0.5 M tungsten-containing catalyst solution. In contrast, nitrogen gas was purged overnight to remove hydrogen chloride gas generated by the reaction of tungsten hexachloride and nonylphenol.

Monomer mixture in which 10 ml of such a solution, 1.0 ml of acetylacetone and silicon halides were added in amounts corresponding to those in Table 1.
500 ml was mixed to prepare a solution A having a tungsten content of 0.001M.

[Preparation of activator component solution] Trioctylaluminum, dioctylaluminum iodide, and diglyme were used at a molar ratio of 85: 15: 100, and 500 ml of the monomer was mixed to obtain an aluminum content of 0.003M.
Solution B was prepared.

The molar ratios of DCP and metathesis polymerizable monomer to silicon halide compound used in the monomer mixture in this solution are shown in Table 1 below.

Regarding the effect of reducing the residual monomer by adding the silicon halide compounds to the solution A in which the polymerization reactivity was deteriorated and the polymerization reaction time was prolonged by leaving it for a longer period (two weeks), the solution of Comparative Example 2 (Comparative Example 1 was Example 10 was carried out using the same solution that was kept at room temperature for a long time (2 weeks). The molar ratios of DCP and metathesis polymerizable monomer to silicon halide compound used in the monomer mixture in this solution are shown in Table 2 below. In Example 10, the amount of silicon halide shown in Table 2 was added to the solution A side.

The above solution A (10 ml) and solution B (10 ml) were heated to a predetermined temperature, and then taken out into a syringe which was sufficiently replaced with nitrogen.

When a liquid was mechanically extruded from such a syringe at a constant speed into a nozzle, where it was molded by an ultra-small RIM machine capable of collision mixing and pouring into a mold, a brown solid plate could be molded.

Cut a 1 g sample from such a plate-like cross-linked molded product 50
After dipping it in ml of toluene to sufficiently extract the residual monomer, unreacted monomer components were found by gas chromatography and the residual monomer amount (% by weight based on the molded product) was measured. The results are shown in Table 3 below.

It can be seen that the residual monomers are greatly reduced in comparison with those in which no silyl halide compound is added.

Example 11, Comparative Example 3 Each of 50 liters of a reactive solution having the same composition as in Example 4 was prepared and mixed and injected into a mold capable of molding a plate-shaped sample using a practical RIM machine manufactured by Niigata Iron Works, A sample plate having a thickness of 3 mm was prepared. The properties were compared with a sample plate (Comparative Example 3) molded under the same composition conditions except that diphenyldichlorosilane was not added (Table 4).

It can be seen that although the impact resistance represented by notched Izod does not change much, the residual monomer is reduced and Tg is improved.

Claims (1)

[Claims] 1. As a catalyst component of a metathesis polymerization catalyst system, alcohol or phenol is added to a salt of tungsten, rhenium, tantalum or molybdenum, and 1 to 1 mol of the salt of tungsten, rhenium, tantalum or molybdenum is added thereto. A reactive solution (solution A) of a metathesis polymerizable monomer containing a catalyst to which 5 mol of a Lewis base or a chelating agent is added, and an organometal of Group I to III of the periodic table as an activator component of the metathesis polymerization catalyst system. A method for producing a crosslinked polymer molded article by mixing a combination of a reactive solution of a metathesis polymerizable monomer containing a compound (solution B) and a reactive solution consisting of at least At least one of the halogenated silicon compounds having a halogen-silicon bond is allowed to coexist. Method for producing a polymer molded product.