JPH0791371B2 - Method for producing polymer molded product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention relates to a method of pouring a metathesis-polymerizable monomer into a molding mold in the presence of a metathesis polymerization catalyst system, and performing molding simultaneously with bulk polymerization in the mold, And a reactive solution therefor. More specifically, the present invention relates to remarkably improving the impact resistance and heat resistance of a crosslinked polymer molded product by allowing a specific polymer to coexist during the polymerization.

b. Prior Art It is known that cyclic olefins are opened by a metathesis polymerization catalyst system to give crosslinked polymers.

Therefore, a method is proposed in which a monomer having two metathesis-polymerizable groups, such as dicyclopentadiene, that can be obtained at low cost is poured into a mold in a liquid state, bulk polymerization is performed in the mold, and molding is performed in one step at the same time as polymerization. (See, for example, JP-A-58-129013).

According to such a method, a large-sized molded product can be obtained by using an inexpensive mold, so that it has a possibility of being used in a wide range of applications. However, there are many applications in which such a large molded article is required to have good impact resistance. However, in general, the impact resistance is often insufficient in the metathesis-polymerizable monomer as described above, particularly in the crosslinkable monomer. As a method for improving it, a method of forming a polymer molded product in the presence of a rubber soluble in a monomer and a method of adding a plasticizer have been proposed. The method of adding a plasticizer generally has a problem of blooming of the added plasticizer, and it cannot be said to be a sufficient method. On the other hand, the method of adding rubber can be said to be an effective method because a considerably large effect is recognized even if it is added in a small amount. However, it has been found that the addition of such a rubber greatly affects the performance thereof, that is, the impact resistance typified by notched Izod impact resistance and the heat resistance typified by heat deformation temperature. It was

That is, generally, impact resistance and heat resistance are contradictory properties,
It has also been found that the addition of a rubber that gives good properties to one side tends to damage one side. Therefore, the present inventor has conducted diligent research to find a rubber having a good balance between the two, and as a result, it has been found that a polymer having a specific composition can improve both these contradictory properties to a very high level. Has reached.

c. Structure of the Invention Generally, a hydrocarbon rubber such as styrene-butadiene rubber, poly-cis-1,4-polybutadiene rubber, poly-
It is known that cis-1,4-isoprene rubber (IR), natural rubber, polyisobutylene rubber, ethylene-propylene rubber, ethylene-propylene-dienta-polymer rubber, etc. can be used for polymer molding by such metathesis polymerization. .

By the way, among these hydrocarbon rubbers, for example, taking styrene-butadiene rubber (SBR) as an example, the heat resistance of the molded product is improved by using SBR having a high styrene content,
Impact resistance Especially at low temperatures, the impact resistance is greatly impaired. In addition, SB with the same styrene content (and roughly the same main chain structure)
Also in R, for example, when the reactive solution for obtaining a metathesis polymerization molded product from a metathesis polymerizable monomer mainly composed of DCP is made to have approximately the same viscosity, SBR having a small molecular weight has a smaller addition amount. It gets bigger,
In such a case, the molded product has good impact resistance but a low heat distortion temperature. Further, in the case of poly-cis-1,4-butadiene (BR), it was found that there is a similar tendency in that the difference becomes more remarkable. That is, it has been found that it is a general phenomenon that the impact resistance and the heat distortion temperature are contradictory as described above.

However, as an elastomer containing ethylene as an essential component, for example, a rubber such as ethylene-propylene-diene-polymer is generally used having an ethylene content of about 60 mol% from the viewpoint of being amorphous, but depending on the use, it may be high. An ethylene content may be desired, but if the ethylene content becomes larger than 80%, the crystallinity becomes too high. In that case, n-
It has been proposed to use butylene to mitigate the effect.

It has been found that the addition of such a polymer makes it possible to obtain a molded product in which the heat distortion temperature and the impact resistance are well balanced.

However, in order to use it to obtain a molded product by adding it to such a reactive solution, it is necessary to have a requirement that it has a solubility that does not cause any inconvenience in use. The present invention has been achieved based on such findings and includes the following inventions.

That is, the present invention is a method for producing a polymer molded product in which a metathesis polymerizable monomer is polymerized and molded simultaneously in the coexistence of a metathesis polymerization catalyst system, in which 75 to 95 mol% of ethylene, butylene and / or non-conjugated diene 25 to 5 is used. To a mixed solvent consisting of 90% by weight of dicyclopentadiene and 10% by weight of ethylidene norbornene, at least one polymer that is substantially soluble at 30% by weight at 30 ° C. is added. It is a method for producing a polymer molded article, which is characterized in that it is carried out.

In the present invention, a) a metathesis polymerizable monomer reactive solution (solution A) containing a metathesis polymerization catalyst system catalyst component, and b) a metathesis polymerizable monomer reactive solution containing a metathesis polymerization catalyst system activator component ( In a combination of reactive solutions consisting of at least solution B) these solutions A
And a solution B comprising at least one of 75 to 95 mol% ethylene, butylene and 25 to 5 mol% non-conjugated diene, and a dicyclopentadiene
It is possible to use a combination of reactive solutions in which 90% by weight and 10% by weight of ethylidene norbornene are mixed with at least one solvent which is substantially soluble in at least 3% by weight at 30 ° C.

Particularly preferred as the polymer used in the present invention is a composition having 80 to 90 mol% of ethylene and 20 to 10 mol% of n-butylene and 0 to 5 mol% of non-conjugated diene (total of 100 mol%). The non-conjugated diene component is not essential for the polymer used in the present invention, but when it is introduced, it tends to increase the solubility, and it is preferable to introduce an appropriate amount. However, if the amount is too large, the number of branches is increased, and the molecular weight distribution tends to be wide, which causes problems in solubility. Therefore, it is generally preferably 5 mol% or less.

As the non-conjugated diene, those having greatly different polymerization reactivity of two unsaturated bonds are preferably used, and practically, ethylidene norbornene (ENB) and dicyclopentadiene (DCP) are exclusively used. The polymers used in the present invention must meet the solubility requirements mentioned above. Here, the term “substantially dissolved” does not necessarily mean that it is completely dissolved in a molecular form, and it exhibits fluidity to such an extent that it can be used as a reactive solution for reaction injection molding that flows out from a thin nozzle under high pressure. It means that it can be dissolved as much as possible.

The amount of the polymer added may be selected in consideration of the balance between the effect of the thickening effect of the reactive solution on the moldability due to the addition and dissolution of the polymer and the effect of improving the physical properties of the molded product. . That is, when it is used for RIM, the viscosity of the liquid is most suitable in the range of 250 to 500 centipoise, and the rubber concentration giving the viscosity may be selected.

In addition, it is necessary to add a polymer additive in addition to it, and if there is a thickening effect for that purpose, it may be adjusted in consideration of it.

Generally, the amount of such a polymer added is in the range of 1 to 15% by weight, particularly preferably 3 to 10% by weight (based on the monomers).

By using such a polymer, for example, DCP as a monomer, SBR or B in a crosslinked polymer molded product using a metathesis catalyst system composed of a tungsten type and an aluminum type is used.
When using materials other than the present invention for R and EPDM, heat distortion temperature (18.5kg / cm ² load) (HDT) 90 ℃
Front and rear notched izods (3 mm thick) of 40-45 Kgcm / cm have HDT at 100 ° C with almost no change in notched izods.
It is possible to exert the effect of improving to the front and back.

Considering that if a similar cross-linked polymer is obtained without adding any rubber, it is possible to obtain only a value of about 90 ° C. in HDT and 10 Kgcm / cm or less in a notched Izod, the addition of rubber, particularly that of the present invention. It is considered that the remarkable effect of the specific polymer can be realized.

On the other hand, with the polymer as described above, the metathesis polymerizable monomer used for forming a molded product may be any one, such as those capable of bulk polymerization by metathesis polymerization to give a molded product, but generally a metathesis polymerizable cyclopolymer. Those containing 1 to 4 alkene groups are used. Those having a norbornene-type bond are particularly preferable. Hydrocarbons are particularly preferable, and specific examples thereof include dicyclopentadiene, dihydrodicyclopentadiene, cyclopentadiene-methylcyclopentadiene co-dimer, 5-ethylidenenorbornene, 5-vinylnorbornene, norbornene, 5-cyclohexenyl. Norbornene, 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, ethylenebis (5-norbornene) and the like can be mentioned. Particularly preferred is dicyclopentadiene or a monomer mixture containing 50% or more, more preferably 70% or more of dicyclopentadiene.

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 polymerizable monomer also preferably has a norbornene structural unit, and the polar group is preferably an ester group, an ether group, a cyano group, an N-substituted imide group or the like.

Such a polar group, as a Lewis base, has an action of controlling the initiation of the metathesis polymerization reaction, and also has an effect of introducing a polar group into the formed polymer molded product, so that the necessity of these actions is satisfied. It is suitably used depending on the situation.

Examples of 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-cyano-1,4,5,8
-Dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, N-butyl nadic imide, 5- (4-pyridyl)
-Norbornene and the like can be mentioned.

Further, a halogen-containing / metathesis polymerizable monomer can be used for improving flame retardancy and softening temperature. Specific examples of such a monomer include 5-chloronorbornene, 5
-Bromonorbornene, 5,5,6-trichloronorbornene, 5,5,6,6-tetrachloronorbornene, 5,6-dibromonorbornene, 5- (2,4-dibromophenyl) norbornene and the like can be mentioned.

It is preferable that the metathesis-polymerizable monomers as described above all have the content of impurities that inhibit the metathesis polymerization catalyst as small as possible.

The metathesis polymerization catalyst system used to obtain polymer moldings in the present invention generally comprises two components, a catalyst component and an activator component, as is known.

However, the metathesis polymerization reaction is generally an exothermic reaction, and once the polymerization is started, the system is further heated to accelerate the reaction.

Therefore, as described above, two solutions, that is, a solution mainly composed of a monomer and a catalyst component (solution A) and a solution mainly composed of a monomer and an activator component (solution B) are prepared in advance and subjected to collision mixing (RIM method). ) Or a static mixer, rapid mixing, immediate injection into a mold, shaping, and curing in a mold can be preferably used. In that case, the composition of the monomer does not have to be the same in both liquids, and can be arbitrarily changed depending on the function of the monomer. Further, the amount of the polymer added can be changed depending on both liquids, but in the reaction injection molding method, it is generally preferable that the viscosity of both liquids is the same because mixing is performed effectively.

As another method for obtaining a polymer molded product, a Lewis base that acts as a regulator that delays the initiation of metathesis polymerization as described above, or a metathesis polymerization monomer having such a Lewis base is added to delay the initiation of polymerization and preliminarily generate it. It is possible to take a method of flowing the prepared premix into the mold. In this case, it is advantageous to obtain a fiber-reinforced molded product by placing a glass fiber mat or the like in the mold in advance.

Salts such as halides of tungsten, rhenium, tantalum, molybdenum, etc. are used as the catalyst component in the metathesis polymerization catalyst system, but tungsten compounds are 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 molybdate can also be used. It has been found that such a tungsten compound immediately starts cationic polymerization when directly added to a monomer, which is not preferable. Therefore, such a tungsten compound is preferably suspended in an inert solvent such as benzene, toluene, chlorobenzene or the like 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, it is preferable to add about 1 to 5 mol of Lewis base or chelating agent to 1 mol of the tungsten compound. Examples of such additives include acetylacetone, acetoacetic acid alkyl esters, tetrahydrofuran and benzonitrile. The polar monomer for copolymerization used in the present invention may be a Lewis base itself as described above, and may have its action even if the above compound is not added.

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

On the other hand, the activator component in the metathesis polymerization catalyst system is preferably an organometallic compound centered on an alkylated compound of a metal of Group I to Group III of the Periodic Table, particularly tetraalkyltin, an alkylaluminum compound, an alkylaluminum halide compound, Specific examples thereof include diethylaluminum chloride, diethylaluminum chloride, trioctylaluminum, dioctylaluminum iodide, and tetrabutyltin. 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 with the above composition as it is, the polymerization reaction is started very quickly, Since curing often occurs before it sufficiently flows into the casting mold, this often causes a problem. Therefore, it is preferable to use the activity modifier as described above.

As such a regulator, Lewis bases are generally used, and ethers, esters, nitriles and the like are used. Specific examples include ethyl benzoate, butyl ether, diglyme and the like. Such a regulator is generally used by adding it to the solution side of the component of the activator of the organometallic compound. When a copolymerization 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 is, for example, when a tungsten compound is used as the catalyst component, the ratio of the tungsten compound to the raw material monomer is about 10 on a molar basis.
When the activator component is an alkylaluminum, the ratio of the aluminum compound to the raw material monomer is about 100 on a molar basis. Around 1 to about 2000 to 1, preferably about 200 to 1 to about 500 to 1 is used. Further, as described above, the masking agent and the regulator can be appropriately adjusted and used depending on the amount of the catalyst system used by experiments.

The polymer molded product according to the present invention may further contain various additives in order to improve or maintain its properties in practical use. Such additives include fillers,
Content, antioxidants, light stabilizers, flame retardants, polymer modifiers, etc. Since such an additive cannot be added after the polymer of the present invention is formed, when it is added, it is necessary to add it to the above-mentioned raw material solution in advance.

The easiest method is the solution A and the solution B.
Although it is possible to cite a method of adding it to either or both of them in advance, in that case, the catalyst component or the activator component having strong reactivity in the liquid does not react to a certain extent with practical use, and It must not interfere with polymerization. In any case, if the reaction is unavoidable but coexistence does not substantially inhibit the polymerization, it can be mixed with the monomer to prepare the third liquid and mixed and used immediately before the polymerization. . Further, in the case of a solid filler, both components are mixed, and immediately before the initiation of the polymerization reaction or during the polymerization, those having a shape capable of sufficiently filling the voids, in the molding mold, It is also possible to fill it.

The reinforcing material or filler as an additive is effective in improving the bending modulus. Examples thereof include glass fiber, mica, carbon black, wollastonite and the like. Those obtained by surface-treating these with a so-called silane gapler 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 it is therefore preferable 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.

In the present invention, it is essential to use the specific polymer as described above, but in addition to that, other rubber or other polymer may be added to the reaction solution and dissolved or suspended to be used. .

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 the catalyst system and the monomer mixture are mixed in advance and the mixed premix is allowed to flow into the mold, and a solution A and a solution B in which the catalyst system is divided into two are collided at the head portion. It is possible to adopt the RIM method in which it is mixed and poured into the mold as it is. 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.

The molded product has an oxide layer on the surface and has good adhesion to commonly used paints such as epoxy and polyurethane due to the polarity of the cyano group.

The molded product thus obtained has improved impact resistance and heat resistance as compared with conventional ones, and members of various transportation devices including automobiles, electric and electronic device housings, etc.
It can be used for a wide range of purposes, including large moldings.

The present invention will be described in detail below with reference to examples. It should be noted that the embodiment is for the purpose of explanation and is not limited thereto.

Examples 1 to 7 and Comparative Examples 1 to 6 (i) Preparation of Catalyst Concentrated Liquid 19.8 Kg (50 mol) of tungsten hexachloride was dispersed in 90 l of dehydrated toluene under a stream of nitrogen, and 0.925 Kg (12.5 mol) therein. Was dissolved in 5 L of dehydrated toluene, and the mixture was stirred for 3 hours under an added nitrogen stream. A solution of 11.05 kg (50 mol) of nonylphenol dissolved in 5 l of dehydrated toluene was added to the mixture, and the mixture was stirred for 3 hours. 10 kg (100 mol) of acetylacetone was added dropwise thereto, and stirring was continued for a whole day and night. Hydrogen chloride generated during these processes is taken out of the system together with nitrogen, neutralized with an aqueous solution of caustic soda, and discarded.

Therefore, a 0.5 M tungsten catalyst concentrate was prepared by supplementing toluene that was partly reduced.

(Ii) Preparation of activator concentrate 5.7 Kg of di-n-octylaluminum iodide, 13.4
A 1.0 M aluminum activator concentrate was prepared by adding a mixture of 2 kg of tri-n-octylaluminum and 13.42 kg of diglyme to 100 l of purified dicyclopentadiene.

(Iii) Preparation of Reactive Solution (A) 964.6 parts of a metathesis polymerizable monomer solution having a predetermined composition in which a predetermined amount of a well-defined polymer having a commercially available composition was dissolved, 15.4 parts of a catalyst concentrate, and Ethanox 702 (ethyl ester) as an oxidation stabilizer. 20 parts (manufactured by the same company) were mixed under a nitrogen stream to prepare 30 kg of reactive solution (A).

(Iv) Preparation of Reactive Solution (B) 978.5 parts of a metathesis polymerizable monomer solution having a predetermined composition in which a predetermined amount of a well-defined polymer having a commercially available composition is dissolved and 21.5 parts of an activator concentrate are mixed under a nitrogen stream. Then, 30 kg of each reactive solution (B) was prepared.

(V) Preparation of polymer molding Using a lance type reaction injection molding machine manufactured by Niigata Iron Works Co., Ltd.
Mixing pressure 60Kg / cm Reactive solutions A and B are injected in equal amounts and the total amount is about 400g / sec. It has a cavity of 50cm × 50cm × 30mm and the mold surface is 70-90 ℃. It was filled inside and cured by reaction to obtain a resin molded product having a thickness of about 3 mm.

Using this plate-shaped molded product, the heat distortion temperature (HDT) under a load of 18.5 Kg / cm, the second-order transition point by DMA (g) Notched Izod at room temperature to low temperature, flexural modulus, flexural modulus and toluene The molded product was extracted with, and the residual monomer in the extract was quantified by gas chromatography, and compared with the comparative example to clarify the effect of adding the polymer.

Table 1 shows the types of polymers used in Examples and Comparative Examples, the compositions, the concentrations in the monomer solutions in which the polymers are dissolved, and the types of monomers.

Table 2 shows the performance of the molded product.

The viscosity of each of the reactive solutions A and B used here was in the range of 300 to 400 cps measured at 30 ° C.

The examples using the polymer specified in the present invention are not limited to typical SBR, BR.IR, and EPDM as shown in the comparative examples, without notch Izod, bending modulus, and bending strength, and HDT. Is 100 ° C or higher and Tg is 155 ° C or higher, even though the same monomer is used, HDT is 10 ° C and Tg is 15 ° C.
The improvement of about 0 ° C. was observed, and it was found that the practicality of the resin molded product was greatly improved, and the usefulness of the added polymer according to the present invention is clear.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area C08L 23:08)

Claims (1)

[Claims] 1. A method for producing a polymer molded product, which comprises simultaneously polymerizing and molding a metathesis polymerizable monomer in the coexistence of a metathesis polymerization catalyst system, comprising: 75 to 95 mol% of ethylene, butylene and / or 25 to 5 of a non-conjugated diene. A polymer comprising 90% by weight of dicyclopentadiene,
A process for producing a polymer molded product, which comprises adding at least one solvent which is substantially soluble at 30% by weight at 30 ° C. to a mixed solvent comprising 10% by weight of ethylidene norbornene.